We have studied precipitate growth and coarsening in ternary alloys using two different phase held models. The first one is a ternary extension of the classical Cahn-Hilliard (C-H) model in which both the phases are characterized using conserved held variables i.e. composition (cB; cC ); mobility matrix and gradient energy efficient are the other input parameters in this model. In the second model, each phase is treated as separate, and phase identify cation is through a (non-conserved) phase held variable ; we have used a grand potential-based (GP) formulation, due to Plapp [1], Choudhury and Nestler [2], where interfacial energy and interface width, as well as free energy and diffusivity matrix for the relevant phases are the input parameters. The first model i.e. the Cahn-Hilliard (C-H) type model is conceptually simple. The model for ternary is a straight forward extension of the binary. The grand potential (GP) formulation has the advantage of being able to incorporate thermodynamic database like Thermocalc in it. We present below a summary of the findings of our research on (a) precipitate growth, precipitate coarsening, and (c) a critical comparison between results from phase held simulations and those from experiments on an Ni-Al-Mo alloy Precipitate growth In our study of precipitate growth in ternary alloys, we end that when both the solute elements have the same diffusivity, precipitate growth behaviour in ternary alloys is identical to that binary alloys; specifically, we recover the temporal power law r2 = kgt relating the particle radius to time, and the growth kg depends only on supersaturation (i.e., equilibrium volume fraction of the precipitate phase), and is independent of the slope of the tie line. However, when one solute element, (say, C) di uses slower than the other (i.e. (DCC =DBB) < 1,(where DBB, DCC are intertie suavities’ in the lab frame of reference), the ux of C at the interface is smaller than that of species B, causing the precipitate to become depleted in C and enriched in B; this process continues until the growth phase enters a scaling regime where we recover the temporal law for growth: r2 = kgt. In this regime, the tie line selected by the precipitate and matrix interfacial compositions is different from the thermodynamic tie line containing the alloy, a result first reported by Coates [3]. After validating our phase held model quantitatively through a critical comparison with Coates' theory of tie line selection, we have characterized the growth behaviour: specifically, we end that growth kg drops with decreasing value of DCC ; the magnitude of this drop is stronger for alloys which (a) are on higher-C tie lines (i.e., the slope of the tie line is higher), and (b) have smaller precipitate volume fractions. Precipitate coarsening In our simulations, we end that precipitate coarsening does indeed enter a scaling regime where the temporal power law r3 = kt (which relates the average precipitate radius r to (b) time t) is valid; the coarsening rate k depends, as expected, not only on precipitate volume fraction, but also on the slope of the tie line and diffusivity ratio (DCC =DBB). (c) (d) When the solutes have equal diffusivity (i.e., (DCC =DBB) = 1), the coarsening behaviour is essentially the same as that in a binary alloy. However, when solute C (say) is the slower di using species, the coarsening rate k drops, with a deeper drop in alloys on higher-C tie lines. Both these conclusions are similar to those from our study of precipitate growth. (e) (f) However, there is a crucial difference between precipitate growth and coarsening in ternary alloys: The suppression in coarsening rate (for DCC < DBB) in ternary alloys is accompanied by another e ect: larger (and growing) precipitates are richer in the faster di using species B, while the smaller and shrinking precipitates are richer in the slower di using C. In other words, during coarsening in ternary alloys, the tie line selected by precipitate and matrix interfacial components depends on precipitate size; during growth, however, the scaling regime is characterized by the same tie line, independent of precipitate size. (g) (h) (i) Critical comparison between theory and experiment (j) (k) (l) We have used the grand potential based phase held model [1] [2] to study coarsening in Ni-Al-Mo alloys. This model has the advantage of ease with which we can incorporate the thermodynamic and kinetic data on real alloys. (m) (n) A comparison of coarsening rate from our 3D simulations with the experimentally observed rate reveals that diffusivity of the faster di using species (which, in Ni-Al-Mo alloys, is aluminium) from our simulations is within an order of magnitude from the experimental value. However the dominant term in the (@ =@c) matrix is underestimated by 2 to 3 orders of magnitude (compared to its value computed from CALPHAD-based thermodynamic data).

Au cours des dernières années, l'utilisation des carbènes N-hétérocycliques (NHCs) en tant qu'organocatalyseurs a connu un succès impressionnant. Dans ce manuscrit, nous présentons le design et la synthèse de nouveaux organocatalyseurs NHC bifonctionnels, et leurs applications pour la chimie énantiosélective des homoénolates. En parallèle de ces études, une approche conceptuellement nouvelle aux carbènes de pyridine est proposée et exploitée dans une réaction à trois composants originale. Globalement, ce travail contribue au progrès de la connaissance sur l'utilisation des carbènes comme organocatalyseurs et intermédiaires réactionnels. / N-heterocyclic carbenes (NHCs) have become extremely popular organocatalysts in last decade. In this manuscript, we present our work in the design and the synthesis of a new class of bifunctional NHC organocatalysts, and their applications in enantioselective reactions with homoenolate equivalents. Additionally, a conceptually new synthetic approach to pyrid-2-ylidene carbenes is proposed and used in an original three-component reaction. In a broad sense, this work contributes to the progress of knowledge on the use of NHCs as organocatalysts and reaction intermediates.

La conception de nouveaux moteurs impose de respecter des normes de sécurité concernant les performances d'allumage et de ré-allumage en conditions critiques. Des campagnes d'essais étant onéreuses, les industriels cherchent donc à disposer d'outils numériques fiables. Afin d'améliorer la simulation des écoulements, le caractère multicomposant du carburant doit être pris en compte. L'objectif de cette thèse est d'étudier l'influence de l'évaporation d'un brouillard de gouttes sur un écoulement réactif. Pour cela, une étude de la propagation d'une flamme laminaire 1D est réalisée à l'aide d'un code de calcul multiphysique (CEDRE). Un train continu de gouttes monodisperse est injecté, les gouttes étant mono ou bicomposant. L'influence de la dynamique d'évaporation sur la combustion est étudiée. Deux cinétiques chimiques réduites multicomposant sont comparées. La composition, le diamètre et la richesse initiale des gouttes ont un impact sur la structure de flamme, la vitesse de flamme et la composition des gaz brûlés. Ensuite, l'effet de l'évaporation est étudié en phase d'allumage pour un brouillard de gouttes polydisperses monocomposant avec un modèle de noyau d'allumage local. L’écoulement instationnaire non-réactif dans un secteur de chambre industriel (MERCATO) est calculé avec une approche LES. Le caractère instationnaire, voire périodique, de la phase dispersée est mis en évidence en certains points de l'écoulement. Les résultats, associés au modèle d'allumage et à des critères, sont utilisées pour réaliser une carte de probabilité d'allumage. Des essais de calcul d'allumage complet de la chambre sont réalisés. Les résultats indiquent une surestimation des termes sources liés à l'évaporation de la phase dispersée et à la combustion. / The design of new aircraft engines needs in particular to comply with safety standards for the performance of stabilized combustion and ignition or re-ignition under critical conditions. Experimental campaigns are expensive, so numerical tools are needed. To improve the accuracy of the models used to simulate flow, the multicomponent nature of the fuel must be taken into account, whether it is kerosene or alternative fuel. The objective of this thesis is to study the influence of a droplet mist vaporization on a reactive flow. For this, an academic study of the propagation of a 1D laminar flame is performed using a CFD code {CEDRE). A continuous stream of monodisperse droplets is injected, the droplets being mono or bicomponent. The influence of the dynamics of evaporation on combustion is particularly studied. Two reduced multicomponent chemical kinetics are compared. The composition, the diameter and the initial equivalent ratio of droplets have an impact on the structure of the flame, the flame speed and composition of the burnt gases. A local ignition kernel model is applied to study the influence ofvaporization on ignition in the case of monocomponent, polydisperse droplets. Experimental data are available for a monosector combustion chamber (MERCATO) so the non-reactive unsteady flow is simulated with a LES approach. The unsteady, sometimes periodic, nature of the dispersed phase is highlighted in some points of the flow. A ignition model is applied to instantaneous flow fields and criteria are analysed to realise an ignition probability map which validates the approach. Finally, ignition of a combustion chamber is tested. The results point out an overestimation of source terms related to the evaporation of the dispersed phase and combustion.

Os fármacos são essenciais para a preservação da saúde do homem e de animais e também na prevenção de doenças. Entretanto, seu alto consumo associado ao descarte incorreto e aos tratamentos ineficientes de águas e efluentes podem trazer grandes prejuízos ao meio ambiente como, por exemplo, a resistência bacteriana. O objetivo deste trabalho foi estudar a remoção de ampicilina (AMP), atenolol (ATN) e paracetamol (PAR), fármacos de três classes distintas, em soluções aquosas através da técnica de adsorção em carvão ativado granular (CAG). Foram realizados experimentos de adsorção em batelada avaliando o efeito dos parâmetros pH, tempo de contato e concentração de sólido adsorvente. O comportamento cinético da adsorção dos fármacos em carvão ativado granular foi avaliado por meio dos modelos de pseudo-primeira ordem, pseudosegunda ordem e difusão intrapartícula. Ainda, isotermas de equilíbrio para estes sistemas foram construídas em diferentes temperaturas (15, 25 e 35 °C) e analisadas através dos modelos de Langmuir, Freundlich e Sips. O processo de adsorção também foi avaliado através de ensaios termodinâmicos. A adsorção em coluna de leito fixo foi avaliada utilizando planejamentos experimentais para os fármacos e os efeitos da massa do leito de adsorvente (0,5 – 1,5 g) e da vazão de alimentação (10 – 15 mL min-1) foram estudados Ainda, a fim de se avaliar o comportamento dos fármacos quando em mistura, foram realizados ensaios de adsorção em batelada e em coluna de leito fixo da mistura de ampicilina e paracetamol. Os melhores resultados encontrados nos ensaios de adsorção batelada foram: pH 6 e concentração de sólido adsorvente de 10 g L-1 para os três fármacos. O tempo de adsorção mais adequado foi de 90 minutos para o ATN e 120 min para AMP e PAR. Nessas condições foi possível obter remoções de 90 %, 94 % e 96 % para a ampicilina, atenolol e paracetamol, respectivamente. O modelo cinético que melhor descreveu o processo de adsorção foi o de pseudo-primeira ordem, para os fármacos ampicilina e paracetamol, e pseudo-segunda ordem para o atenolol. As isotermas obtidas para os fármacos indicaram que o processo de adsorção é de natureza endotérmica, ou seja, a adsorção é favorecida com o aumento da temperatura. Para a AMP, o melhor ajuste das isotermas foi obtido pelo modelo de Langmuir nas temperaturas de 15 ºC e 25 ºC e pelo modelo de Sips na temperatura de 35 ºC. Para o ATN, o melhor ajuste foi obtido pelo modelo de Freundlich e, para o PAR, o modelo de Sips, nas três temperaturas estudadas. Os ensaios termodinâmicos indicaram que o processo de adsorção dos fármacos é favorável e espontâneo e comprovou a natureza endotérmica do processo Em relação aos resultados obtidos na adsorção em coluna de leito fixo foi observado que os tempos de ruptura e de saturação aumentam com o aumento da massa de sólido presente no leito e diminuem com o aumento da vazão. A massa de adsorvente apresentou efeito negativo sobre a fração de leito utilizado e foi significativa no processo de adsorção dos três fármacos. Já a vazão de alimentação só foi significativa na adsorção em leito fixo da AMP e apresentou efeito positivo na fração de leito utilizado. Os maiores volumes de efluente tratado foram obtidos com a maior massa de sólido utilizada (1,5 g) e com a menor vazão de alimentação testada (10 mL min-1). Na adsorção multicomponente em batelada, verificou-se que há concorrência entre os fármacos pelos sítios ativos do CAG disponíveis para adsorção. Os resultados obtidos nos ensaios das isotermas de adsorção mostraram que o comportamento dos fármacos em mistura é o mesmo que quando comparados individualmente. Os modelos que melhor se ajustaram aos dados experimentais foram os mesmos obtidos nos ensaios monocomponente, Langmuir para a AMP e Sips para o PAR. Da mesma forma que para os experimentos em coluna monocomponente, os ensaios multicomponentes demostraram que os tempos de ruptura e de saturação são maiores para o PAR. Entretanto, esses valores são menores do que na adsorção individual indicando que houve concorrência entre os fármacos pelos sítios do adsorvente. Os resultados encontrados indicam que a adsorção é uma alternativa viável para a remoção de fármacos, contribuindo, assim, para o avanço das pesquisas relacionadas ao tratamento de efluentes contaminados por estes poluentes. / Drugs are essential for preservation of human and animal health as well as for disease prevention. However, its high consumption associated with incorrect disposal and inefficient treatment of water and effluents can cause great damage to the environment such as bacterial resistance, for example. The objective of this work was to study the removal of ampicillin (AMP), atenolol (ATN) and paracetamol (PAR), drugs of three different classes, in aqueous solutions by adsorption technique in granular activated carbon (GAC). Adsorption experiments were carried out in batch evaluating the effect of parameters pH, contact time and concentration of solid adsorbent. The kinetic behavior of the adsorption of drugs in granular activated carbon was evaluated through the pseudofirst order, pseudo-second order and intraparticle diffusion models. Furthermore, equilibrium isotherms for these systems were made at different temperatures (15, 25 and 35 ° C) and analyzed using the Langmuir, Freundlich and Sips models. The adsorption process was also evaluated through thermodynamic tests. The fixed bed column adsorption was evaluated by experimental planning for drugs and the effects of mass of the adsorbent bed (0.5 to 1.5 g) and feed rate (10 - 15 ml min-1) were studied Also, in order to evaluate the behavior of the drugs when in mixture, adsorption tests were carried out in batch and in fixed bed column for the mixture of ampicillin and paracetamol. The best results found in the batch adsorption tests were: pH 6 and concentration of adsorbent solid of 10 g L-1 for the three drugs. The most suitable adsorption time was 90 minutes for ATN and 120 min for AMP and PAR. Under these conditions it was possible to obtain removals of 90%, 94% and 96% for ampicillin, atenolol and paracetamol respectively. The kinetic model that best described the adsorption process was the pseudo-first order for the ampicillin and paracetamol drugs and pseudo-second order for atenolol. The isotherms obtained for the drugs indicated that the adsorption process is of endothermic nature, that is, the adsorption is favored with the increase in temperature. For the AMP, the best isotherm adjustment was obtained by the Langmuir model at temperatures of 15 °C and 25 °C and by the Sips model at temperature of 35 °C. For the ATN, the best fit was obtained by the Freundlich model and, for PAR, the Sips model at the three temperatures studied. The thermodynamic tests indicated that the adsorption process of the drugs was favorable and spontaneous and confirmed the endothermic nature of the process Regarding the results obtained in adsorption in fixed bed column, it was observed that rupture and saturation times increase with the increase of the mass of solid present in the bed and decrease with the increase of flow. The adsorbent mass had a negative effect on the used bed fraction and was significant in the adsorption process of the three drugs. The feed flow was only significant in the adsorption in fixed bed of the AMP and had positive effect in the used bed fraction. The highest volumes of treated effluent were obtained with the largest mass of solid used (1,5 g) and with the lowest feed rate tested (10 mL min-1). In multicomponent adsorption in batch, it was found that there is competition between the drugs by the active sites of GAC available for adsorption. The results obtained in the adsorption isotherms tests showed that the behavior of the drugs in mixture is the same as when compared individually. The models that best fit the experimental data were the same ones obtained in the monocomponent tests, Langmuir for AMP and Sips for PAR. Similarly as for the monocomponent column experiments, the multicomponent tests showed that the break and saturation times are larger for the PAR. However, these values are lower than in individual adsorption indicating that there was competition between the drugs for the sites of the adsorbent. The results indicate that adsorption is a viable alternative for the removal of drugs, thus contributing to the advancement of research related to the treatment of effluents contaminated by these pollutants.

Les superpositions d'ondes modulées en amplitude et en fréquence (modes AM--FM) sont couramment utilisées pour modéliser de nombreux signaux du monde réel : cela inclut des signaux audio (musique, parole), médicaux (ECG), ou diverses séries temporelles (températures, consommation électrique). L'objectif de ce travail est l'analyse et la compréhension fine de tels signaux, dits "multicomposantes" car ils contiennent plusieurs modes. Les méthodes mises en oeuvre vont permettre de les représenter efficacement, d'identifier les différents modes puis de les démoduler (c'est-à-dire déterminer leur amplitude et fréquence instantanée), et enfin de les reconstruire. On se place pour cela dans le cadre bien établi de l'analyse temps-fréquence (avec la transformée de Fourier à court terme) ou temps-échelle (transformée en ondelettes continue). On s'intéressera également à une méthode plus algorithmique et moins fondée mathématiquement, basée sur la notion de symétrie des enveloppes des modes : la décomposition modale empirique. La première contribution de la thèse propose une alternative au processus dit ``de tamisage'' dans la décomposition modale empirique, dont la convergence et la stabilité ne sont pas garanties. \`A la place, une étape d'optimisation sous contraintes ainsi qu'une meilleure détection des extrema locaux du mode haute fréquence garantissent l'existence mathématique du mode, tout en donnant de bons résultats empiriques. La deuxième contribution concerne l'analyse des signaux multicomposantes par la transformée de Fourier à court terme et à la transformée en ondelettes continues, en exploitant leur structure particulière ``en ridge'' dans le plan temps-fréquence. Plus précisément, nous proposons une nouvelle méthode de reconstruction des modes par intégration locale, adaptée à la modulation fréquentielle, avec des garanties théoriques. Cette technique donne lieu à une nouvelle méthode de débruitage des signaux multicomposantes. La troisième contribution concerne l'amélioration de la qualité de la représentation au moyen de la ``réallocation'' et du ``synchrosqueezing''. Nous prolongeons le synchrosqueezing à la transformée de Fourier à court terme, et en proposons deux extensions inversibles et adaptées à des modulations fréquentielles importantes, que nous comparons aux méthodes originelles. Une généralisation du synchrosqueezing à la dimension 2 est enfin proposée, qui utilise le cadre de la transformée en ondelettes monogène. / Many signals from the physical world can be modeled accurately as a superposition of amplitude- and frequency-modulated waves. This includes audio signals (speech, music), medical data (ECG) as well as temporal series (temperature or electric consumption). This thesis deals with the analysis of such signals, called multicomponent because they contain several modes. The techniques involved allow for the detection of the different modes, their demodulation (ie, determination of their instantaneous amplitude and frequency) and reconstruction. The thesis uses the well-known framework of time-frequency and time-scale analysis through the use of the short-time Fourier and the continuous wavelet transforms. We will also consider a more recent algorithmic method based on the symmetry of the enveloppes : the empirical mode decomposition. The first contribution proposes a new way to avoid the iterative ``Sifting Process'' in the empirical mode decomposition, whose convergence and stability are not guaranteed. Instead, one uses a constrained optimization step together with an enhanced detection of the local extrema of the high-frequency mode. The second contribution analyses multicomponent signals through the short-time Fourier transform and the continuous wavelet transform, taking advantage of the ``ridge'' structure of such signals in the time-frequency or time-scale planes. More precisely, we propose a new reconstruction method based on local integration, adapted to the local frequency modulation. Some theoretical guarantees for this reconstruction are provided, as well as an application to multicomponent signal denoising. The third contribution deals with the quality of the time-frequency representation, using the reassignment method and the synchrosqueezing transform: we propose two extensions of the synchrosqueezing, that enable mode reconstruction while remaining efficient for strongly modulated waves. A generalization of the synchrosqueezing in dimension 2 is also proposed, based on the so-called monogenic wavelet transform.

Esta tese esta dividida em três capítulos: Primeiro capítulo -­ Resolução cinética enzimática de sulfetos, selenetos e teluretos em CO2 supercrítico. Inicialmente, a estabilidade dos &#946;-hidróxi organocalcogenetos foi avaliada em CO2 supercrítico. Como a variação da pressão e temperatura afeta a densidade do fluído de forma não linear, um estudo sistemático foi realizado para avaliação desses parâmetros, visando altos excessos enantioméricos para os &#946;-­hidróxi-­ sulfetos e -­selenetos, os quais foram determinados por cromatografia líquida de alta eficiência (CLAE). Os &#946;-­hidróxi-­teluretos não se apresentaram estáveis sob as mesmas condições. Desta maneira, um novo método para determinar o excesso enantiomérico dos &#946;-­hidróxi-­teluretos foi desenvolvido, utilizando RMN de 125Te. Capítulo 2 -­ Utilização de teluroferrocenos quirais como sondas quirais para a determinação de excessos enantioméricos usando RMN de 125Te. Teluroferrocenos quirais, substituídos por grupos amidas, oxazolinas e aminas foram preparados. Tais moléculas contendo telúrio interagem com amostras quirais, formando complexos diastereoisoméricos, nos quais os átomos de telúrio são submetidos a diferentes ambientes químicos, o que resulta em diferentes deslocamentos químicos para cada complexo diastereoisomérico. A integração dos sinais de 125Te permite a determinação do excesso enantiomérico de amostras quirais. Terceiro capítulo - Calcogenação de olefinas ativadas. Organocalcogenolatos de lítio gerados in situ reagiram com olefinas ativadas. Na presença de uma fonte de prótons, foram formados os calcogenetos &#946;-­funcionalizados. Em meio anidro, o enolato intermediário pode ser capturado com compostos carbonílicos em reações tandem tri-­ componentes, gerando precursores de Morita-­Baylis-­Hillman, quando Y = S, Se. / This thesis contains three chapters: 1st chapter - Kinetic enzymatic resolution of sulfides, selenides and tellurides in supercritical CO2. Initialy, the stability of the &#946;-­hydroxy organochalcogenides in suprecritical CO2 was evaluated. As the variation in the pressure and temperature affect the fluid density in a non-­linear way, a systematic study on the influence of these parameters was performed, aiming a high enantiomeric excess for the products. The enantiomeric excesses of the &#946;-­hydroxy sulfides and selenides were determined by high performance chiral liquid chromatography (HPLC). The &#946;-­hydroxy tellurides were not stable under the same conditions. In view of this fact, a new method to determine the enantiomeric excess of the &#946;-­hydroxy tellurides was developed, using 125Te NMR spectroscopy for this end. 2nd chapter - Use of chiral telluroferrocenes as chiral probes for the enantiomeric excess determination using 125Te NMR spectroscopy. Chiral telluroferrocenes, substituted by amides, oxazolines and amines were prepared. These chiral tellurium containing molecules interact with chiral samples, forming diastereomeric transient complexes in which the tellurium atoms are submitted to different chemical environments, what leads to different 125Te chemical shifts for each diastereomeric complex integration of the 125Te NMR spectra allowing the determination of the enantiomeric excess of the chiral samples. 3rd chapter - Chalcogenation of activated olefines. In situ gererated lithium organochalcogenolates were reacted with activated olefines. In the presence of a proton source, the &#946;-functionalized chalcogenides were formed. Under anhydrous conditions, the intermediate enolate can be trapped with carbonyl compounds in a three components process to give precursors of Morita-­Baylis-­Hillman adducts when Y = S, Se.

Made available in DSpace on 2016-12-08T15:56:17Z (GMT). No. of bitstreams: 1 TESE_ ELIANA FRANCO.pdf: 10762116 bytes, checksum: 0473839f89cd4764137c8cf282af6c0d (MD5) Previous issue date: 2014-06-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Materials or coatings for tools are of primary importance for industrial development. This work proposes the development of tools materials through two routes, one of them using cermets based Fe-NbC as a raw material and the other through thermochemical treatments in steel tool substrates. The specific objectives were planning the processing, manufacture and analyze of Fe-NbC cermets; and to develop a coating composed by B, Nb and C by diffusion thermoreactive in solid-state in M2 high speed steel substrates. There are some studies, even applications of cermets using iron as a matrix, such as cermets with TiC or Ti (C, N) carbides. The Brazilian Society of Mining and Metallurgy (Companhia Brasileira de Metalurgia e Mineração - CBMM) produced the Fe-NbC cermets with different contents of Al and other elements added during the obtaining of cermets. In this work thermal analyzes and calculations of phases equilibrium were performed through ThermoCalc® software to study the thermal behavior of these materials. Also, C and Fe were added to these materials and consolidations by conventional powder metallurgy and by Field Assisted Hot Pressing (FAHP). The results showed that these cermets had a temperature of formation of liquid phase around 1200o C. The Fe and C addition resulted in the disappearance of undesirable phases. The cermet FeNbC5Al exhibited higher hardness with or without additions, 820 HV10 without additions elements and after consolidation by FAHP and annealing. For the development of surface coatings, multicomponent boriding with Nb treatments were performed on substrates of M2; treatments in stages, with diffusion of Nb and B separately; and simultaneous treatments, with diffusion of Nb and B at the same time. Treatments were carried out by the thermoreactive diffusion method on solid-state; calculations were made by ThermoCalc® to estimate the pack composition and treatment temperature. The results showed that by the treatment performed in stages, a coating formed by NbB and NbC phase with hardness 2300 HV was obtained. The wear volume of the material showed high dispersion of results, which can be improved by producing a more homogeneous niobized layer; a suggestion to obtain that layer is using a substrate with a small addition of alloying elements or niobizing in liquid bath. / O interesse por materiais ou recobrimentos para ferramentas é de suma importância para o desenvolvimento industrial. Este trabalho propõe o desenvolvimento de ferramentas através de duas rotas, uma utilizando como matéria prima cermets a base de Fe-NbC e outra por meio de tratamentos termoquímicos em substratos de aço ferramenta. Os objetivos específicos foram planejar o processamento, fabricar e analisar cermets Fe-NbC; e desenvolver um recobrimento a base de B, Nb e C por difusão termorreativa em meio sólido, em substratos de aço rápido M2. Há alguns estudos, e até mesmo aplicações de cermets que utilizam ferro como matriz, como os cermets com carbonetos de TiC ou Ti(C,N). A Companhia Brasileira de Metalurgia e Mineração (CBMM) produziu os cermets Fe-NbC com diferentes teores de Al, bem como outros elementos, adicionados durante a obtenção dos cermets. Neste trabalho realizaram-se análises térmicas e cálculos de equilíbrio de fases através do software ThermoCalc® para estudar o comportamento térmico destes materiais. Também se fizeram adições de C e Fe a esses materiais e consolidações por metalurgia do pó convencional e por compactação a quente assistida por campo (FAHP). Os resultados mostraram que esses cermets apresentaram uma temperatura de formação de fase líquida em torno de 1200o C. A adição de C e Fe resultou no desaparecimento de fases indesejáveis. O cermet FeNbC5Al exibiu maior dureza com ou sem adições, 820 HV10 sem adição de elementos e após consolidação assistida por campo e recozimento. Para desenvolvimento dos recobrimentos de superfície, realizaram-se tratamentos de boretação multicomponente com Nb sobre substratos de M2; tratamentos em etapas, com difusão de B e Nb separadamente; e tratamentos simultâneos, com difusão de B e Nb ao mesmo tempo. Realizaram-se os tratamentos pelo método de difusão termorreativa em meio sólido, se fizeram cálculos por ThermoCalc® para a estimativa da composição da mistura e temperatura de tratamento. Os resultados mostraram que através do tratamento em etapas, se obteve um recobrimento formado por fases de NbB e NbC com dureza de 2300 HV. O volume de material removido desse material apresentou alta dispersão de resultados, o que pode ser melhorado através da produção de uma camada niobizada mais homogênea; uma sugestão para obtenção de uma camada mais homogênea é através da utilização de um substrato com pouca adição de elementos de liga ou da realização de niobização em banho líquido.

Made available in DSpace on 2014-12-17T14:16:33Z (GMT). No. of bitstreams: 1 PolyanneNM_DISSERT_Parcial.pdf: 770580 bytes, checksum: 39b0d43a294576d304dce8d402da84aa (MD5) Previous issue date: 2013-02-28 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The benznidazole (BNZ) is the only alternative for Chagas disease treatment in Brazil. This drug has low solubility, which restricts its dissolution rate. Thus, the present work aimed to study the BNZ interactions in binary systems with beta cyclodextrin (?-CD) and hydroxypropyl-beta cyclodextrin (HP-?-CD), in order to increase the apparent aqueous solubility of drug. The influence of seven hydrophilic polymers, triethanolamine (TEA) and 1-methyl-2- pyrrolidone (NMP) in benznidazole apparent aqueous solubility, as well as the formation of inclusion complexes was also investigated. The interactions in solution were predicted and investigated using phase solubility diagram methodology, nuclear magnetic resonance of protons (RMN) and molecular modeling. Complexes were obtained in solid phase by spray drying and physicochemical characterization included the UV-Vis spectrophotometric spectroscopy in the infrared region, scanning electron microscopy, X-ray diffraction and dissolution drug test from the different systems. The increment on apparent aqueous solubility of drug was achieved with a linear type (AL) in presence of both cyclodextrins at different pH values. The hydrophilic polymers and 1-methyl-2-pyrrolidone contributes to the formation of inclusion complexes, while the triethanolamine decreased the complex stability constant (Kc). The log-linear model applied for solubility diagrams revealed that both triethanolamine and 1-methyl-2-pyrrolidone showed an action cosolvent (both solvents) and complexing (1-methyl-2-pyrrolidone). The best results were obtained with complexes involving 1-methyl-2-pyrrolidone and hydroxypropylbeta- cyclodextrin, with an increased of benznidazole solubility in 27.9 and 9.4 times, respectively. The complexes effectiveness was proven by dissolution tests, in which the ternary complexes and physical mixtures involving 1-methyl- 2-pyrrolidone and both cyclodextrins investigated showed better results, showing the potential use as novel pharmaceutical ingredient, that leads to increased benznidazole bioavailability / A doen?a de Chagas tem como ?nica alternativa para tratamento, no Brasil, o benznidazol (BNZ). Este f?rmaco possui baixa solubilidade, o que restringe sua velocidade de dissolu??o. Diante disto, o presente trabalho teve como objetivo o estudo das intera??es do BNZ em sistemas bin?rios com a beta-ciclodextrina (?-CD) e a hidroxipropil-beta-ciclodextrina (HP-?-CD), com o intuito de aumentar a solubilidade aquosa do f?rmaco. A influ?ncia de sete pol?meros hidrof?licos, da trietanolamina (TEA) e da metil-1-pirrolidona-2 (NMP) na solubilidade aquosa aparente do benznidazol, assim como na forma??o dos complexos de inclus?o, tamb?m foi investigada. As intera??es em solu??o foram previstas e investigadas usando os diagramas de solubilidade de fases, espectroscopia de ressonancia magn?tica nuclear de pr?tons (RMN) e modelagem molecular. Diferentes complexos foram obtidos em fase s?lida por secagem por atomiza??o em aparelho de spray dryer e a caracteriza??o f?sico-qu?mica destes incluiu a espectrofotometria UV-Vis, a espectroscopia na regi?o do infravermelho, a microscopia eletr?nica de varredura, a difra??o de raios-X e os ensaios de dissolu??o do f?rmaco a partir das diferentes amostras. O aumento da solubilidade aquosa aparente do f?rmaco foi alcan?ada de forma linear (perfil AL) na presen?a de ambas as ciclodextrinas em diferentes valores de pH. A presen?a dos pol?meros hidrof?licos e da metil-1-pirrolidona-2 contribui para a estabiliza??o dos complexos formados, enquanto a trietanolamina diminuiu a constante de estabilidade (Kc) dos complexos formados. O modelo do log linear aplicado aos diagramas de solubilidade revelou que a trietanolamina e a metil-1-pirrolidona-2 mostraram uma a??o cossolvente (ambos solventes) e complexante (metil-1-pirrolidona-2). Os melhores resultados foram obtidos com os complexos envolvendo a metil-1-pirrolidona-2 e a hidroxipropil-beta-ciclodextrina, com um aumento de solubilidade do f?rmaco em 27,9 e 9,4 vezes, respectivamente. A efic?cia dos complexos foi comprovada pelos ensaios de dissolu??o, nos quais os complexos tern?rios e misturas f?sicas envolvendo a metil-1-pirrolidona-2 e as ciclodextrinas investigadas apresentaram os melhores resultados, demonstrando a possibilidade de uso como um novo insumo farmac?utico, que leve ao aumento da biodisponibilidade do benznidazol / 2020-01-01

Os fármacos são essenciais para a preservação da saúde do homem e de animais e também na prevenção de doenças. Entretanto, seu alto consumo associado ao descarte incorreto e aos tratamentos ineficientes de águas e efluentes podem trazer grandes prejuízos ao meio ambiente como, por exemplo, a resistência bacteriana. O objetivo deste trabalho foi estudar a remoção de ampicilina (AMP), atenolol (ATN) e paracetamol (PAR), fármacos de três classes distintas, em soluções aquosas através da técnica de adsorção em carvão ativado granular (CAG). Foram realizados experimentos de adsorção em batelada avaliando o efeito dos parâmetros pH, tempo de contato e concentração de sólido adsorvente. O comportamento cinético da adsorção dos fármacos em carvão ativado granular foi avaliado por meio dos modelos de pseudo-primeira ordem, pseudosegunda ordem e difusão intrapartícula. Ainda, isotermas de equilíbrio para estes sistemas foram construídas em diferentes temperaturas (15, 25 e 35 °C) e analisadas através dos modelos de Langmuir, Freundlich e Sips. O processo de adsorção também foi avaliado através de ensaios termodinâmicos. A adsorção em coluna de leito fixo foi avaliada utilizando planejamentos experimentais para os fármacos e os efeitos da massa do leito de adsorvente (0,5 – 1,5 g) e da vazão de alimentação (10 – 15 mL min-1) foram estudados Ainda, a fim de se avaliar o comportamento dos fármacos quando em mistura, foram realizados ensaios de adsorção em batelada e em coluna de leito fixo da mistura de ampicilina e paracetamol. Os melhores resultados encontrados nos ensaios de adsorção batelada foram: pH 6 e concentração de sólido adsorvente de 10 g L-1 para os três fármacos. O tempo de adsorção mais adequado foi de 90 minutos para o ATN e 120 min para AMP e PAR. Nessas condições foi possível obter remoções de 90 %, 94 % e 96 % para a ampicilina, atenolol e paracetamol, respectivamente. O modelo cinético que melhor descreveu o processo de adsorção foi o de pseudo-primeira ordem, para os fármacos ampicilina e paracetamol, e pseudo-segunda ordem para o atenolol. As isotermas obtidas para os fármacos indicaram que o processo de adsorção é de natureza endotérmica, ou seja, a adsorção é favorecida com o aumento da temperatura. Para a AMP, o melhor ajuste das isotermas foi obtido pelo modelo de Langmuir nas temperaturas de 15 ºC e 25 ºC e pelo modelo de Sips na temperatura de 35 ºC. Para o ATN, o melhor ajuste foi obtido pelo modelo de Freundlich e, para o PAR, o modelo de Sips, nas três temperaturas estudadas. Os ensaios termodinâmicos indicaram que o processo de adsorção dos fármacos é favorável e espontâneo e comprovou a natureza endotérmica do processo Em relação aos resultados obtidos na adsorção em coluna de leito fixo foi observado que os tempos de ruptura e de saturação aumentam com o aumento da massa de sólido presente no leito e diminuem com o aumento da vazão. A massa de adsorvente apresentou efeito negativo sobre a fração de leito utilizado e foi significativa no processo de adsorção dos três fármacos. Já a vazão de alimentação só foi significativa na adsorção em leito fixo da AMP e apresentou efeito positivo na fração de leito utilizado. Os maiores volumes de efluente tratado foram obtidos com a maior massa de sólido utilizada (1,5 g) e com a menor vazão de alimentação testada (10 mL min-1). Na adsorção multicomponente em batelada, verificou-se que há concorrência entre os fármacos pelos sítios ativos do CAG disponíveis para adsorção. Os resultados obtidos nos ensaios das isotermas de adsorção mostraram que o comportamento dos fármacos em mistura é o mesmo que quando comparados individualmente. Os modelos que melhor se ajustaram aos dados experimentais foram os mesmos obtidos nos ensaios monocomponente, Langmuir para a AMP e Sips para o PAR. Da mesma forma que para os experimentos em coluna monocomponente, os ensaios multicomponentes demostraram que os tempos de ruptura e de saturação são maiores para o PAR. Entretanto, esses valores são menores do que na adsorção individual indicando que houve concorrência entre os fármacos pelos sítios do adsorvente. Os resultados encontrados indicam que a adsorção é uma alternativa viável para a remoção de fármacos, contribuindo, assim, para o avanço das pesquisas relacionadas ao tratamento de efluentes contaminados por estes poluentes. / Drugs are essential for preservation of human and animal health as well as for disease prevention. However, its high consumption associated with incorrect disposal and inefficient treatment of water and effluents can cause great damage to the environment such as bacterial resistance, for example. The objective of this work was to study the removal of ampicillin (AMP), atenolol (ATN) and paracetamol (PAR), drugs of three different classes, in aqueous solutions by adsorption technique in granular activated carbon (GAC). Adsorption experiments were carried out in batch evaluating the effect of parameters pH, contact time and concentration of solid adsorbent. The kinetic behavior of the adsorption of drugs in granular activated carbon was evaluated through the pseudofirst order, pseudo-second order and intraparticle diffusion models. Furthermore, equilibrium isotherms for these systems were made at different temperatures (15, 25 and 35 ° C) and analyzed using the Langmuir, Freundlich and Sips models. The adsorption process was also evaluated through thermodynamic tests. The fixed bed column adsorption was evaluated by experimental planning for drugs and the effects of mass of the adsorbent bed (0.5 to 1.5 g) and feed rate (10 - 15 ml min-1) were studied Also, in order to evaluate the behavior of the drugs when in mixture, adsorption tests were carried out in batch and in fixed bed column for the mixture of ampicillin and paracetamol. The best results found in the batch adsorption tests were: pH 6 and concentration of adsorbent solid of 10 g L-1 for the three drugs. The most suitable adsorption time was 90 minutes for ATN and 120 min for AMP and PAR. Under these conditions it was possible to obtain removals of 90%, 94% and 96% for ampicillin, atenolol and paracetamol respectively. The kinetic model that best described the adsorption process was the pseudo-first order for the ampicillin and paracetamol drugs and pseudo-second order for atenolol. The isotherms obtained for the drugs indicated that the adsorption process is of endothermic nature, that is, the adsorption is favored with the increase in temperature. For the AMP, the best isotherm adjustment was obtained by the Langmuir model at temperatures of 15 °C and 25 °C and by the Sips model at temperature of 35 °C. For the ATN, the best fit was obtained by the Freundlich model and, for PAR, the Sips model at the three temperatures studied. The thermodynamic tests indicated that the adsorption process of the drugs was favorable and spontaneous and confirmed the endothermic nature of the process Regarding the results obtained in adsorption in fixed bed column, it was observed that rupture and saturation times increase with the increase of the mass of solid present in the bed and decrease with the increase of flow. The adsorbent mass had a negative effect on the used bed fraction and was significant in the adsorption process of the three drugs. The feed flow was only significant in the adsorption in fixed bed of the AMP and had positive effect in the used bed fraction. The highest volumes of treated effluent were obtained with the largest mass of solid used (1,5 g) and with the lowest feed rate tested (10 mL min-1). In multicomponent adsorption in batch, it was found that there is competition between the drugs by the active sites of GAC available for adsorption. The results obtained in the adsorption isotherms tests showed that the behavior of the drugs in mixture is the same as when compared individually. The models that best fit the experimental data were the same ones obtained in the monocomponent tests, Langmuir for AMP and Sips for PAR. Similarly as for the monocomponent column experiments, the multicomponent tests showed that the break and saturation times are larger for the PAR. However, these values are lower than in individual adsorption indicating that there was competition between the drugs for the sites of the adsorbent. The results indicate that adsorption is a viable alternative for the removal of drugs, thus contributing to the advancement of research related to the treatment of effluents contaminated by these pollutants.

As ligas de ferro fundido branco multicomponente são aços rápidos resistentes ao desgaste em temperaturas elevadas. Estes aços apresentam carbonetos eutéticos do tipo MC e M2C quando no estado bruto de fundição. Neste trabalho foi caracterizada a microestrutura dos produtos de decomposição após tratamentos térmicos do carboneto eutético metaestável M2C de uma liga de ferro fundido multicomponente com composição (em % peso): 2 wt% de C e 5 wt% de cada um dos elementos V, Cr, Mo e W, o restante é Fe. A liga de ferro fundido multicomponente foi tratada isotermicamente a 950°C e a 1.050°C por tempos crescentes em forno poço com sal fundido e em forno mufla inseridas em ampolas de sílica sob vácuo. Os tempos de tratamento foram: 10s, 100s, 600s, 1.800s, 1 hora, 2 horas e 15 horas. As técnicas de caracterização envolvidas foram: difração de raios X de carbonetos extraídos, metalografia através de ataques seletivos, microscopia eletrônicas de varredura (SEM), microscopia eletrônica de transmissão e varredura (STEM), espectrometria por energia dispersiva de raios X (EDS) e difração de elétrons por área selecionada (SAED). Os resultados sugerem que além dos carbonetos MC, M2C irregular e regularcomplexo e M7C3 descritos na literatura, observa-se a presença de um novo tipo de carboneto M2C metaestável rico em cromo na liga no estado bruto de fundição. Os carbonetos metaestáveis M2C se decompõem em carbonetos M6C, em carbonetos M7C3 e finalmente MC globular com o aumento da temperatura e/ou com tempos crescentes de tratamento térmico. O carboneto M7C3 após tratamento térmico de longa duração passa por um processo de esferoidização e depois engrossamento. / Multicomponent White Cast Iron are high temperature wear resistant ferrous alloys, presenting eutectic MC and M2C carbides in their as cast structure. In the present work the decomposition microstructures of the metastable M2C carbide after heat treatments was characterized in a model multicomponent white cast iron with composition (in weight): 2 wt% C and 5 wt% of each of the carbide forming alloying elements V, Cr, Mo and W, and with the balance Fe. The model multicomponent alloy was isothermally treated at 950°C and 1.050°C for increasing time periods using a salt bath pit furnace and a muffle furnace using samples encapsulated in silica glass ampoules under vacuum. Treatment times were: 10s, 100s, 600s, 1.800s, 1 hour, 2 hours and 15 hours. Characterization techniques used were: X Ray diffraction of extracted carbides, optical microscopy metallography with selective etching techniques, scanning electron microscopy (SEM), X ray energy dispersive spectroscopy (EDS), transmission and scanning electron microscopy (STEM) and selected area electrons diffraction (SAED). Besides the MC, irregular and regular-complex M2C and M7C3 described in the literature, it was found in the as cast alloy also a hitherto unknown chromium rich M2C carbide. The metastable M2C carbides decompose into M6C carbides, then M7C3 and finally globular MC with increasing temperatures and/or increasing times at heat treatment temperatures. After long times heat treatments the M7C3 carbides, spheroidize and coarsen.