Orientador: Marco Aurélio Cremasco / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-23T11:02:30Z (GMT). No. of bitstreams: 1 Moreira_JeanVinicius_M.pdf: 3509735 bytes, checksum: 14df3cf30ed160fd0f79db993d4a1a65 (MD5) Previous issue date: 2013 / Resumo: O piperonal (ou heliotropina) apresenta aplicações industriais no ramo de cosméticos como fixador de fragrâncias, além de ser matéria prima para componentes de maior valor agregado, como a piperina que é empregada como antiiflamatorio; a vanila que tem aplicações antioxidantes; o pirebidil e a L-dopa que são agentes anti Parkinson. A síntese do piperonal, a partir do óleo essencial da pimenta longa (Piper hispidinervum C. DC), não gera um produto 100 % puro, dessa forma vê-se a importância de estudar uma maneira de separar o piperonal dos demais compostos, safrol, isosafrol e terpinoleno, também presentes no produto final da síntese. Dentre os métodos de purificação há a cromatografia líquida de alta eficiência, que ao longo do tempo mostrou-se eficaz na purificação e separação de diversos compostos. O método de separação baseada em cromatografia líquida de alta eficiência depende de diversos fatores, tais como a escolha da fase estacionária e da fase móvel, bem como estudos preliminares para a posterior implementação das variáveis definidas em uma escala semi preparativa ou preparativa. Na presente Dissertação a fase estacionária utilizada foi à sílica C18 e a fase móvel uma mistura binária 70/30 (v/v) de etanol e água. A escolha da fase móvel binária deveu-se aos bons resultados de resolução obtidos entre o componente de interesse, o piperonal, e o safrol, isosafrol e terpinoleno. A resolução alcançada para o piperonal com relação aos demais componentes, safrol e isosafrol foi de 2,986 e para o terpinoleno 6,900, a literatura relata que valores acima de 1,5 representam uma completa separação. A estimativa de parâmetros chave para a coluna, como a porosidade da partícula e a fração de vazios do leito, foram obtidas por meio do método dos momentos e as isotermas de adsorção por análise frontal. As isotermas foram determinadas entre 20 e 35 ºC, com passo de 5 ºC, apresentaram uma configuração linear. De posse das isotermas, foi possível estimar os valores das constantes modificadas de Henry e as grandezas termodinâmicas ?G, ?H e ?S para o sistema, por meio do gráfico de van't Hoff. Os valores de entalpia apontam que o piperonal é o composto menos retido, pois apresenta uma entalpia igual a -1,134 KJ mol-1, o maior valor se comparado com os obtidos para o safrol, isosafrol e terpinoleno, o que demonstra a baixa interação com a fase estacionária, e consequentemente um baixo tempo de retenção do composto na coluna. Esse efeito foi comprovado com os resultados obtidos para a entropia, o piperonal foi o composto que apresentou o maior valor (6,812 J mol K-1). Ao passo que o terpinoleno apresentou um valor igual a -6,485 J mol K-1. Estes valores descrevem que a retenção do piperonal é menor se comparada com a retenção do terpinoleno. Essas distinções proporcionaram a separação entre os compostos / Abstract: Piperonal (or heliotropine) presents industrial applications in the field of cosmetics as fragrance fixative, besides being the raw material for value-added components such as piperine which is employed as anti-inflammatory, vanilla which has antioxidants applications, pirebidil and L -dopa which are anti Parkinson's disease. The synthesis of piperonal, from the Piper hispidinervum C. DC, does not generate 100% pure product, that way we can see the importance of studying a way to purify piperonal from the others compounds, safrole, isosafrole and terpinoleno, also presente in the final product of the synthesis. A method to be studied is high performance liquid chromatography, which has been proved as an effective in the purification and separation of various compounds. The separation method based on high performance liquid chromatography depends on several factors, such as the choice of stationary phase and mobile phase, as well as preliminary studies for further implementation of the defined variables in a semi-preparative or preparative scale. In the present study silica gel C18 was used as stationary phase and mobile phase was a binary mixture 70/30 (v / v) ethanol and water, respectively. The choice of the binary mobile phase was due to the good results of resolution between the component of interest, piperonal, and others; safrole, isosafrole and terpinolene. The resolution achieved for piperonal in relation to other components, safrole and isosafrole was 2.986 and 6.900 for terpinoleno. The literature reports that values above 1.5 represent a complete separation. The estimation of key parameters for the column, such as the porosity of the particle and the bed porosity were obtained by the moment method and adsorption isotherms by frontal analysis. The isotherms determined between 20 and 35 º C, with steps of 5 º C showed a linear configuration. With the isotherms in hands, it was possible to estimate the values of the Henry constants and the thermodynamics parameters for the system through the van't Hoff graphical. The enthalpy values point out that piperonal is the less retained compound, because it shows an enthalpy value equal to -1.134 KJ mol-1, the greater value if we compare to the safrol, isosafrol and terpinoleno values, this value demonstrate low interaction with the stationary phase and, consequently, a low retention time of the compound in the column. This effect was proved by the entropy values, piperonal showed the greater entropy (6.812 J mol K-1). The terpinoleno showed a value equal to -6.485 J mol K-1. These values describe that piperonal retention is smaller if we compare to terpinoleno retention. This difference makes possible the separation between the compounds / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Orientadores: Antonio José de Almeida Meirelles, Jürgen Gmehling / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-23T15:44:16Z (GMT). No. of bitstreams: 1 Belting_PatriciaCastro_D.pdf: 4041052 bytes, checksum: 985b093f692b3bc9a1072474787582f8 (MD5) Previous issue date: 2013 / Resumo: Propriedades termodinâmicas são úteis para a realização de projetos confiáveis, otimização e modelagem de processos que envolvam separação térmica e para a seleção de solventes usados em processos de extração. Tais propriedades são também necessárias no desenvolvimento de novos modelos termodinâmicos e no ajuste de parâmetros de modelos preditivos. Este trabalho de tese teve como objetivo principal ampliar o banco de dados de propriedades termodinâmicas para compostos graxos através da determinação sistemática do coeficiente de atividade à diluição infinita ( ), entalpia de excesso ( ) e dados de equilíbrio líquido-vapor (ELV) de sistemas contendo ácidos graxos e óleos vegetais. A primeira parte deste trabalho apresenta os dados de para vários solutos orgânicos diluídos em ácidos graxos saturados e insaturados, medidos pelo método de cromatografia gás-líquido na faixa de temperatura entre 303,13 K e 368,19 K. Através dos resultados obtidos, puderam ser identificadas diferentes tendências para compostos polares e não polares, tanto na série de ácidos graxos como também em relação à temperatura. Foi verificado que tanto a presença quanto o número de insaturações na cadeia carbônica do ácido graxo têm influência nas interações solvente-soluto e, consequentemente, nos valores de . A segunda parte deste trabalho tratou de medidas realizadas em sistemas contendo óleos vegetais refinados. Os óleos de soja, girassol e canola foram submetidos a determinações de , e ELV. As medidas de para n-hexano, metanol e etanol diluídos nos óleos vegetais foram determinadas pela técnica do Dilutor na faixa de temperatura entre 313,15 K e 353,15 K. Os dados experimentais obtidos foram comparados com os resultados gerados pelos métodos UNIFAC original e modificado (Dortmund) e para este último modelo, foi proposta uma extensão para os triacilgliceróis. Os dados de foram medidos para 11 misturas contendo solventes e os óleos vegetais relacionados anteriormente na faixa de temperatura de 298,15 K a 383,15 K. Todos os sistemas investigados apresentaram desvio em relação ao comportamento ideal e os valores de apresentaram-se, na maioria, positivos. Dados isotérmicos de ELV foram medidos para misturas entre os mesmos óleos vegetais e metanol, etanol e n-hexano a 348,15 K e 373,15 K através de um método estático. Para misturas com n-hexano, foi observado desvio negativo da lei de Raoult e um comportamento homogêneo, enquanto que as misturas com álcool apresentaram desvio positivo da idealidade e imiscibilidade. Os dados experimentais de ELV foram representados satisfatoriamente pelo modelo UNIQUAC, enquanto que os modelos UNIFAC modificado (Dortmund) e sua extensão proposta para triacilgliceróis foram capazes de predizer os sistemas apenas de forma qualitativa. Finalmente, dados isobáricos de ELV foram medidos para misturas com etanol + óleo de soja a 101,3 kPa e n-hexano + óleo de algodão a 41,3 kPa utilizando o ebuliômetro de Othmer modificado. Os resultados da correlação UNIQUAC também apresentaram boa concordância com os dados experimentais. Este trabalho resultou em um total de 1829 novos dados que irão expandir o banco de dados disponível para compostos graxos, permitindo uma descrição mais precisa do comportamento real de sistemas contendo tais substâncias / Abstract: Thermodynamic properties are useful for the reliable design, optimization and modelling of thermal separation processes as well as for the selection of solvents used in extraction processes. They are also required for the development of new thermodynamic models and for the adjustment of reliable model parameters. In order to improve the thermodynamic properties data bank of fatty compounds, the systematic determination of activity Coefficients at infinite dilution ( ), excess enthalpies ( ) and vapor-liquid equilibria (VLE) data of systems containing fatty acids and vegetable oils was performed. The first part of this work presents data for several organic solutes dissolved in saturated and unsaturated fatty acids measured by gas-liquid chromatography at temperatures from 303.13 K to 368.19 K and the comparison to available literature data. Different trends for polar and non-polar compounds could be identified both in the series of fatty acids and as function of temperature. It appears that both the presence and the number of cis double bonds in the fatty acid alkyl chain have influence on the solvent-solute interactions and hence on the values of . The second part of this work deals with measurements performed on systems with refined vegetable oils. Soybean, sunflower and rapeseed oils were submitted to measures of , , and VLE. The measurements of for n-hexane, methanol and ethanol dissolved in these vegetable oils were determined by gas stripping method (dilutor technique) in the temperature range of 313.15 K to 353.15 K. The experimental data were compared with the results of the group contribution methods original UNIFAC and modified UNIFAC (Dortmund) and an extension of the latter method to triacylglycerols was proposed. The data were measured for eleven mixtures containing solvents (organic and water) and the prior mentioned vegetable oils in the temperature range from 298.15 K to 383.15 K. All systems investigated showed deviation from the ideal behavior and their experimental data are mostly positive. Isothermal VLE data have been measured for methanol, ethanol, and n-hexane with the same vegetable oils at 348.15 K and 373.15 K using a computer-driven static apparatus. For mixtures with n-hexane it was observed a negative deviation from Raoult¿s law and a homogeneous behavior, while mixtures with alcohols had a positive deviation from ideal behavior and, in some cases, with miscibility gap. The experimental VLE data were satisfactorily represented by the UNIQUAC model, while the mod. UNIFAC (Dortmund) method and its proposed extension for triacylglicerols were capable of predicting the experimental data only in a qualitative way. Finally, isobaric VLE data were measured for mixtures of ethanol with refined soybean oil at 101.3 kPa and for n-hexane and cottonseed oil at 41.3 kPa using a modified Othmer-type ebulliometer. The results of the UNIQUAC correlation also showed good agreement with the experimental results. This work resulted in a total of 1829 new data that will expand the available fatty compounds data base, allowing a more accurate description of the real behavior of fatty systems / Doutorado / Engenharia de Alimentos / Doutora em Engenharia de Alimentos

Orientador: Marco Aurelio Cremasco / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T16:19:52Z (GMT). No. of bitstreams: 1 Oliveira_CarlosEduardoLimade_M.pdf: 2139178 bytes, checksum: a60210b4b807de0c845fa8804f6ebb27 (MD5) Previous issue date: 2012 / Resumo: As espécies vegetais Lippia gracilis, popularmente conhecida como "alecrim-da-chapada" ou "alecrim-de-tabuleiro", são arbustos caducifólios, ramificados, com caule quebradiço, de até 2 m de altura...Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital / Abstract: The plant species Lippia gracilis, popularly known as "alecrim-da-chapada" or "alecrim-de-tabuleiro", are deciduous shrubs, branched, with brittle stems, up to 2 m tall. Belong to the family Verbenaceae and are widely distributed in America and Africa, mainly in tropical countries. ...Note: The complete abstract is available with the full electronic document / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Orientador: Fernando Antonio Cabral / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-03T18:03:27Z (GMT). No. of bitstreams: 1 Perozin_Denise_M.pdf: 4208838 bytes, checksum: 377d3d931173564bc306e6c756a7f8bb (MD5) Previous issue date: 2003 / Resumo: A modelagem termodinâmica que usa a EOS de Peng-Robinson foi empregada no equilíbrio de fases de sistemas aquosos de açúcares em condições atmosféricas de pressão (onde existem dados experimentais de equilíbrio), para posteriormente ser aplicada em condições de equikíbrio à altas pressões. Dados experimentais de atividade de água dos sistemas binários água-açúcares foram coletados da literatura e os parâmetros de interação binária água-açúcar foram obtidos pelo ajuste ao modelo. Foi avaliada a capacidade do modelo predizer o equilíbrio multicomponente (comparando com valores experimentais disponíveis na literatura), utilizando-se dos parâmetros de interação binária açúcar-água ajustados e adotando como nulos os parâmetros de interação binária açúcar-açúcar. Teve também como objetivo, avaliar as características do equilíbrio quando se aplica pressão elevada. Os parâmetros de interação binária foram obtidos pelo ajuste do modelo termodinâmico a dados experimentais do equilíbrio líquido-vapor (dados de atividade de água em sistemas binários). As fugacidades, ou pressão de sublimação, dos açúcares no estado sólido foram obtidas a partir de dados de solubilidade, calculando a fugacidade do açúcar na solução aquosa saturada. Os resultados obtidos indicam que a modelagem termodinâmica à pressão atmosférica correlaciona bem os dados experimentais dos sistemas binários, apresentando um desvio médio de 5% na fração mássica do açúcar ou o equivalente a O) 7% de desvio médio em atividade de água. Um desvio um pouco maior, de 7% em média, foi observado para o equilíbrio líquido-vapor multicomponente. Valores de fugacidade do açúcar no estado sólido foram estimados e quando comparados a valores de pressão de sublimação, extrapolando os dados experimentais, para glicose e para a xilose, mostraram que os valores são coerentes em ordem de grandeza com os experimentais, principalmente para a xilose, no entanto a modelagem não reproduziu bem os dados experimentais do equilíbrio sólido-líquido. A pressões elevadas, os cálculos usando a modelagem termodinâmica com parâmetros obtidos a baixa pressão indicam que a solubilidade da sacarose decresce com o aumento de pressão e a solubilidade da glicose tem um leve acréscimo com o aumento da pressão, sugerindo com isto que o uso de pressões elevadas pode vir a ser uma técnica para processos de separações / Abstract: The thermodynamic model that use the Equation of State of Peng-Robinson was used in the phase equilibrium of sugars aqueous at atmospheric pressure (where there are experimental data of equilibrium), for to afterwards to employ it at high pressures systems. Water activity experimental data of the binary systems water-sugars were collected of the literature and the binary interaction parameters of water-sugar were obtained fitting the model to these experimental binary equilibrium data. It was evaluated the capacity of the model to predict the equilibrium of the multicomponent system (comparing with available experimental values in the literature), using the binary interaction parameters fittings to the sugar-water system and considering null the binary interaction parameters of the sugarsugar system. It were evaluated also the characteristics of equilibrium of these binary systems at high pressure when it applies elevated pressure. The binary interaction parameters were obtained by the fitting of the thermodynamic model to the experimental data of the vapour - liquid equilibrium (data of water activity in binary systems). The fugacity, or sublimation pressure, of the sugars in the solid state were obtained by the solubility data, calculating the fugacity of the sugar in the saturated aqueous solution. The results indicate that the thermodynamic modeling, shawed a good correlation to the experimental data of the binary systems (at atmospheric pressure), showing an average deviation of 5% in the sugar mass fraction, equivalent to 0,17% of average deviation in water activity. For the multicomponent vapour-liquid equilibrium was observed a deviation of 7% on average. Values of sugar fugacity in the solid state were estimate and when compared to the sublimation pressure values, extrapolated from the experimental data, for glucose and xylose, showed that the values are coherent, and in the same order with the experimental data, most1y for xylose. However the modeling did not showed a good reproduction the solid-liquid equilibrium of the experimental data. The calculations using the thermodynamic modeling with at high pressure the parameters obtained at low pressure, indicate that the solubility of the saccharose decreases with the pressure and the solubility of the glucose increase with the pressure, showing that the use of the elevated pressures can become a technique for separations processes / Mestrado / Mestre em Engenharia de Alimentos

Lors du traitement de nitruration, la diffusion de l'azote dans les aciers entraîne la transformation des carbures de revenu en nitrures. Durant cette transformation, du carbone est relâché dans la matrice ferritique. L'étude expérimentale a mis en avant que cette décarburation est observable quel que soit le type de nitruration et pouvait aller jusqu'à 20 % dans le cas où la couche nitrurée ne comportait pas de couche de combinaison. Cette décarburation est induite par la réaction du carbone relâché au cours de la transformation de la cémentite avec l'hydrogène issu de la décomposition de l'ammoniac pour former une espèce carbonée, cette réaction a lieu tant qu'aucune couche de combinaison n'est présente à la surface. Cette redistribution du carbone influe sur la microstructure et les profils de contraintes résiduelles des couches nitrurées. Grâce aux résultats expérimentaux, ce phénomène a été implémenté dans le modèle de simulation de la nitruration développé au laboratoire. Cette implémentation porte essentiellement sur les conditions initiales et aux limites qui ont été obtenues en complétant les résultats expérimentaux par une simulation thermodynamique permettant de simuler des profils d'azote et de carbone proches de ceux obtenus expérimentalement. Le modèle permet également de calculer la variation de volume accompagnant la précipitation et ainsi de calculer les champs des contraintes résiduelles générées à la température de nitruration et leurs modifications lors du refroidissement. Le caractère polyphasé du matériau est pris en compte, la simulation permettant de connaître les contraintes résiduelles dans la ferrite, les précipités et les contraintes résiduelles macroscopiques grâce à un modèle micromécanique de transition d'échelles de type auto-cohérent. Cette approche multiphysique est applicable à l'ensemble des aciers au carbone allié (Cr, Mo, V). Ce modèle a été plus particulièrement appliqué à la nuance industrielle 33CrMoV12-9. L'ensemble de cette étude a permis de comprendre l'influence du carbone sur les propriétés mécaniques des couches nitrurées et de mettre au point un cycle industriel de nitruration en se basant sur les résultats expérimentaux et la simulation. / During the nitriding treatment, the diffusion of nitrogen in the steels causes the transformation of initial carbides into nitrides. During this transformation, carbon is released into the ferritic matrix. The experimental study has highlighted that the decarburization of the nitride layer occurs regardless of the type of nitriding and could reach 20% when the nitriding surface is not composed of compound layer This decarburization is induced by the reaction of the carbon released during the transformation of the cementite, with the hydrogen produced by the decomposition of ammonia to give a carburized species ?, this reaction occurs as long as any compound layer exists at the surface of the sample. This carbon redistribution has an influence on the microstructure and the residual stresses of the nitride layers. Based on experimental results, this phenomenon has been implemented in the nitriding simulation model developed in the laboratory. This implementation focuses on initial and boundary conditions obtained by complementing the experimental results with a thermodynamic simulation, to simulate nitrogen and carbon profiles close to those obtained experimentally. The model also calculates the volume change due to ? the precipitation and calculates the fields of residual stresses generated at the nitriding temperature and their evolution during cooling.. The multiphase character of the material is taken into account; the simulation allowing knowing the residual stresses in the ferrite, the precipitates and macroscopic residual stresses through a micromechanical model of scale transition like self-consistent. This multiphysics approach is applicable to all alloy carbon steels (Cr, Mo, V). This model has specifically been applied to industrial grade 33CrMoV12-9. The entire study allows understanding the influence of carbon on the mechanical properties of nitrided layers and the development of an industrial nitriding cycle based on experimental results and simulation

Ligand NOTPOEt was synthesized. Protonation constants and stability constants of Cu(II), Zn(II), Ni(II) and Ga(III) complexes were determined by potentiometric titrations. Cu(II) complex was characterized by UV-VIS spectroscopy and formation of Ga(III) complex was studied by NMR spectroscopy. The work was aimed at characterisation of the ligand with respect to potential application in biomedical imaging techniques.

Le retraitement des combustibles nucléaires usés par le procédé PUREX (Plutonium and Uranium Refining by Extraction) repose sur une étape préliminaire de dissolution qui se déroule en milieu acide nitrique concentré et chaud. Le pouvoir oxydant important des milieux de dissolution peut induire un phénomène de corrosion et fragiliser les équipements de structure qui y sont exposés, notamment les aciers inoxydables tel que l’acier 304L. Bien que l’acide nitrique, milieu réactionnel de dissolution, soit responsable des phénomènes de corrosion, la présence d’ions oxydants (Pu, Np…) peut changer la réaction cathodique et porter l’acier dans son domaine transpassif où il peut subir une corrosion intergranulaire. Par conséquent, la connaissance des ions oxydants, leur degré d’oxydation, leur comportement en solution et en corrosion est une nécessité pour mieux appréhender les phénomènes de corrosion et prédire les risques associés. Tout d’abord, une modélisation thermodynamique basée sur les capacités calorifiques et les enthalpies libres a permis d’estimer les coefficients d’activité stœchiométrique, activités de l’eau et coefficients de dissociation du mélange binaire HNO3-H2O à des températures supérieures à 25°C. Le recueil de ces données constitue une première étape dans la compréhension du comportement en corrosion des aciers inoxydables en milieu acide nitrique en présence d’ions oxydants. Ensuite, une étude expérimentale électrochimique couplée à des techniques analytiques ont permis d’appréhender le comportement électrochimique du plutonium en milieu HNO3, notamment l’oxydation du Pu(IV) en Pu(V) qui n’était pas identifiée dans ce milieu à ce jour. L’acquisition des données nécessaires à une modélisation électrochimique étant limitée par des facteurs physicochimiques (température et concentration en HNO3), une étude paramétrique à l’aide d’un analogue chimique non radioactif (Ce(IV)/Ce(III)) a été entreprise. La détermination d’analogie Pu-Ce (loi d’équivalence) a alors permis d’estimer les évolutions des constantes thermodynamiques et cinétiques du plutonium dans des conditions de température et de concentration en HNO3 supérieures aux limites physicochimiques. Enfin, l’étude du comportement en corrosion de l’acier 304L en milieu HNO3 en présence d’ions oxydants se compose de deux études complémentaires. Dans un premier temps une étude de la corrosion électrochimique a été réalisée en présence de Pu(VI) ou de Ce(IV). Cette étude révèle d’une part que le Pu(VI) ne contrôle pas le mécanisme de réduction contrairement au Ce(IV). Par conséquent, le Ce(IV) n’est pas un analogue du Pu(VI) en corrosion. D’autre part, elle montre que les produits de corrosion n’ont pas d’influence sur le mécanisme de corrosion et met en évidence un complexe Ce(IV)-Cr(III) qui inhibe la réduction du Ce(IV). Dans un second temps une étude de la corrosion chimique via des essais d’immersion a été entreprise. Elle a permis d’améliorer la connaissance du mécanisme de dissolution notamment en mettant en évidence la présence d’une couche de Cr(VI) en extrême surface qui pourrait avoir un lien avec le marquage des grains et les prémices de la corrosion intergranulaire. / The reprocessing of spent nuclear fuels by the PUREX process (Plutonium and Uranium Refining by Extraction) is based on a preliminary stage of dissolution which takes place in hot concentrated nitric acid. The high oxidizing power of dissolution media can induce corrosion phenomena and weaken the structural equipment exposed to it, especially stainless steels such as 304L steel. Although nitric acid is responsible of corrosion, the presence of oxidizing ions (Pu, Np ...) can change the cathodic reaction and bring the steel in its transpassive area where it may undergo intergranular corrosion. Therefore knowledge of oxidizing ions, their oxidation state, their behavior in solution and corrosion is necessary to lead to a better understanding and predict the corrosion associated risks.First, a thermodynamic model based on the heat capacity and the free enthalpies was developed to estimate the stoichiometric activity coefficients, water activities and dissociation coefficients of the binary mixture HNO3-H2O at temperatures above 25°C. The acquisition of these data is a first step in understanding the corrosion behavior of stainless steels in nitric acid in the presence of oxidizing ions.Then, an electrochemical experimental study coupled to analytical techniques enabled to understand the electrochemical behavior of the plutonium in HNO3 medium, in particular the oxidation of Pu(IV) to Pu(V) which was not identified in this medium. The acquisition of data needed for an electrochemical modeling was limited by physicochemical factors so a parametric study with a non-radioactive chemical analogue (Ce(IV)/Ce(III)) was undertaken. The determination of some analogies between plutonium and cerium has enabled to estimate the evolution of thermodynamic and kinetic constants of plutonium in condition of temperature and concentration in HNO3 higher than physicochemical limitations.Finally, the study of the corrosion behavior of 304L steel in HNO3 medium in the presence of oxidizing ions consists of two complementary studies. First a study of the electrochemical corrosion was carried out in the presence of Pu(VI) or Ce(IV). On one hand, it reveals that the Pu(VI) does not control the reduction mechanism (contrary to Ce(IV)). On the other hand, it shows that the corrosion products do not have any influence on the corrosion mechanism and highlights a Ce(IV)-Cr(III) complex which inhibits the reduction of Ce(IV). Secondly a study of chemical corrosion was undertaken through immersion tests. It has improved the knowledge of the dissolution mechanism including highlighting the presence of an extreme surface layer of Cr(VI) that could be related to a grain marking and a preliminary step of intergranular corrosion.

Within the context of the imminent implementation of the Pb-free soldering in Europe in 2006, this thesis addresses the gap in understanding that has emerged in the fundamental materials issues between well-understood and mature lead-containing solders and a plethora of new, Pb-free solders for which there are neither long term reliability data nor understanding of the materials behaviour and how these might be influenced by manufacture and in-service conditions. In addition, this thesis also addresses the question as to whether the solder joint size and geometry could become a reliability issue and therefore affect the implementation of the Pb-free solders in ultrafine micro joints. Thermodynamic calculations using MTDATA (developed by the National Physical Laboratory, NPL, UK) together with a thermodynamic database for solders under either equilibrium or Scheil conditions, have shown their usefulness in Pb-free solder design and processing, generating a wealth of information in respect of the temperature dependence of phase formation and composition. The predictions from MTDATA on a number of selected systems is generally in good agreement with the results from experimental work, and has assisted in the understanding of the microstructure and mechanical properties of the Pb-free solders and the implications of their interactions with a tin-lead solder. However, further critical assessment and the addition of new elements into the solder database, such as Ni and P, are required to make MTDA TA a more effective computational tool to assist the optimization of processing parameters and cost-effective production in using Pb-free solders. Molten solder can interact with the under bump metallizations (UBM) and/or board level metallizations on either side of the solder bump to form intermetallic compounds (IMCs) during solder reflow. In the modelling of the kinetics of the dissolution process of UBM into the liquid solder, the commonly used NernstBrunner (N-B) equation is found to have poor validity for these calculations for micro joints at 100 μm in diameter or less. Three bumping techniques, i.e. solder dipping (SD), solder paste stencil printing followed by reflow (SPR) and electroplating of solders and subsequent reflow (EPR), are used to investigate the interfacial interactions of molten Sn/Sn-rich solders, i.e. pure Sn, Sn-3.5Ag, and Sn-3.8AgO.7Cu, on electroless nickel immersion gold (ENIG) and copper pads at 240°C. The resultant bulk and interfacial microstructures from a variety of pad sizes, ranging from 1 mm down to 25 μm, suggest that in general the small bumps contain smaller β-Sn dendrites and Ag₃Sn IMC particles, nevertheless the interfacial IMC is thicker in the smalI bumps than in the large bumps. In addition, one and two-dimensional combined thermodynamic and kinetic models have been developed to assist the understanding of the kinetics of interdiffusion and the formation of interfacial intermetallic compounds during reflow. Both the experimental results and theoretical predictions suggest that the solder bump size and geometry can influence the as-soldered microstructure, and therefore this factor should be taken into consideration for the design of future reliable ultrafine Ph-free solder joints.

This thesis seeks to improve our understanding of the processes involved in continental collision zones, with a particular focus on subduction-exhumation. The main objective of this work has been to define the tectonometamorphic evolution of the deeply subducted Seve Nappe Complex (SNC) in the Scandinavian Caledonides. I utilize mineralogy, petrology and geochronology to constrain the P-T-t paths of the SNC rocks in Sweden. The research has focused on the high grade rocks of the SNC and resulted in the discovery of metamorphic diamonds within the gneisses in west-central Jämtland and southern Västerbotten. Microdiamonds provided evidence for the ultra-high pressure metamorphism (UHPM) and subduction of continental rocks to mantle depths. The UHPM in these rocks was confirmed by calculations of the P-T conditions. The UHPM is further recorded by eclogites and garnet pyroxenites from northern Jämtland and eclogites from Norrbotten. All these findings provide compelling evidence for regional UHPM of vast parts of the SNC (at least 400 km along the strike of this allochthonous unit). The SNC rocks followed nearly isothermal decompression paths and paragneisses have locally experienced partial melting during exhumation. Formation of the peculiar Ba- and Ti-enriched dark mica in the Tväråklumparna metasediments is related to the latter stage. In-situ monazite dating of the diamond-bearing gneisses from west-central Jämtland supports previous geochronological data inferring that the peak of metamorphism is probably Middle Ordovician and was followed by Early Silurian partial melting. The exact timing of the UHPM here still remains to be resolved. The Lu-Hf garnet and U-Pb zircon dating of eclogite and gneiss from northern Jämtland confirms the Middle Ordovician age of the UHP-HP metamorphism of the SNC rocks. The chemical dating of monazite from the Marsfjället gneiss suggests an earlier UHP history of the Seve rocks in southern Västerbotten as a post-UHP uplift is dated to ca. 470 Ma. Based on the P-T-t data obtained in this thesis, particularly on the evidence for Middle Ordovician UHPM and subsequent Silurian exhumation, a new tectonic model for the Scandinavian Caledonides has been proposed. The outcomes of this thesis therefore improve our understanding of the tectonometamorphic history of the Caledonides.

The first project in this work used classical molecular dynamics to study the ice recrystallization inhibition potential of a series of carbohydrates and alcochols, using the hydration index, partial molar volumes and isothermal compressibilities as parameters for measuring their cryogenic efficacy. Unfortunately, after 8 months of testing, this work demonstrates that the accuracy and precision of the density extracted from simulations is not sufficient in providing accurate partial molar volumes. As a result, this work clearly demonstrates that current classical molecular dynamics technology cannot probe the volumetric properties of interest with sufficient accuracy to aid in the research and development of novel cryoprotectants.The second project in this work used molecular dynamics simulations to evaluate the Gibbs free energy change of substituting CO2 in sI clathrate hydrates by N2,CH4, SO2 and H2S flue gas impurities under conditions proposed for CO2 capture (273 K, 10 bar). Our results demonstrate that CO2 substitutions by N2 in the small sI cages were thermodynamically favored. This substitution is problematic in terms of efficient CO2 capture, since the small cages make up 25% of the sI clathrate cages, therefore a significant amount of energy could be spent on removing N2 from the flue gas rather than CO2. The thermodynamics of CO2 substitution by CH4, SO2 and H2S in sI clathrate hydrates was also examined. The substitution of CO2 by these gases in both the small and large cages were determined to be favorable. This suggests that these gases may also disrupt the CO2 capture by sI clathrate hydrates if they are present in large concentrations in the combustion flue stream. Similar substitution thermodynamics at 200 K and 10 bar were also studied. With one exception, we found that the substitution free energies do not significantly change and do not alter the sign of thermodynamics. Thus, using a lower capture temperature does not significantly change the substitution free energies and their implications for CO2 capture by sI clathrate hydrates.