No / We report the structure of the electrical double layer, determined from molecular dynamics simulations, for a range of saline solutions (NaCl, KCl, MgCl2 and CaCl2) at both 0.16 and 0.60 mol kg(-1) on different facets of the gold and silver aqueous interfaces. We consider the Au/Ag(111), native Au/Ag(100) and reconstructed Au(100)(5×1) facets. For a given combination of metallic surface and facet, some variations in density profile are apparent across the different cations in solution, with the corresponding chloride counterion profiles remaining broadly invariant. All density profiles at the higher concentration are predicted to be very similar to their low-concentration counterparts. We find that each electrolyte responds differently to the different metallic surface and facets, particularly those of the divalent metal ions. Our findings reveal marked differences in density profiles between facets for a given metallic interface for both Mg(2+) and Ca(2+), with Na(+) and K(+) showing much less distinction. Mg(2+) was the only ion for which we find evidence of materials-dependent differences in interfacial solution structuring between the Ag and Au. / Veski, Air Force Office for Scientific Research grant #FA9550-12-1-0226

Advances in molecular-simulation methods allow for ever larger systems of particles to be studied and on longer timescales. Calculations are reaching such a scale that they can be used to address a vast range of key questions across chemistry, physics, and engineering. In this work, molecular dynamics and Monte Carlo simulations are employed to address two key areas: the structure and dynamics of simple aqueous ionic salt solutions at high concentrations; and the structure, dynamics, and phase behaviour of dipolar fluids (such as colloidal ferrofluids). The first part of the work begins with a study of the structure and dynamics in metastable, supersaturated, aqueous solutions of potassium chloride, and the possible relevance of these to the phenomenon of non-photochemical laser-induced nucleation (NPLIN). It is thought that the potassium and chloride ions form long-lived, amorphous clusters that may, under the influence of nanosecond laser pulses, undergo structural reorganisation to form post-critical crystal nuclei. It is found that spontaneous nucleation does not occur on the simulation timescale, but that amorphous clusters do form with cluster lifetimes comparable to those of the shortest laser pulses that can be used in NPLIN ( 100 picoseconds). Next, an alternative scenario for NPLIN involving rapid laser heating of impurity particles is examined by simulating heated carbon nanoparticles in saturated aqueous solutions of sodium chloride. The concentration at which an aqueous sodium chloride solution first crystallises on the simulation timescale is determined. A spherical carbon impurity is then added to a system with concentration close to, but lower than, the concentration at which crystallisation occurs on the simulation timescale. The effects that adding, and heating, this impurity has on the structure of this near-crystallising system are then observed. The second part of the work discusses model dipolar fluids, of direct relevance to colloidal ferrofluids (suspensions of magnetised nanoparticles in simple carrier liquids). The two-body, dipole-dipole interaction is long-ranged and anisotropic, and it is computationally expensive to handle in molecular simulations. Here a new method is proposed that relies on a formal mapping between the partition function of a dipolar fluid and that of a hypothetical fluid with many-body, short-ranged, isotropic interactions. Only the leading-order two-body interactions (akin to the van der Waals attraction) and three-body interactions (corresponding to the Axilrod-Teller potential) are retained. It is shown that this simple model is sufficient to reproduce the characteristic particle chaining and the associated disappearance of the vapour-liquid phase transition of dipolar fluids. Finally, the dynamical response of ferrofluids to oscillating magnetic fields (the dynamic magnetic susceptibility [DMS]) is studied. The DMS of ferrofluids, predicted by a new theory that takes into account the leading-order effects of dipole-dipole interactions, are critically compared to those found using Brownian-dynamics simulations of monodisperse systems of dipolar particles. This new theory is found to provide more accurate predictions of the DMS than previous theories, with the DMS predicted to a high degree of accuracy for systems with dipolar coupling strength in the experimentally achievable region.

Das Projekt „Collaboration-Grid für Virtuelle Unternehmen“ (VU-Grid) ist ein Forschungsverbundprojekt, an dem die Fakultät Informatik der Technischen Universität Dresden sowie der mittelständische IT-Dienstleister SALT Solutions GmbH beteiligt sind. Das Vorhaben wird von der Sächsischen Aufbaubank gefördert. Ziel des Forschungsvorhabens ist die prototypische Entwicklung einer Integrationsplattform (Collaboration-Grid) für die Unterstützung der veränderlichen, unternehmensübergreifenden Geschäftsprozesse im Umfeld eines IT-Dienstleisters am Beispiel der SALT Solutions GmbH. Theoretische Basis der Realisierung ist dabei das Konzept des Virtuellen Informationssystems, das im Rahmen des Dissertationsvorhabens von D. Neumann erarbeitet wurde.

Das Projekt „Collaboration-Grid für Virtuelle Unternehmen“ (VU-Grid) ist ein Forschungsverbundprojekt, an dem die Fakultät Informatik der Technischen Universität Dresden sowie der mittelständische IT-Dienstleister SALT Solutions GmbH beteiligt sind. Das Vorhaben wird von der Sächsischen Aufbaubank gefördert. Ziel des Forschungsvorhabens ist die prototypische Entwicklung einer Integrationsplattform (Collaboration-Grid) für die Unterstützung der veränderlichen, unternehmensübergreifenden Geschäftsprozesse im Umfeld eines IT-Dienstleisters am Beispiel der SALT Solutions GmbH. Theoretische Basis der Realisierung ist dabei das Konzept des Virtuellen Informationssystems, das im Rahmen des Dissertationsvorhabens von D. Neumann erarbeitet wurde.

Made available in DSpace on 2017-07-10T19:25:09Z (GMT). No. of bitstreams: 1 vanderleia.pdf: 906737 bytes, checksum: 213629aa00849fbaa6d109c60133bf7f (MD5) Previous issue date: 2012-02-02 / The bean (Phaseolus vulgaris L) is a typical leguminous in Brazil. Its consumption should be encouraged due to the benefits of its quantity of protein, fiber, folic acid and minerals such as iron and potassium. However, its long cooking process consequently makes many consumers often avoid eating this product, which results in a decrease of production and demand. The possibility of offering a product previously processed, as well as keeping its technological characteristics with a short time of preparation, is an option for consumers who look for convenience and quality. Techniques as soaking and bleaching beans are presented as options for grains preprocessing. Thus, this study aim was investigating the effects of grains preprocessing with blanching and soaking applied under salt solutions according to the carioca bean quality parameters in order to obtain a dry product with a short cooking time. The maintenance of technological quality characteristics of in natura grain through the use of experimental design techniques was also considered. A Plackett and Burman experimental design was applied to evaluate the effects of nine factors in preprocessing: soaking time, soaking in sodium chloride concentration, soaking in sodium bicarbonate concentration, soaking temperature, blanching temperature, blanching time, concentration of sodium chloride under soaking, concentration of sodium bicarbonate under soaking and drying temperature based on responses as cooking time, splitting percentage and color difference (Δe*) of preprocessed grains related to control. In the optimization, a DCCR 23 plan was used only with factors of the maceration step which mainly contributed to reduce cooking time. The increased concentration of sodium bicarbonate used in the soaking of beans significantly reduced the cooking time, but it increased the damage level in the product and darkened the bean integument. This contributed to greater differences in color of preprocessed grains when compared to the control treatment. The factors that most influenced the studied answers were soaking time, concentration of sodium bicarbonate under soaking and drying temperature. The desirability technique allowed the answers simultaneous evaluation and the definition of optimal conditions for this process. This process presented overall desirability of 56.53%, thus the factors levels were defined according to the following conditions: soaking time of 13.1 hours, concentration of NaHCO3 under soaking solution of 2.3% and drying temperature of 50 °C. Under these conditions, it is possible to reduce the cooking time by 58% with an index of damaged grains near 9.13% and color difference of 8.39. The obtained results may contribute to future researches that aim at developing bean preprocessing quality in a shorter cooking time. / O feijão (Phaseolus vulgaris L) é uma leguminosa típica para o brasileiro. O consumo do grão deve ser incentivado devido aos benefícios relativos ao seu conteúdo de proteínas, fibras, ácido fólico e minerais, como o ferro e o potássio. Porém, o tempo necessário para o processo de cozimento dos grãos de feijão, faz que muitos consumidores deixem de utilizar frequentemente o produto, implicando diminuição do consumo e da demanda por produção. A possibilidade de oferecer um produto previamente processado, mantendo-se as características tecnológicas com o tempo de preparo reduzido é uma opção para consumidores que buscam conveniência e qualidade. Técnicas como a maceração e o branqueamento do feijão, apresentam-se como opções para pré-processamento dos grãos. O objetivo deste trabalho foi verificar os efeitos do pré-processamento dos grãos com as operações de branqueamento e maceração em soluções salinas nos parâmetros de qualidade do feijão carioca, visando obter um produto seco com tempo de cozimento reduzido e manutenção das características de qualidade tecnológica do grão in natura, utilizando técnicas de planejamento experimental. Foi utilizado um planejamento tipo Plackett e Burman que avaliou os efeitos de nove fatores no pré-processamento: tempo de maceração, concentração de cloreto de sódio na maceração, concentração de bicarbonato de sódio na maceração, temperatura da solução de maceração, temperatura de branqueamento, tempo de branqueamento, concentração de cloreto de sódio no branqueamento, concentração de bicarbonato de sódio no branqueamento e temperatura de secagem, sob as respostas tempo de cozimento, porcentagem de grãos danificados e diferença de cor (Δe*) dos grãos pré-processados em relação ao controle. Na otimização foi utilizado um planejamento DCCR 23, apenas com os fatores da etapa de maceração e que contribuíram principalmente para redução do tempo de cozimento dos grãos. O aumento da concentração de bicarbonato de sódio utilizado na maceração do feijão reduziu consideravelmente o tempo de cozimento, porém, aumentou o nível de dano no produto e escureceu o tegumento do feijão contribuindo para maiores diferenças de cor dos grãos pré-processados em relação ao controle. Os fatores que mais influenciaram nas respostas avaliadas foram o tempo de maceração, a concentração de bicarbonato de sódio na maceração e a temperatura de secagem. A técnica de desejabilidade permitiu a avaliação simultânea das respostas e as condições ótimas para o processo foram definidas. O processo apresentou desejabilidade global de 56,53%, sendo os níveis dos fatores definidos na seguinte condição: tempo de maceração de 13,1 horas, concentração de NaHCO3 na solução de maceração igual a 2,3% e temperatura de secagem igual a 50 ºC. Nestas condições é possível reduzir o tempo de cozimento em aproximadamente 58%, com índice de grãos danificados próximo de 9,13% e diferença de cor de 8,39. Os resultados obtidos poderão contribuir para pesquisas que visem o desenvolvimento de tecnologias de pré-processamento do feijão com tempo de cozimento reduzido.

Made available in DSpace on 2017-05-12T14:48:32Z (GMT). No. of bitstreams: 1 vanderleia.pdf: 906737 bytes, checksum: 213629aa00849fbaa6d109c60133bf7f (MD5) Previous issue date: 2012-02-02 / The bean (Phaseolus vulgaris L) is a typical leguminous in Brazil. Its consumption should be encouraged due to the benefits of its quantity of protein, fiber, folic acid and minerals such as iron and potassium. However, its long cooking process consequently makes many consumers often avoid eating this product, which results in a decrease of production and demand. The possibility of offering a product previously processed, as well as keeping its technological characteristics with a short time of preparation, is an option for consumers who look for convenience and quality. Techniques as soaking and bleaching beans are presented as options for grains preprocessing. Thus, this study aim was investigating the effects of grains preprocessing with blanching and soaking applied under salt solutions according to the carioca bean quality parameters in order to obtain a dry product with a short cooking time. The maintenance of technological quality characteristics of in natura grain through the use of experimental design techniques was also considered. A Plackett and Burman experimental design was applied to evaluate the effects of nine factors in preprocessing: soaking time, soaking in sodium chloride concentration, soaking in sodium bicarbonate concentration, soaking temperature, blanching temperature, blanching time, concentration of sodium chloride under soaking, concentration of sodium bicarbonate under soaking and drying temperature based on responses as cooking time, splitting percentage and color difference (Δe*) of preprocessed grains related to control. In the optimization, a DCCR 23 plan was used only with factors of the maceration step which mainly contributed to reduce cooking time. The increased concentration of sodium bicarbonate used in the soaking of beans significantly reduced the cooking time, but it increased the damage level in the product and darkened the bean integument. This contributed to greater differences in color of preprocessed grains when compared to the control treatment. The factors that most influenced the studied answers were soaking time, concentration of sodium bicarbonate under soaking and drying temperature. The desirability technique allowed the answers simultaneous evaluation and the definition of optimal conditions for this process. This process presented overall desirability of 56.53%, thus the factors levels were defined according to the following conditions: soaking time of 13.1 hours, concentration of NaHCO3 under soaking solution of 2.3% and drying temperature of 50 °C. Under these conditions, it is possible to reduce the cooking time by 58% with an index of damaged grains near 9.13% and color difference of 8.39. The obtained results may contribute to future researches that aim at developing bean preprocessing quality in a shorter cooking time. / O feijão (Phaseolus vulgaris L) é uma leguminosa típica para o brasileiro. O consumo do grão deve ser incentivado devido aos benefícios relativos ao seu conteúdo de proteínas, fibras, ácido fólico e minerais, como o ferro e o potássio. Porém, o tempo necessário para o processo de cozimento dos grãos de feijão, faz que muitos consumidores deixem de utilizar frequentemente o produto, implicando diminuição do consumo e da demanda por produção. A possibilidade de oferecer um produto previamente processado, mantendo-se as características tecnológicas com o tempo de preparo reduzido é uma opção para consumidores que buscam conveniência e qualidade. Técnicas como a maceração e o branqueamento do feijão, apresentam-se como opções para pré-processamento dos grãos. O objetivo deste trabalho foi verificar os efeitos do pré-processamento dos grãos com as operações de branqueamento e maceração em soluções salinas nos parâmetros de qualidade do feijão carioca, visando obter um produto seco com tempo de cozimento reduzido e manutenção das características de qualidade tecnológica do grão in natura, utilizando técnicas de planejamento experimental. Foi utilizado um planejamento tipo Plackett e Burman que avaliou os efeitos de nove fatores no pré-processamento: tempo de maceração, concentração de cloreto de sódio na maceração, concentração de bicarbonato de sódio na maceração, temperatura da solução de maceração, temperatura de branqueamento, tempo de branqueamento, concentração de cloreto de sódio no branqueamento, concentração de bicarbonato de sódio no branqueamento e temperatura de secagem, sob as respostas tempo de cozimento, porcentagem de grãos danificados e diferença de cor (Δe*) dos grãos pré-processados em relação ao controle. Na otimização foi utilizado um planejamento DCCR 23, apenas com os fatores da etapa de maceração e que contribuíram principalmente para redução do tempo de cozimento dos grãos. O aumento da concentração de bicarbonato de sódio utilizado na maceração do feijão reduziu consideravelmente o tempo de cozimento, porém, aumentou o nível de dano no produto e escureceu o tegumento do feijão contribuindo para maiores diferenças de cor dos grãos pré-processados em relação ao controle. Os fatores que mais influenciaram nas respostas avaliadas foram o tempo de maceração, a concentração de bicarbonato de sódio na maceração e a temperatura de secagem. A técnica de desejabilidade permitiu a avaliação simultânea das respostas e as condições ótimas para o processo foram definidas. O processo apresentou desejabilidade global de 56,53%, sendo os níveis dos fatores definidos na seguinte condição: tempo de maceração de 13,1 horas, concentração de NaHCO3 na solução de maceração igual a 2,3% e temperatura de secagem igual a 50 ºC. Nestas condições é possível reduzir o tempo de cozimento em aproximadamente 58%, com índice de grãos danificados próximo de 9,13% e diferença de cor de 8,39. Os resultados obtidos poderão contribuir para pesquisas que visem o desenvolvimento de tecnologias de pré-processamento do feijão com tempo de cozimento reduzido.

The role and behavior of fluids in hydrothermal and magmatic environments have been studied. Experimental studies have been carried out to determine fluid properties, in natural environments and in both synthetic and natural fluid and melt inclusions. One of these studies dealt with the effect of composition on the critical P-T-X properties of aqueous salt solutions approximated by the H₂O-NaCl-KCl-CaCl₂ system. The results indicate a systematic variation in critical properties as a function of composition over the range of P-T-X studied. A technique for analyzing individual H₂O-CO₂ inclusions using Raman spectroscopy has also been developed. The resulting empirical equation relating Raman intensities and composition is valid for compositions ≤50mol% CO₂. The technique has been applied to H₂O-CO₂ inclusions from the Butte, MT Porphyry Cu-Mo deposit and the results agree with compositions estimated from microthermometric and petrographic observations. The aim of another study was to study water loss from melt inclusions during laboratory heating. Melt inclusions had lost insignificant amounts of water when held at experimental conditions (800°C, 1 kbar) for ≤24 hours. However, significant water loss was observed for longer duration experiments. Ocelli, which are globular bodies of felsic minerals are interpreted as products of magmatic melt immiscibility. As such, the carbonate aggregates in Cretaceous lamprophyres from Hungary with similar petrographic characteristics have also generally been interpreted to be products of magmatic immiscibility. Petrographic and geochemic studies have shown three three distinct genetic groups for these aggregates, none of which were consistent with a magmatic origin. / Ph. D.

On désigne habituellement par retrait-gonflement des sols argileux les variations de volume qu’un massif d’argile peut subir sous l’effet des variations de la pression interstitielle négative (succion) de l’eau, lors d’une humidification ou d’un séchage. L’objectif de ce travail est de compléter les connaissances expérimentales sur le comportement hydromécanique des sols gonflants rencontrés dans les travaux de génie civil, de géotechnique et de géotechnique de l’environnement afin de mieux en tenir compte dans les modèles de calcul. De nombreux travaux ont montré l'intérêt de réaliser des essais œdométriques pour caractériser le potentiel et la cinétique de gonflement des sols. Ils ont révélé également l’influence de l’humidification ou du séchage sur le gonflement ou le retrait, avec des pertes ou des augmentations de rigidité des éprouvettes. En revanche, l’influence de plusieurs cycles de séchage/humidification sur le comportement mécanique n’a été que très rarement analysée. Cette thèse rapporte les résultats d’études expérimentales effectuées à l’œdomètre avec imposition de succion par la méthode osmotique sur des matériaux gonflants compactés lâches et naturels denses. Plusieurs cycles de séchage/humidification ont été appliqués sur ces matériaux sous trois faibles charges mécaniques constantes. Pendant ces cycles, les éprouvettes manifestent un retrait cumulé pour le sol lâche et un gonflement cumulé pour le sol dense. Les résultats montrent que dans les deux cas, les déformations volumiques convergent vers un état d’équilibre où le sol présente un comportement réversible. A la fin des cycles de succion, un cycle de chargement/déchargement a été effectué sous les succions constantes. Les valeurs de la pression de préconsolidation p0(s), de l’indice de compression vierge [lambda(s]] et de l’indice de compression élastique [kappa] dépendent directement des chemins de contrainte suivis. L’ensemble des résultats expérimentaux permet de déterminer les surfaces de charge : la limite de séparation de micro/macro (Lm/M) ; la surface de chargement-effondrement (LC : Loading Collapse du modèle BBM) et la surface de comportement saturé (SCS). La succion limite entre la micro- et la macrostructure (Lm/M) dépend parfaitement de la structure interne et du diamètre qui délimite les deux familles de pores. L’évolution de la pression de préconsolidation en fonction de la succion imposée est présentée par la surface LC. Les courbes de compressibilité sous différentes succions convergent vers la courbe correspondant à l’état saturé sous de fortes contraintes appliquées. La pression à partir de laquelle, le sol continue son chemin sur la courbe du comportement normalement consolidé est appelée la pression de saturation (Psat). Plus la succion imposée est élevée, plus la charge nécessaire pour atteindre cette pression de saturation est importante. La surface SCS présente la variation de la pression de saturation en fonction de la succion imposée. Nous pouvons considérer que les surfaces de charge SCS et LC sont uniques pour les sols denses cependant elles se superposent à la fin des cycles de succion pour les sols lâches. Les cycles hydriques augmentent aussi la limite (Lm/M) entre la micro- et la macrostructure pour les deux sols / We usually define the swelling-shrinkage of the swelling soils by the volume variation of a clayey layer exposed to the negative water pore pressure (suction) variations during the wetting and drying periods. In this research, we try to complete our experimental knowledge on the hydromechanical behaviour of the swelling soils used in civil engineering, geotechnical engineering and geoenvironmental engineering, to better modelize these soils in our numerical calculations. Several authors have used the oedometer tests to characterize the capacity and the process of the soil expansion. They have also studied the influence of the wetting and drying on the soil swelling or shrinkage which can decrease or increase the soil rigidity. However, the influence of several hydraulic cycles on the mechanical behaviour has been rarely studied. This thesis presents an experimental study performed on compacted loose and natural dense expansive soils using osmotic oedometers. Several successive cycles were applied under three different low constant vertical net stresses. The loose soil presents a significant shrinkage accumulation while the dense one produces the swelling accumulation during the suction cycles. The suction cycles induced an equilibrium stage which indicates an elastic behaviour of the samples. At the end of suction cycles, a loading/unloading test was performed at the constant suctions for both materials. The mechanical parameters, i.e. the virgin compression index [lambda(s)], the apparent preconsolidation stress p0(s) and the elastic compression index values [kappa] ?are completely dependent on the followed stress paths. The whole experimental results made it possible to define the yielding surfaces: suction limit between micro and macrostructure (Lm/M), loading collapse (LC) and saturation curve (SCS). The suction limit (Lm/M) depends completely to the soil fabrics and to the diameter separating the micro- and macrostructure. The preconsolidation stress variation with suction is represented by the LC surface. The compression curves at different imposed suctions converge towards the saturated state for the high applied vertical stresses. We consider the saturation pressure (Psat) as the necessary pressure to reach the saturated state for an imposed suction. The higher the suction, the higher the saturation pressure. The yielding surface representing this pressure as a function of suction is called the saturation curve (SCS). Generally we can state that the suction cycles unified the LC and SC surfaces and increased the (Lm/M) up to a higher value