Nesse trabalho foi proposto investigar a estabilidade de fases do sistema zircônia-escândia (ScSZ) por meio do estudo termodinâmico de nanopartículas, na faixa de 0 a 20% em mol de Sc2O3, e a partir da introdução de um segundo aditivo (Dy2O3 e Nb2O5) ao ZrO2 contendo 10% em mol de Sc2O3 (10ScSZ). A estabilidade de fases do ScSZ foi avaliada com base em dados termodinâmicos determinados pelas técnicas de microcalorimetria de adsorção de água e calorimetria de dissolução à alta temperatura. As soluções sólidas foram sintetizadas pelo método de coprecipitação de hidróxidos. Dados termodinâmicos foram determinados para as formas polimórficas encontradas (monoclínica, tetragonal, cúbica, romboédrica β e γ) por difração de raios X no ScSZ. Esse trabalho resultou no diagrama de fases em nanoescala de tamanho de partícula-composição. Os efeitos produzidos pela introdução de aditivos na matriz de 10ScSZ foram investigados visando obter a possível estabilização da estrutura cúbica (c) e a supressão da transformação de fase c-β, característica do sistema binário. As composições foram sintetizadas por coprecipitação de hidróxidos e por reações em estado sólido para fins comparativos. Os materiais foram sinterizados convencionalmente e por sinterização assistida por campo elétrico. A estabilização completa da fase cúbica ocorreu a partir de teores molares de 1% de Dy2O3 e 0,5% de Nb2O5. O menor teor de Nb2O5 necessário para a estabilização da fase foi atribuído à provável formação da fase líquida durante a sinterização e ao menor tamanho do íon Nb5+. Os resultados de difratometria de raios X em alta temperatura e análise térmica mostraram que houve supressão da transição c-β. As amostras contendo 0,5% mol de Nb2O5 apresentaram valores de condutividade iônica similares aos do 10ScSZ sem aditivos em uma ampla faixa de temperatura com elevada estabilidade em um período de 170 h a 600 °C. / In this work, the phase stability of scandia-zirconia (ScSZ) system was investigated by the thermodynamic study of nanoparticles, within the range of 0 to 20 mol% Sc2O3, and by codoping of ZrO2-10 mol% Sc2O3 (10ScSZ) with Dy2O3 and Nb2O5. The phase stability of ScSZ was evaluated based on thermodynamic data collected by water adsorption microcalorimetry and high temperature oxide melt solution. Nanostructured zirconia-scandia solid solutions were synthesized by coprecipitaion method. Thermodynamic data were determined for ScSZ polymorphs (monoclinic, tetragonal, cubic, rhombohedral β and γ) found by X-ray diffraction. This systemic work resulted in an unprecedented phase diagram at the nanoscale of particle size-composition. The effects of additives on 10ScSZ were investigated aiming to stabilize the cubic (c) structure at room temperature and to suppress the characteristic cubic-rhombohedral β phase transformation. Compositions were prepared by coprecipitation and solid state reaction. Materials were sintered by conventional and spark plasma sintering. Full stabilization of the cubic phase was attained by 1 mol% Dy2O3 and 0.5 mol% Nb2O5 additions. The smallest Nb2O5 content required for cubic phase stabilization was attributed to liquid phase formation during sintering and to small ionic radius of Nb5+. Results of high temperature X-ray diffraction and thermal analysis show suppression of the c-β transformation. Samples containing 0.5 mol% Nb2O5 show total ionic conductivity similar to 10ScSZ without additives within a broad temperature range with high stability during 170 h at 600 °C.

Os motores a jato são componentes importantes e complexos de engenharia cuja eficiência e desempenho estão diretamente ligados à temperatura de operação na câmara de combustão, ou seja, quanto maior a temperatura dos gases nesta região, maior a eficiência global do processo, resultando em economia de combustível e maior potência. A superliga aeronáutica a base de níquel é o material atualmente utilizado nestes componentes mais críticos das turbinas, mas o seu desenvolvimento está chegando cada vez mais próximo do limite e, por isso, existe uma demanda de materiais que possam substituí-las. Os materiais constituídos de microestruturas multifásicas, como as ligas MR-Si-B (MR= Metal Refratário) apresentam potencial para a substituição das superligas nestas aplicações. Estudos recentes no sistema Ta-Si-B identificaram a existência de uma fase ainda não catalogada, denominada φ. No entanto, a sua estrutura cristalina permanece indefinida devido à dificuldade em se obter uma amostra com grande fração volumétrica de φ. A substituição do silício por germânio nesse sistema pode aumentar o campo de estabilidade de φ possibilitando assim, a obtenção de uma amostra através da qual a estrutura cristalina dessa fase possa ser determinada. Entretanto, para o estudo do ternário Ta-Ge-B, é importante o conhecimento dos binários que o compõem (Ta-Ge, Ta-B, Ge-B) e não foi encontrada na literatura uma proposta para o diagrama binário Ta-Ge nem informações suficientes para construí-lo. Este trabalho, portanto, tem como objetivo propor um diagrama de fases para o sistema Ta-Ge, e investigar a possível existência da fase φ no sistema ternário Ta-Ge-B. Para isto foram confeccionadas amostras, a partir de matérias primas (tântalo, germânio e boro) de alta pureza, em toda a extensão composicional do sistema Ta-Ge e na região rica em tântalo do sistema Ta-Ge-B. As amostras, em seu estado bruto de fusão bem como após tratamentos térmicos, foram caracterizadas por microscopia eletrônica de varredura (MEV), microanálise eletrônica por energia dispersiva (EDS) e difratometria de raios X (DRX). Com os resultados obtidos neste trabalho foi proposto um diagrama para o sistema Ta-Ge. A temperatura do eutético na região rica em Ta (2444°C) foi medida através de pirometria ótica. Devido a dificuldades encontradas em fundir a arco amostras com altos teores de Ge, novos experimentos serão necessários para melhor determinar esta região do diagrama de fases. Os resultados obtidos nas amostras ternárias sugerem que a fase ternária φ é estável no sistema Ta-Ge-B. / Jet engines are important and complex engineering devices, whose efficiency and performance are directly related to the operating temperature of the combustion chamber, the higher the gas temperature in this region, the greater the overall efficiency of the process, resulting in economy of fuel and more efficiency. Ni-based superalloys are currently used in the most critical jet engine components. Their development is coming close to a temperature limit and, therefore, there is a demand for new materials to replace them. Materials with multiphase microstructures, such as MR-Si-B alloys (MR = Refractory Metal), have a good potential for substituting superalloys in these applications. Recent studies in the Ta-Si-B system shows the stability of a phase φ whose crystal structure remains unknown due to the difficulty in obtaining a sample with large volume fraction of φ. The substitution of silicon by germanium in this system may increase the stability of φ, enabling the production of a sample by which the crystal structure of this phase can be determined. The study of the Ta-Ge-B ternary system requires the knowledge of the phase relations on its limiting binaries. However, there is no Ta-Ge phase diagram available in the literature, nor enough experimental information to propose one. Therefore, the present work aims at the experimental investigation of the phase relations on the Ta-Ge system, and of the stability of phase φ on the Ta-rich region of the Ta-Ge-B ternary system. Samples were prepared by arc melting high purity materials (tantalum, germanium and boron) under Ti-gettered argon. Their microstructures, in the as cast state as well as after heat treatments were characterized by scanning electron microscopy (SEM), energy dispersive electron probe microanalysis (EDS) and X-ray diffraction (XRD). A Ta-Ge binary phase diagram is proposed based on the results of the present work. The temperature of the Ta-rich eutetic (2444°C) was measured by optical pirometry. Due to the difficulty of arc melting samples with high Germanium contents, further investigation is still necessary for this region of the phase diagram. The results for the ternary samples suggest the stability of the φ phase in the Ta-Ge-B system.

In order to understand some of the superconducting mechanisms involving external electric fields at nanometric scales, a Lorentz-covariant extension of the phenomenological Ginzburg-Landau theory has been developed by analogy with the Higgs model of particle physics. Among the specific properties of this model, it has been shown that the phase diagram of some particular geometry submitted to crossed electric and magnetic fields in a stationary situation provides a criterion involving the applied electric field, which could discriminate between the usual Ginzburg-Landau theory and its covariant extension. A sub-microscopic device has been manufactured using microelectronics lithography techniques and was used to perform transport measurements at very low temperatures. However, the experimental measurements of the phase diagram do not reproduce the expectations based whether on the usual or the extended model, suggesting a screening of the electric field by some mechanism which is not accounted for by these phenomenological approaches. A microscopic approach has therefore been developed to extend the s-wave channel of the BCS theory in a relativistic framework, using the functional integral formalism of Finite Temperature Field Theory. In particular, the effective action related to the Ginzburg-Landau free energy was obtained up to second order in the fluctuations of the electromagnetic field and of the superconducting condensate density. This allowed for the identification of the electric and magnetic penetration lengths, inclusive of their dependences on temperature and the chemical potential, which fully explain the experimental results. Several analytic expressions have also been provided for the effective potential in the full range of temperatures between 0 K and the critical temperature, among which the Ginzburg-Landau potential was shown to reproduce this effective potential within the limited range of temperatures where it is expected to be valid.

The Fe-C-Cr-Mn-Ni-O system is of fundamental importance when describing the influence of oxygen on high alloyed steels. Both solid and liquid phases are of great interest: The solid phases regarding oxidation processes like the formation of oxide layers, inner oxidation, sintering processes and high temperature corrosion. The liquid phase is of interest concerning the interaction between steel and its slag in a metallurgical context. In this thesis the thermodynamic properties of this system is described using the Calphad technique. The main idea of the Calphad technique is to describe the Gibbs energy of all phases in the system as a function of temperature, pressure and composition using appropriate thermodynamic models. When thermodynamic descriptions of all phases taking part in the system are modelled and described in a database, the equilibrium state could be calculated with a software that minimizes the total Gibbs energy. Models within the compound energy formalism are used for all solution phases, among them the ionic two-sublattice liquid model, to describe both the metallic and oxide melts. All simple spinels (Cr3O4, FeCr2O4, Fe3O4, FeMn2O4, Mn3O4, MnCr2O4, NiCr2O4, NiFe2O4, NiMn2O4) within this system are described using a four-sublattice model. In this thesis several binary and ternary systems have been assessed or partly reassessed. The Fe-C-Cr-Mn-Ni-O database achieved can be used with an appropriate thermodynamic software to calculate thermodynamic properties, equilibrium states and phase diagrams. In general, the agreement between calculated and experimental values is good. / QC 20100723

In this study, pharmaceutical-grade and food-grade linker-based lecithin self-emulsifying delivery systems (SEDS) were developed with a combination of lipophilic and hydrophilic linkers. These additives at suggested concentrations are safe for pharmaceutical and food applications. The ratio of surfactant lecithin and linkers in these systems was optimized to develop surfactant in oil preconcentrates. The preconcentrates containing different surfactant concentrations and oil were diluted with fed state simulated intestinal fluid to produce pseudo-ternary phase diagrams and to identify the formulations that produced self-emulsifying or self-microemulsifying delivery systems. Optimal SEDS preconcentrates were evaluated using a dialyzer model to simulate intestinal uptake. An uptake of 39.6 mg/cm2 for the pharmaceutical-grade SEDS was obtained within 72 minutes, which promises substantial improvement in the bioavailability of hydrophobic actives. The optimal uptake of 12.2 mg/cm2 for food-grade SEDS suggests enhancement in the bioavailability of omega-3 fatty acids.

Metallic fuels have an important role to play in "fast breeder" Gen-IV type nuclear reactors, and U-Pu-Zr is one of the prototypical systems. Because of the variability in fuel chemistry during burn-up, it is important to understand the effect of minor actinides and fission products on phase stability. Within this framework, we present a study on phase equilibria in the binary Np-Zr alloy system on which little work has been published. To resolve the contradictory reports on the ordering/ clustering trends of the bcc phase, a thermodynamic study is performed using the CALPHAD method. The calculated Np-Zr phase diagram is consistent with two sets of data: formation enthalpies of the bcc phase that are calculated with ab initio KKR-ASA-CPA electronic-structure method and lattice stabilities of solution phases obtained from first-principles technique. Another important feature in the Np-Zr alloy system is the non-stoichiometric delta-NpZr2 phase that forms in a hexagonal C32 structure similar to the delta-phase in the U-Zr system and the w-phase in pure Zr. An increase in the homogeneity range of the delta-phase when going from Pu to Np and to U is attributed to a lowering of its heat of formation that is caused by an increase in d-band occupation. Two different possibilities for the stability of the delta- and w- phases have been proposed in the present work. Additionally, calculated changes in enthalpy versus temperature are plotted for two alloy compositions of the Np-Zr system to guide future experimental work in resolving important issues in this system. Finally, an ab initio study, implemented with the L(S)DA U formalism, is performed for pure Np that reveals a transition from a non-magnetic to a magnetic state at a critical U parameter.

Zielstellung dieser Arbeit ist die experimentelle Aufklärung und computergestützte Simulation von Phasengleichgewichten im binären System Kupfer-Sauerstoff und im quaternären System Eisen-Samarium-Zirkonium-Molybdän. Damit wird ein Beitrag zu Phasendiagrammen in den Stoffgruppen der keramischen Materialien und der Seltenerd-basierenden magnetischen Materialien geleistet. Zur Charakterisierung der einzelnen Systeme und ihrer Subsysteme nach der CALPHAD-Methode werden die Stöchiometrie der einzelnen Phasen, ihre Phasenanteile in den jeweiligen Legierungen sowie ihre druckabhängige und thermische Stabilität unter angenäherten Gleichgewichtsbedingungen betrachtet. Zusammen mit den kristallographischen und magnetischen Eigenschaften der Phasen ergeben sich daraus thermodynamische Modelle, die durch ihre parametrisierte Darstellungsweise eine Optimierung an die jeweiligen experimentellen Befunde gestatten. Durch Extra- und Interpolation der so gewonnenen Zustandsfunktionen der einzelnen Phasen ergibt sich ein möglichst weitgehendes Bild aller wesentlichen, das stoffliche Gesamtsystem charakterisierenden thermodynamischen Zustände, welches auch über die experimentellen Einschränkungen hinaus noch Aussagen über die Phasenkonstitution, etwa die Primärkristallisation von Phasen bei hohen Drücken und Temperaturen sowie die Phasenstabilität in höherkomponentigen Systemen, ermöglicht. Schließlich werden die thermodynamischen Funktionen in einer Datenbank zusammengefasst, womit auch die Möglichkeit ihrer Weiterverwendung in anderen Systemen besteht. Die Arbeit kann in den Bereich der Grundlagenuntersuchungen zu den behandelten Stoffsystemen mit werkstoffwissenschaftlichem Hintergrund eingeordnet werden.

<p>The main focus in the present work concerns calculations on steel/slag equilibria. Thermodynamic software and databases are now powerful and accurate enough to give reliable results when applied to complex metallurgical processes. One example is the decarburization process of high alloyed steels. It is shown that using advanced thermodynamic models, without a complicated kinetic description of the system, reasonable agreement with experimental data is obtained. The calculations are performed using the Thermo-Calc software.</p><p>Within this work a Java interface for Thermo-Calc has been implemented. Java gives graphical possibilities and a graphical interface has been created that facilitates calculations that involve both metallic phases as well as oxides and make them feasible also for an industrial user.</p>

<p>X-ray and neutron crystallography are the predominant methods for obtaining atomic-scale information on bimolecular macromolecules. Despite the success of these techniques, generating well diffracting crystals critically limits going from protein to structure. In practice, the crystallization process proceeds through knowledge-informed empiricism. Better physico-chemical understanding remains elusive because of the large number of variables involved, hence little guidance is available to systematically identify solution conditions that promote crystallization. </p><p>The fields of structural biology and soft matter have independently sought out fundamental principles to rationalize protein crystallization. Yet the conceptual differences and limited overlap between the two disciplines may have prevented a comprehensive understanding of the phenomenon to emerge. Part of this dissertation focuses on computational studies of rubredoxin and human uniquitin that bridge the two fields.</p><p>Using atomistic simulations, the protein crystal contacts are characterized, and patchy particle models are accordingly parameterized. Comparing the phase diagrams of these schematic models with experimental results enables the critical review of the assumptions behind the two approaches, and reveals insights about protein-protein interactions that can be leveraged to crystallize proteins more generally. In addition, exploration of the model parameter space provides a rationale for several experimental observations, such as the success and occasional failure of George and Wilson's proposal for protein crystallization conditions and the competition between different crystal forms.</p><p>These simple physical models enlighten the connection between protein phase behavior and protein-protein interactions, which are, however, remarkably sensitive to the protein chemical environment. To help determine relationships between the physico-chemical protein properties and crystallization propensity, statistical models are trained on samples for 182 proteins supplied by the Northeast Structural Genomics consortium. Gaussian processes, which capture trends beyond the reach of linear statistical models, distinguish between two main physico-chemical mechanisms driving crystallization. One is characterized by low levels of side chain entropy and has been extensively reported in the literature. The other identifies specific electrostatic interactions not previously described in the crystallization context. Because evidence for two distinct mechanisms can be gleaned both from crystal contacts and from solution conditions leading to successful crystallization, the model offers future avenues for optimizing crystallization screens based on partial structural information. The availability of crystallization data coupled with structural outcomes analyzed through state-of-the-art statistical models may thus guide macromolecular crystallization toward a more rational basis.</p><p>To conclude, the behavior of water in protein crystals is specifically examined. Water is not only essential for the correct functioning and folding of proteins, but it is also a key player in protein crystal assembly. Although water occupies up to 80% of the volume fraction of a protein crystal, its structure has so far received little attention and it is often overly simplified in the structural refinement process. Merging information derived from molecular dynamics simulations and original structural information provides a way to better understand the behavior of water in crystals and to develop a method that enriches standard structural refinement.</p> / Dissertation

Asymmetric simple exclusion process (ASEP) is a driven stochastic lattice model of particles that move preferentially in one direction. If particles move only in one direction, the model is known as totally asymmetric process. Conventionally, preferred direction of motion is chosen to be to the right. Particles interact through the hard core exclusion rule, meaning that no more than one particle is allowed to occupy one lattice site. In this work following ASEP models are presented. First we study square diagonal lattice with particles that occupy one lattice site and move along the square diagonals. Mean-field theory was developed for this model. The results that were obtained are the dependency of the current on density of the particles, spatial density distribution along the horizontal direction and the phase diagram of the system. Mean-field theory results were compared to simulations. Next model was lattice with extended particles, i.e. particles that occupy more than one lattice site. Unlike the first model, in this system the particle-hole symmetry is broken. Results for current flow, density distribution and phase diagrams were obtained both by mean-field theory and Monte-Carlo (MC) simulations. Another system was the lattice with vertical particle drift. Now particles that occupy one lattice site jump not only in one preferred horizontal directions but there is also one preferred vertical direction for particle flow. Both mean-field theory and simulations were studied for this system and results were compared. Also we explore the system with immovable obstacle. Obstacle is one or several particles located at fixed positions. In this model we observe increase in particle density in front of the obstacle and "shadow" behind it. It is expected that the shape and size of those formations are symmetrical in transverse direction.