O estudo de soluções proteicas visando à modelagem e à simulação de processos de recuperação e purificação de bioprodutos passa necessariamente pelo estudo da não idealidade, em sentido termodinâmico, destas soluções. Para sistemas em que a concentração de proteína seja baixa, situação comumente presente nestes processos, a principal maneira de avaliar experimentalmente a não idealidade é por meio da determinação da pressão osmótica gerada pela proteína. Deste modo, os objetivos deste trabalho foram: estudar a influência de co-solventes na pressão osmótica de soluções proteicas, verificar a integridade das estruturas secundária e terciária das proteínas nessas soluções, e modelar termodinamicamente os dados de pressão osmótica obtidos. A pressão osmótica foi determinada diretamente por osmometria de membrana, usando soluções de referência com mesma concentração de co-solvente e pH, mas isentas de proteínas. Obtiveram-se dados de pressão osmótica, em função da concentração proteica, de cinco diferentes proteínas (albumina de soro bovino, imunoglobulina G humana, ovalbumina, -lactoglobulina e lisozima) em soluções contendo co-solventes como o polietileno glicol (de diversos tamanhos de cadeia) e sais (sulfato de amônio, sulfato de sódio e cloreto de sódio). Cada conjunto de dados foi obtido em pH e concentração de co-solvente constantes. Observou-se que a presença de co-solventes altera a pressão osmótica, mas este efeito é dependente da proteína, do co-solvente e sua concentração, e do pH da solução. Medidas de fluorescência e de dicroísmo circular das mesmas proteínas permitiram confirmar que elas mantêm sua integridade estrutural nesses meios, o que justifica o uso de equações volumétricas de estado com parâmetros constantes. Os dados de pressão osmótica em função da concentração proteica foram correlacionados por meio de uma equação volumétrica de estado, que combina um termo de esferas rígidas adesivas e um termo de perturbação de ordem zero (aproximação aleatória). O modelo proposto, embora simples, foi suficiente para correlacionar adequadamente o comportamento experimental. / The study of protein solutions aiming at the modeling and simulation of downstream processes entails the study of non-ideality (in thermodynamic sense) of these solutions. For systems wherein the protein concentration is low a situation often encountered in these processes the most important technique to experimentally evaluate this non-ideality is the determination of the osmotic pressure generated by the protein in solution. Thus, the objectives of this work were: to study the influence of co-solvents on the osmotic pressure of protein solutions, to verify the absence of change in the secondary and tertiary structure of proteins in these solutions, and to thermodynamically model the obtained osmotic pressure data. The osmotic pressure was directly measured through membrane osmometry, using protein-free reference solutions with the same pH and co-solvent concentration. The data of osmotic pressure were obtained as a function of protein concentration for five different proteins (bovine serum albumin, human immunoglobulin G, ovalbumin, - lactoglobulin and lysozyme) in solution with co-solvents such as polyethylene glycol (of various chain sizes) and salts (ammonium sulfate, sodium sulfate and sodium chloride). Each data set was obtained at constant pH and co-solvent concentration. It was observed that the presence of co-solvents do shift the osmotic pressure, but this effect is dependent on the protein, the co-solvent and its concentration, and the solution pH. Measurements of fluorescence and circular dichroism of these proteins confirmed that they maintain their structure unchanged in the media, which corroborates the use of volumetric equations of state with constant parameters. The osmotic pressure data as a function of protein concentration were correlated using a osmotic equation of state comprising a repulsive term of adhesive hard spheres and a zero-order perturbation term (random approximation). The proposed model, though simple, was sufficient to properly correlate the experimental behavior.

O principal programa de pesquisa do Grupo de Diagrama de Fases e Termodinâmica Computacional do DEMAR/EEL-USP é o estudo de estabilidade de fases em ligas dos sistemas Me-Si-B (Me = Metal Refratário), os quais apresentam um interesse crescente na área de ligas com potencial para aplicações em altas temperaturas. Destes estudos, este Grupo está construindo uma base de informações termodinâmicas com a finalidade de extrapolá-las para sistemas de ordem superior. Diversos sistemas já foram ou estão sendo estudados. Dando continuidade a este programa, os objetivos principais deste trabalho são a avaliação experimental do sistema ternário Ta-Si-B em sua região rica em Ta e a modelagem termodinâmica dessa mesma região. A projeção liquidus e a seção isotérmica a 1900 ºC, ambas na região rica em Ta, de Ramos (2005), são as únicas informações experimentais para o sistema ternário Ta-Si-B encontradas na literatura. Ramos (2005) identifica em várias de suas amostras a presença de uma nova fase ternária, denominada φ, de estrutura ainda não determinada. A pesquisa de Ramos (2005) foi realizada sempre com amostras produzidas por fusão em forno a arco, a partir de pedaços de Ta, Si e B puros. Nessa condição de preparação das amostras, houve dificuldade em se alcançar o equilíbrio termodinâmico, mesmo após tratamentos térmicos prolongados (1900 oC por 48 horas). Já, neste trabalho, as amostras foram, em sua maioria, produzidas por tratamento térmico de pastilhas prensadas a partir de pós de Ta, Ta5Si3 e TaB. Com essa mudança na forma de confeccionar os experimentos conseguiu-se maior facilidade na obtenção da condição de equilíbrio termodinâmico das amostras durante os tratamentos térmicos, embora ainda com resultados não totalmente satisfatórios. De uma forma geral, os resultados de Ramos (2005) são confirmados no presente trabalho. Uma proposta de relação de fases a 2000 ºC é apresentada para a região envolvendo as fases TaSS, Ta2B, T2, Ta3B4 e TaB. A estabilidade da fase D88, proposta por Nowotny, Lux e Kudielka (1956), também é confirmada e os resultados sugerem que sua estequiometria seja Ta5Si3B. Nenhuma modelagem termodinâmica para este sistema ternário é encontrada na literatura. A otimização do sistema binário Ta-B é realizada por Kaufman (1991) e Chad (2003). A otimização do sistema binário Ta-Si é realizada por Vahlas, Chevalier e Blanquet (1989) e Kaufman (1991). A otimização do sistema binário Si-B é realizada por Fries e Lukas (1991), Zaitsev e Kodentsov (2001) e Fiorani e Coelho (2006). A única otimização adotada completamente é a de Fiorani e Coelho para o sistema binário Si-B. Para o sistema binário Ta-B é adotada a otimização de Chad (2003) com a inclusão de uma nova fase, denominada φ, de alta temperatura, a mesma do sistema ternário, que teria sua origem nesse sistema binário. Já, para o sistema binário Ta-Si é necessária uma nova otimização, por haver algumas inconsistências termodinâmicas nas otimizações anteriores, que poderiam levar a uma descrição inadequada das relações de fases no sistema ternário Ta-Si-B e em sistemas de ordem superior. Neste trabalho é apresentada uma proposta para a modelagem termodinâmica do sistema ternário, que reproduz satisfatoriamente os resultados experimentais disponíveis. / Currently, the main research program of the Phase Diagram and Computational Thermodynamics Group of DEMAR/EEL-USP is the study of phase stability in ternary Me-Si-B systems (Me = Refractory Metal), which presents an increasing interest in the area of alloys with potential for applications at high temperatures. It includes the development of a thermodynamic database to evaluate systems of higher order. Several systems have already been studied. Giving continuity to this program, the main objectives of this work are the experimental evaluation of the ternary Ta-Si-B system in the Ta-rich region and the thermodynamic modeling of this system. The liquidus projection and an isothermal section at 1900 ºC from Ramos (2005), both in the Ta-rich region, are the only experimental information found in literature. Ramos (2005) identifies in several of her samples the presence of a new ternary phase, named as φ, of structure not yet determined. The research of Ramos (2005) is carried out with samples produced from pure Ta, Si and B via arc melting. In this method of sample preparation, it is difficult to obtain thermodynamic equilibrium conditions during heat treatments at 1900 ºC for 48 h. In the present work, the majority of samples were produced via sintering of pressed pellets from Ta, Ta5Si3 and TaB powders. With this method of sample preparation, the attainment of equilibrium conditions was easier during the heat treatments, even though not completely satisfactory. In general, the results of Ramos (2005) were confirmed. A proposal for the phase relations at 2000 ºC is presented for the region involving the phases TaSS, Ta2B, T2, Ta3B4 and TaB. The stability of the D88 phase, proposed by Nowotny, Lux and Kudielka (1956), is also confirmed and the results suggest that its stoichiometry is near Ta5Si3B.No thermodynamic modeling for this ternary system is found in literature. The optimization of the binary Ta-B system is carried out by Kaufman (1991) and Chad (2003). The optimization of the binary Ta-Si system is carried out by Vahlas, Chevalier and Blanquet (1989) and Kaufman (1991). The optimization of the Si-B binary system is carried out by Fries and Lukas (1991), Zaitsev and Kodentsov (2001) and Fiorani and Coelho (2006). In this work the thermodynamic data from Fiorani and Coelho (2006) is used for the Si-B system. For the binary Ta-B system it was adopted the optimization from Chad (2003) with the inclusion of the high temperature φ phase, the same one of the ternary system, which has its origin in this binary system. In addition, for the binary system Ta-Si a new optimization is necessary, since some thermodynamic inconsistencies in the previous optimizations would lead to an inadequate description of the phase relations in the Ta-Si-B and systems of higher order. Thus, in this work presents for the first time a thermodynamic modeling for the Ta-Si-B system, which reproduces the available experimental results satisfactorily.

Orientador: Waldyr Luiz Ribeiro Gallo / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-25T19:17:11Z (GMT). No. of bitstreams: 1 BritoLopes_AlissonVinicius_M.pdf: 16369458 bytes, checksum: e72c2c680cdccf96557c9588ce37e602 (MD5) Previous issue date: 2014 / Resumo: Um modelo de simulação fenomenológico de motores Diesel foi desenvolvido. O modelo permite a simulação das fases aberta e fechada do ciclo. A combustão é modelada utilizando um modelo de liberação de energia finita. É levado em conta um modelo unidimensional para escoamento sobre as válvulas e um modelo para a transmissão de calor instantânea entre os gases e a parede do cilindro. Por se tratar de um modelo paramétrico, uma série de estudos pode ser feita no sentido de avaliar as influências dos diversos parâmetros sobre os valores finais de eficiência global do motor. As curvas características e as eficiências do motor correspondem aos resultados finais obtidos após o processo iterativo. Um motor é comparado quando simulado em duas situações: com e sem cruzamento de válvulas. Ao simular o caso base (sem cruzamento de válvulas) foi possível comparar a potência efetiva de eixo declarada pelo fabricante (49 kW) e constatar que a potência calculada pelo modelo foi de 51.3 kW indicando assim que as hipóteses adotadas foram bastante razoáveis. Além disso, o modelo forneceu valores para eficiência volumétrica, consumo específico e eficiência térmica condizentes com os valores usualmente encontrados nas referências bibliográficas. Constatou-se que ao gozar de um curto cruzamento de válvulas o motor teve seus parâmetros de eficiência aumentada em 3%, além de uma redução de 3.3% no consumo específico de combustível, valores esses quando comparados ao caso base. O algoritmo desenvolvido permitiu também analisar a influência do ponto de injeção na curva de pressão de combustão, a influência da rotação na curva de taxas mássicas na admissão/escape e a influência da quantidade de combustível injetada sobre as potências de atrito, efetiva e indicada / Abstract: A phenomenological simulation model of Diesel engine was developed. The model is able to simulate the open and closed phase of the cycle. The combustion process is modeled by using a finite heat release model. A one-dimensional model is applied for the flow through the valves and the instantaneous heat transfer between gases and cylinder wall. As the model is parameterized, a series of studies can be done to evaluate the influence of several parameters on the final values of the overall engine efficiency. Typical engine curves and the engine efficiencies are obtained as a result of the interactive process. An engine is compared when simulated in two situations: with and without valve overlapping. By simulating the baseline case (without valve overlapping) it was possible to compare the brake power informed by the engine manufacturer (49 kW) and that obtained by model was (51.3 kW), showing that the hypothesis adopted was reasonable. Furthermore, the model provides values for the volumetric efficiency, specific fuel consumption and thermal efficiency in agreement with values usually found in both the bibliographic references and manufacturer¿s data. It was found that when the engine operated with a short valve overlapping, the engine achieved 3% of improvement in the efficiency parameters and 3.3% of reduction in specific fuel consumption, these values are compared with the base case. The algorithm developed also allowed to analyze the influence of the injection start point in the combustion pressure curve, the influence of engine rotation in the mass rate in intake and exhaust process and the influence of equivalence ratio on the friction, effective and indicated power / Mestrado / Termica e Fluidos / Mestre em Engenharia Mecânica

The polarization response such as ferroelectric and ferroelastic switching in ferroelectrics is the important feature for ferroelectric and electromechanical applications. In polycrystalline form ferroelectrics, effects of the microstructural parameters such as texture, grain size, and residual stress are there and have not fully been understood. Among these effects, (1) the origin of grain size effects on ferroelastic switching, (2) mechanical stress effects on polarization switching, and (3) ferroelectric switching kinetics and the relationship to grain boundaries are investigated.<br>Firstly, the microscopic origin of ferroelastic switching suppression in smaller grains is discovered using a microscopic probing technique (piezoresponse force microscopy). It is demonstrated that there is no independent grain size effect on ferroelastic switching; the grain size affects the domain structure in a grain, and the domain structure plays an important role in the ferroelastic switching suppression. This result suggests that the grain size is not an independent critical parameter for the electromechanical property degradation in a grain < 1 m as the ferroelastic switching is a dominant component for the electromechanical property.<br>The study about the mechanical stress effects on the electric field induced polarization switching rationalizes the emergence of the electric field induced low-symmetry phases observed in tetragonal Pb(Zr,Ti)O3 and BaTiO3 ceramics after poling. It is demonstrated that a shear stress plays an important role in stabilizing the monoclinic phase in Pb(Zr,Ti)O3 whereas a normal stress along the polarization axis is a key for the monoclinic phase in BaTiO3 with a thermodynamic approach. It is suggested that the fraction of the low-symmetry phase, which is important for the large electromechanical property, can be engineered by applying an appropriate stress.<br>For the work about ferroelectric switching kinetics, the first direct Barkhausen noise associated with ferroelectric switching is measured. The domain switching time is quantified by the frequency of the Barkhausen noise. It is discovered that the dominant domain wall pinning site is grain boundaries based on the domain wall jump distance between pinning sites calculated from the switching time. This result suggests that the technique is a good tool for understanding the relationship between microstructure – domain wall kinetics.<br>In sum, the mechanisms of the polarization switching suppression due to domain structure and grain boundaries, and the emergence of the low symmetry phases due to stresses are revealed. These discoveries facilitate further improvements of the device performances with engineering the domain structure, grain boundaries and residual stress.<br>

The stacking fault energy (SFE) of seven austenitic stainless steels with the compositions x(Cr)=20 at%, 8≤x(Ni)≤20 at% and 0≤x(Mn)≤8 at% have been calculated at room temperature using the thermodynamics-based Olson and Cohen modeling approach [1]. Modeling has been performed using the TCFE7 database together with the Thermo-Calc 3.0 software. Experimental SFE values from transmission electron microscopy (TEM) measurements and theoretical SFE values from ab initio calculations were used for comparison. The results of the SFE from TCFE7 were not in agreement with the values reported in the literature. After an evaluation of the thermodynamic parameters in the database, a new assessment of the SFE in the ternary and quaternary Fe-Cr-Ni and Fe-Cr-Ni-Mn system was proposed which resulted in SFE values in fairly good agreement with the literature.

No description available.

This dissertation develops computational techniques to aid in efficiently studying petrologic systems that would otherwise be challenging. It then focuses on a case study in which the transition from diagenesis to syn-magmatic heating led to a recrystallization and sulfur mobilization. A Markov-chain Montecarlo-based methodology is developed to allow for the assessment of uncertainty in calculated phase assemblage diagrams. Such phase equilibria are ubiquitous in modern petrology, but uncertainties are rarely considered. Methods are discussed for visualizing and quantifying emergent patterns as phase diagrams are re-calculated with input data modified within permitted uncertainty bounds, and these are implemented in a new code. Results show that uncertainty varies significantly across pressure-temperature space and that in some conditions, estimates of stable mineral assemblage are known with very little confidence. A Machine-Learning (ML) based methodology is developed for automatically identifying unknown phases using Electron-dispersion spectra (EDS) in concert with a Random Forest Classification algorithm. This methodology allows for phase identification that it is insensitive to overfitting and noisy spectra. However, this tool is limited by the amount of reference spectra available in the dataset on which the ML algorithm is trained. The approximately 250 EDS spectra in the current training database must be supplemented to make the tool more widely useful, though it currently has an excellent success rate for correctly identifying various sulfide and oxide minerals. An analysis of paragenesis associated with Central Atlantic Magmatic Province (CAMP) intrusions helps to better constrain the dynamics of magma emplacement, while also providing a method for estimating the amount of sedimentary sulfide-sequestered sulfur mobilized as a result of magnetite formation associated with igneous activity. This method demonstrates that dike emplacement can trigger liberation of sedimentary sulfur with no direct cooling impact on climate. / Doctor of Philosophy / Determining how rocks and minerals form is fundamental to the geosciences. Here I present two computer-based techniques that can help address this essential problem. One method involves carefully determining uncertainty in thermodynamic modeling. Knowing the amount of uncertainty ultimately allows us to know the degree of confidence we can have in our model-based conclusions. The second computer-based technique involves using Machine Learning to automate the identification of minerals using an Electron-dispersion spectra (EDS) measured using a Scanning Electron Microscope (SEM). In theory, computers are much better than humans at quickly and repeatedly processing large sets of data such as EDS. This technique works well when the computer is successfully 'trained' on a large set of data but is somewhat limited in this case because there isn't diverse enough data available to train the computer. We therefore need better training data so that we can more fully benefit from this mineral identification tool. A third project I worked on involved assessing the impact of magma intruding into sedimentary rocks of the Culpeper Basin in northern Virginia. This occurred roughly 200 million years ago during the rifting of Pangea. The sedimentary rock around the magma heated up so much that water in the rock boiled and caused the rock to become fractured. After this a hydrothermal system was established that helped convert pyrite to magnetite, removing sulfur from the rocks in the process.

Cette thèse a pour objectif l’étude et la mise au point d’un procédé de fabrication, par cristallisation, de sel thermal enrichi en magnésium, à partir d’eaux minérales naturelles chlorurées sodiques fortes. Un modèle dynamique a d’abord été développé pour la simulation du procédé. Ce modèle est basé sur la description des phénomènes physico-chimiques intervenant dans les équilibres thermodynamiques multiphasiques (liquide, vapeur, solides). Puis, un pilote de laboratoire a été mis en place pour vérifier la faisabilité du procédé et valider le modèle développé. Le pilote proposé est constitué de deux réacteurs en série entre lesquels est placé un système de filtration. Une étude expérimentale et par modélisation du procédé avec l’eau thermale de Salies-de-Béarn a ensuite été réalisée. Cette étude montre qu’il est possible de produire un sel thermal ou une eau-mère naturellement enrichis en magnésium. / The aim of this thesis is the study and the development of a production process, by cristallization, of thermal salt enriched in magnesium, from highly chlorinated natural waters. At first, a dynamic model was developed for the process simulation. This model is based on the description of physical-chemical phenomena occurring in multiphase thermodynamic equilibrium (liquid, vapor, solids). Then, a laboratory pilot was set up to check the process feasibility and to validate the developed model. The proposed pilot is a series of two reactors between which is placed a filtration system. Finally, an experimental and modeling study of the process has been realized with thermal water of Salies-de-Béarn as raw-material. This study shows that it is possible to produce a thermal salt or mother liquor naturally enriched in magnesium.

This thesis aims to provide a better understanding of the role of mountain building in the carbon cycle. The amount of CO2 released into the atmosphere due to metamorphic processes is largely unknown. To constrain the quantity of CO2 released, fluid-driven reactions in metamorphic rocks can be studied by tracking fluid-rock interactions along ancient fluid flow pathways. The thesis is divided into two parts: 1) modeling of fluid flow rates and durations within shear zones and fractures during greenschist- and blueschist-facies metamorphism and 2) the assessment of possible mechanisms of fluid infiltration into rocks during greenschist- to epidote-amphibolite-facies metamorphism and controlling chemical and mineralogical factors of reaction front propagation. On the island Syros, Greece, fluid-rock interaction was examined along a shear zone and within brittle fractures to calculate fluid flux rates, flow velocities and durations. Petrological, geochemical and thermodynamic evidence show that the flux of CO2-bearing fluids along the shear zone was 100-2000 times larger than the fluid flux in the surrounding rocks. The time-averaged fluid flow velocity and flow duration along brittle fractures was calculated by using a governing equation for one-dimensional transport (advection and diffusion) and field-based parameterization. This study shows that fluid flow along fractures on Syros was rapid and short lived. Mechanisms and controlling factors of fluid infiltration were studied in greenschist- to epidote-amphibolite-facies metabasalts in SW Scotland. Fluid infiltration into metabasaltic sills was unassisted by deformation and occurred along grain boundaries of hydrous minerals (e.g. amphibole) while other minerals (e.g. quartz) prevent fluid infiltration. Petrological, mineralogical and chemical studies of the sills show that the availability of reactant minerals and mechanical factors, e.g. volume change in epidote, are primary controls of reaction front propagation. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript. Paper 4: Manuscript.</p><p> </p>

Understanding transcriptional regulation quantitatively is a crucial step towards uncovering and ultimately utilizing the regulatory semantics encoded in the genome. Transcription of a gene is induced by the binding of site-specific transcription factors (TFs) to so-called cis-regulatory-modules (CRMs). The frequency and duration of the binding events are influenced by the concentrations of the TFs, the binding affinities and location of the transcription factor binding sites (TFBSs) in the CRM as well as the properties of the TFs themselves (e.g. effectiveness, competitive interaction with other TFs). Modeling these interactions using a mathematical approach, based on sound biochemical and thermodynamic foundations, enables the understanding and quantitative prediction of transcriptional output of a target gene. In the thesis I introduce the developed framework for modeling, visualizing, and predicting the regulation of the transcription rate of a target gene. Given the concentrations of a set of TFs, the TFBSs in a regulatory DNA region, and the transcription rate of the target gene, the method will optimize its parameters to generate a predictive model that incorporates the regulatory mechanism of the observed gene. I demonstrate the generalization ability of the model by subjecting it to standard machine learning and hypothesis testing procedures. Furthermore, I demonstrate the potential of the approach by training the method on a gene in D. melanogaster and predicting the output of the homologous genes in 12 other Drosophila species where the regulatory sequence has evolved substantially but the regulatory mechanism was conserved. Finally, I investigate the proposed role-switching behaviour of TFs regulating the development of D. melanogaster, which suggests that SUMOylation is the biological mechanism facilitating the switch.