Time- and rate-dependent materials such as polymers, bituminous materials, and soft materials clearly display all four fundamental responses (i.e. viscoelasticity, viscoplasticity, viscodamage, and healing) where contribution of each response strongly depends on the temperature and loading conditions. This study proposes a new general thermodynamic-based framework to specifically derive thermo-viscoelastic, thermo-viscoplastic, thermo-viscodamage, and micro-damage healing constitutive models for bituminous materials and asphalt mixes. The developed thermodynamic-based framework is general and can be applied for constitutive modeling of different materials such as bituminous materials, soft materials, polymers, and biomaterials. This framework is build on the basis of assuming a form for the Helmohelotz free energy function (i.e. knowing how the material stores energy) and a form for the rate of entropy production (i.e. knowing how the material dissipates energy). However, the focus in this work is placed on constitutive modeling of bituminous materials and asphalt mixes. A viscoplastic softening model is proposed to model the distinct viscoplastic softening response of asphalt mixes subjected to cyclic loading conditions. A systematic procedure for identification of the constitutive model parameters based on optimized experimental effort is proposed. It is shown that this procedure is simple and straightforward and yields unique values for the model material parameters. Subsequently, the proposed model is validated against an extensive experimental data including creep, creep-recovery, repeated creep-recovery, dynamic modulus, constant strain rate, cyclic stress controlled, and cyclic strain controlled tests in both tension and compression and over a wide range of temperatures, stress levels, strain rates, loading/unloading periods, loading frequencies, and confinement levels. It is shown that the model is capable of predicting time-, rate-, and temperature-dependent of asphalt mixes subjected to different loading conditions.

Thesis (M.S.); Submitted to Iowa State Univ., Ames, IA (US); 12 Dec 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2547" Elizabeth M. Lenihan. 12/12/2003. Report is also available in paper and microfiche from NTIS.

Submitted by Dilene Paulo (dilene.fatima@ufcg.edu.br) on 2018-04-13T15:41:27Z No. of bitstreams: 1 RIVANA MABEL LUCENA OLIVEIRA - DISSERTAÇÃO (PPGEQ) 2017.pdf: 1154206 bytes, checksum: 45fbf5b56861974e34403f5a5215119d (MD5) / Made available in DSpace on 2018-04-13T15:41:27Z (GMT). No. of bitstreams: 1 RIVANA MABEL LUCENA OLIVEIRA - DISSERTAÇÃO (PPGEQ) 2017.pdf: 1154206 bytes, checksum: 45fbf5b56861974e34403f5a5215119d (MD5) Previous issue date: 2017 / Capes / Sequências de destilação extrativa têm recebido uma atenção especial dos pesquisadores devido ao alto consumo energético e à baixa eficiência termodinâmica associados a esse processo. A eficiência termodinâmica vem sendo abordada de forma bastante simplificada pela literatura, e neste trabalho, este termo foi abordado intrinsecamente, de modo que o sentido físico dos termos: trabalho mínimo, trabalho equivalente, trabalho perdido e produção de entropia, relacionados à eficiência, foram discutidos do ponto de vista físico e matemático. Técnicas de intensificação vem recebendo destaque no que se refere a redução do consumo energético e custos de processos de destilação, e a integração térmica surge como alternativa para reduzir o consumo energético de processos de destilação. As sequências de destilação extrativa convencional sem e com integração térmica foram abordadas neste trabalho dos pontos de vista ótimo econômico, termodinâmico e energético, utilizando o parâmetro teor de solvente como principal parâmetro de análise. Além do alto consumo energético e baixa eficiência termodinâmica, os processos de destilação extrativa incluem ainda uma fonte de irreversibilidade que é relatado como responsável pela baixa eficiência termodinâmica desses processos, e este foi outro ponto de análise para os fluxogramas abordados. Os estudos de caso foram as misturas azeotrópicas etanol-água e acetona-metanol utilizando etileno glicol e água, como solventes, respectivamente. Usando o procedimento proposto, as sequências com e sem integração térmica foram analisadas considerando o sistema como um todo, para os termos econômicos e termodinâmicos, e, cada coluna (extrativa e de recuperação) em separado para termos termodinâmicos, além da avaliação do efeito remixing. Os resultados mostram que a configuração com integração térmica não só é termodinamicamente mais eficiente quando comparada a configuração sem integração, como também apresentou menores valores de TAC e consumo energético, mesmo quando valores negativos para eficiência termodinâmica são encontrados, e que os termos termodinâmicos devem ser comparados para casos que envolvem a separação da mesma mistura. / Extractive distillation sequences have received special attention from researchers due to the high energy consumption and the low thermodynamic efficiency associated to this process. The thermodynamic efficiency has been simplified in the literature, but in this work it was approached intrinsically, thus the physical meaning of the terms related to efficiency like minimum work, work equivalent, lost work and entropy production were discussed from a physical and mathematical point of view. Process intensification alternatives have been highlighted in the reduction of energy consumption and costs in the distillation processes. Likewise, thermal integration is an alternative to reduce the energy consumption of distillation processes. The conventional extractive distillation sequences with and without thermal integration were approached in this work. They were analyzed from the economic, thermodynamic and energy optimum points of view and the main parameter of analysis was the solvent content. In addition to the high energy consumption and low thermodynamic efficiency, the extractive distillation also include a irreversibility that is reported as responsible for the low thermodynamic efficiency of this process, and this was another point of analysis on the flowcharts studied. The study cases were the azeotropic mixtures formed from ethanol-water and acetone-methanol using ethylene glycol and water as solvents, respectively. The sequences with and without thermal integration were studied considering the proposed procedure and the whole system was analyzed for the economic and thermodynamic terms, also each column (extractive and recovery columns) was separately analyzed for thermodynamic terms, besides the evaluation of the remixing effect. The results show that the configuration with thermal integration is thermodynamically more efficient when compared to the non-integration configuration, moreover the configuration with thermal integration presented lower values of TAC and energy consumption, even when negative values for thermodynamic efficiency are found, and that the thermodynamic terms must be compared to cases involving the separation of the same mixture.

In their attempts to understand the unwritten past of human technology and progression, archaeologists have borrowed aspects of the natural sciences to answer big questions. In one such pursuit, fundamental aspects of the sciences have been employed towards the chemical compositional analysis of copper-based artifacts, often to simply classify which is bronze, brass, or pure copper, and to explain why they are significant in limited space and time. This thesis takes the variety of identified metal types and compositions from these analyses and builds the beginnings of an ambitious thermodynamic model based on the accepted premise of consistent and widespread recycling of ancient metals over time. Following the laws of thermodynamics, in systems at equilibrium, the model predicts the outcome of metal losses over the course of ancient pyrometallurgical processes from molten systems through both volatilization and oxidation using rigorous and established mathematics and theory. Elemental loss likelihoods are modeled for all binary copper-based metals, using activity coefficients, and ternary copper and zinc-based systems, with the excess Gibbs free energy, respectively. The calculations are performed using custom-written software designed to account for hundreds of thousands of compositional permutations after the method described by Redlich and Kister (1948). The results of these calculations are given as activity (binary) and isoactivity (ternary) contour lines. Quantified tables for the oxidation and volatilization of elements from a copper melt at 1200 ºC and 1 atm are also given as rough indicators of element loss in ancient pyrometallurgical systems. A proof of concept of the models viability is also provided for binary Cu-M and ternary Cu-M-Zn (M = Ag, As, Au, Bi, Co, Fe, Ni, Pb, Sb, Sn, Zn), Cu-Sn-Pb, and Cu-Sb-As systems from the Late Bronze Age to post-medieval periods in Britain, which is based on several substantial artifact chemical datasets. For each ternary system, the interaction parameters used for higher-order calculations from the fitted behavior of each contributing binary systems are provided. Comparison of the calculated models to available experimental system assessments, and to published archaeological chemical datasets, show that in both respects the proposed modeling of ancient copper-based metal losses works. And given the near ubiquity of ancient metal use around the world, the consistency in metal production and recycling technology, and the chemical analyses available, this preliminary model can be applied virtually anywhere the technology for smelting and recycling existed. In addition to loss modeling, this thesis has the additional offshoots of predicting ancient furnace conditions based on the calculated behavior of interacting metals, and of the controlling thermodynamic factors in the ancient calamine process.

[pt] O presente trabalho visa dois objetivos. 0 primeiro, didático, é de apresentar algumas versões da Termodinâmica dos Meios Contínuos, elucidando suas semelhanças e diferenças várias formas da segunda lei são apresentadas, questionando-se em alguns casos as suas supostas generalidades. O segundo objetivo, de pesquisa, desenvolve na versão de Serrin os conceitos de Estabilidade Termodinâmica e Exergia, aplicando-os no estudo dos ciclos de Carnot e de Rankine. Através do conceito de função de acumulação introduz-se uma nova maneira de se determinar a eficiência dos referidos ciclos. Ainda na versão de Serrin, aplica-se a teoria de processos de transição no estudo do efeito Joule-Thomson. Os fluidos de trabalho são um gás ideal, caracterizado pela convexidade do seu espaço de estados, e um fluido de Van der Halls, que não possui a mesma característica. Finalmente, no contexto da Termodinâmica de Processos Irreversíveis é feita uma comparação entre as soluções de problemas de condução de calor em meios rígidos e elásticos lineares isotrópicos. / [en] The present work has two purposes. The first one is didactic. It intend to present many versions of the Continuun Thermodynamics discussing their resemblances and diferences. Many forms of the second law are presented and in some cases their supposed generalities are questioned. The second purpose lies on the basic research. It is carried out applying the Serrin s version the concepts of Thermodynamic Stability and Availability in the studied of the Carnot s and Rankine s cycles. By meaning of the accumulation function concept a newform to determine the efficience of the above cycles is introduced. On the other hand in the Serrin s version the theory of transition processes can be applied in the study of the Joule-Thomson effect. The working fluids are an ideal gas which is characterized by the convexity of it s state space and the Van der Waals fluid which is not provided of such characteristic. Finally in the context of the Irreversible Thermodynamics is made a comparison between the solutions of heat conduction problems in rigid and linear isotropic elastic continuum.

La méthode des éléments discrets est utilisée pour étudier deux types d'intéraction dans les matériaux granulaires pour deux applications différentes.La première application introduit un couplage hydromécanique pour étudier le comportement des matériaux granulaires partiellement saturés. Un modèle numérique en régime pendulaire pour les grains sphériques permettant la détermination des aires interfaciales et tenant compte de la rugosité des grains est développé. Sur cette base, l'énergie libre des interfaces est définie, et sa variation se trouve à équilibrer le travail mécanique exercée par le pont liquide sur les particules d'un système à deux grains conformément à la première loi de la thermodynamique. Le modèle permet de détecter l'evolution de l'énergie libre dans les systèmes granulaires deformés et simulés avec la méthode des éléments discrets. Des simulations sur des assemblages réguliers et aléatoires sont présentés pour discuter le concept de la contrainte effective et vérifier si l'expression Love-Weber de contrainte moyennée décrit bien le comportement des matériaux granulaires partiellement saturés pour différentes configurations et aspects mécaniques. Bien souvent censé jouer le rôle de la contrainte effective dans les systèmes multiphasiques, la contrainte moyennée de Love-Weber n'est valable que pour des assemblages réguliers en régime élastique. En cas d'assemblages aléatoires, elle ne compare pas toujours avec les variations de l'énérgie libre élastique. Au pic pour la résistance au cisaillement, Love-Weber vérifie une enveloppe de rupture Mohr-Coulomb unique pour les assemblages avec une granulometrie uniforme; elle peut alors être défini comme une possible formulation de contrainte effective micromécanique dans ce cas. Il est cependant montré que cette hypothèse n'est pas valable pour toutes les configurations de granulometrie possibles.Le modèle pendulaire est couplé avec le modèle funiculaire de Yuan et. al. (2015), ce qui permet la simulation d'un drainage complet. Les résultats montrent que l'addition des ménisques a un impact important sur le comportement mécanique des sols non saturés .La deuxième application incarne les interactions des grains avec un milieu élastique continu pour étudier la compaction des agents de soutènement qui est d'une grande importance dans l'industrie de la production pétrolière. Un tas granulaire est compactée entre deux plaques rigides. La répartition des contraintes induites par le tas d'agents de soutènement sur les plaques est étudiée et reliée à l'ouverture de la fissure et la zone de contact sur chaque plaque. L'influence de l'angle de frottement entre les grains et entre les grains et les plaques sont également étudiés. Les plaques rigides sont remplacés dans une deuxième partie par un bloc rocheux élastique simulé à l'aide de la DEM,en collant des particules entre elles par une très forte cohésion ajoutée aux contacts. La DEM est trouvée capable de simuler un milieu de continu élastique, vue que la comparaison de l'analyse d'un problème d'inclusion d'un disque rigide dans le bloc rocheux discrèt avec les résultats analytiques de Selvadurai (1994) est très proche. La forme dus tas de soutènement déposé à partir du trou de forage par gravité et la géométrie de la fracture pour différentes valeurs de contrainte verticales sont finalement présentés. / The discrete element method is used to study two interaction types in granular materials for two different applications.The first application embodies hydromechanical coupling to study the behavior of unsaturated granular materials. An extended numerical model of pendular bridge for spherical grains is introduced, enabling the determination of interfacial areas and taking into account the roughness of the grains. On this basis, the free energy of interfaces is defined, and its changes are found to balance the mechanical work exerted by the bridge on the particles of a two grain system, following the first law of thermodynamics. The model enables tracking the changes of free energy in deforming granular systems simulated with the discrete element method. Simulations of regular and random packings are presented to discuss the effective stress concept and check whether the Love-Weber expression of averaged stress is able to describe well the behavior of partially saturated granular materials for different configurations and mechanical aspects. Though frequently supposed to play the role of effective stress in multiphase systems, the Love-Weber stress is found to be valid only for regular packings to describe the deformation behavior in the elastic regime. In random packings, it does not compare consistently with the changes of elastic free energy.At the peak for shear strength, Love-Weber stress can be defined as a possible micromechanical effective stress formula for some configurations. It verifies a unique Mohr-Coulomb rupture envelop when the envelops are plotted in $p_{cont},q_{cont}$ in the case of random packings with rough /smooth grains and tightly graded particle size distributions. It is however shown that this property does not hold for all the possible particle size distributions.The pendular bridge model is coupled with the funicular model of Yuan et. al. (2015) allows the simulation of a full drainage process where it is shown that the addition of the menisci have a noticeable impact on the behavior of unsaturated soils.The second application embodies particle-elastic continuum interaction to study the compaction of proppant region that is of big importance in the oil and gas production industry. A granular pile is compacted between two rigid plates. The stress distribution induced by the pile of proppants on the plates is investigated and related to the opening of the fracture and the contact zone on each plate. The influence of friction angle between the grains and the grains and the plates are also investigated. The rigid plates are replaced in a second part by an elastic rock block simulated using DEM, gluing particles together with elastic contacts. DEM is shown to be adequate to simulate an elastic continuum medium as the comparison of the analysis of a rigid disc inclusion problem in the discrete rock block with analytical results of Selvadurai (1994) fit very well. The shape of the proppant pile deposited from the borehole by gravity and the geometry of the fracture for different overburden stress values are presented.

Le massif de l'Agly a subit un métamorphisme hercynien haute température – basse pression dont le gradient apparent est comparable à celui des zones volcaniques actuelles (120°C.km-1). Ce gradient anormal a donné lieu à plusieurs hypothèses (i) des déformations structurales (amincissement crustal, délamination), (ii) un apport thermique (activité magmatique).Les affleurements du massif de l'Agly permettent l'observation d'une succession sans hiatus apparent des faciès métamorphiques de schistes verts à granulites. Le socle est constitué de gneiss précambriens et d'orthogneiss cambriens. En discordance sur le socle repose une couverture de sédiments paléozoïques. De nombreux granitoïdes tardi-carbonifère se sont mis en place à dans le massif.Nous avons actualisé les données thermobarométrique selon deux approches (la modélisation thermodynamique NKFMASHTL et des calibrations thermobarométrique). Les résultats barométriques indiquent une pression maximale de 4,5 ± 0,5 kbar pour les terrains les plus profonds et un hiatus de l’ordre de 1,5 kbar entre socle et couverture. Le pic du métamorphisme est suivi par des réactions correspondant à une décompression.Une modélisation thermique de la conduction de sills nous a permis de tester l'effet de différents paramètres : conductivité, capacité calorifique ; géotherme initial ; épaisseur de la croûte ; réactions métamorphiques ; fréquence, géométrie, température et profondeur d'injection des sills. Un amincissement crustal ou un apport de chaleur mantellique purement conductif ne sont pas suffisant, sans la mise en place de sills à une profondeur équivalente à celle du haut du socle, pour expliquer les observations. / The Agly massif undergone a high temperature - low pressure metamorphism which shows an apparent thermal gradient comparable to that of present-day volcanic zones (120°C.km-1). Such abnormal thermal gradients have given way to various hypotheses, including structural deformations (crustal thinning, delamination), or heat input due to a magmatic activity.The outcrops through the Agly massif allow the study of an apparently hiatus-free succession of metamorphic facies ranging from greenschists to granulites. The massif is composed of a basement of precambrian gneisses and cambrian orthogneisses. The basement is unconformably overlain by a paleozoïc sedimentary cover. The late-Carboniferous granitoïds, associated to mafic intrusions, are observed at all levels.We have used thermodynamic modelling and thermobarometric calibrations to revisited the thermobarometric data for both cover and basement rocks. Both methods provide consistent barometric results, 4,5 ± 0,5 kbar for the deepest parts of the massif and a hiatus in the range of 1,5 kbar between the basement and the cover. Post-peak reactions correspond to a decompression. A conductive thermal modelling of sills injection allow us to test the influence of various parameters on the heat flow through the crust modeled : thermal conductivity and heat capacity ; initial geotherm ; crust thickness ; metamorphic reactions ; timing, geometry, temperature and depth of sill injection. Crustal delamination, thinning or magma emplacement in the lower crust cannot reproduce the observed HT-LP metamorphic conditions, unless associated with magma injection at the depth corresponding to the one of the top of the Agly basement.

BATISTA JÚNIOR, Francisco Florêncio. Propriedades termodinâmicas, eletrônicas e de transporte de sistemas curvos semicondutores. 2014. 104 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2014. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-09-12T20:11:36Z No. of bitstreams: 1 2014_tese_ffbatistajunior.pdf: 17233595 bytes, checksum: 9f4c5f7e5b2bbf9bf2975c26ed164fb9 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-09-12T20:23:03Z (GMT) No. of bitstreams: 1 2014_tese_ffbatistajunior.pdf: 17233595 bytes, checksum: 9f4c5f7e5b2bbf9bf2975c26ed164fb9 (MD5) / Made available in DSpace on 2014-09-12T20:23:03Z (GMT). No. of bitstreams: 1 2014_tese_ffbatistajunior.pdf: 17233595 bytes, checksum: 9f4c5f7e5b2bbf9bf2975c26ed164fb9 (MD5) Previous issue date: 2014 / We study thermodynamic properties of an electron gas confined in a two-dimensional cylindrical surface under the action of a magnetic field perpendicular to the cylinder axis. We observed that the applied magnetic field has a similar effect to that produced by a non-homogeneous magnetic field on a flat system. We calculate the energy spectrum of the system for different values of curvature and symmetry of the magnetic field to the surface. We show that the physical properties of these systems are strongly connected to the symmetry imposed by the magnetic field by calculating the density of states, specific heat and chemical potential. We investigate how the curvature of a semiconductor film affects its electronic and transport properties. We study how the geometry-induced potential resulting exclusively from periodic ripples in the film modifies its band structure by inducing electronic confinement. For fixed curvature parameters, this confinement can be easily tuned by an external electric field, so that features of the band structure such as the energy gaps and band curvature can be controlled by an external parameter. We also show that, for some values of curvature and electric field, it is possible to obtain massless Dirac bands for a smooth structure. Moreover, we use a wave packet propagation method to demonstrate that the ripples are responsible for a significant inter-sub-band transition, specially for moderate values of the ripple height. / Neste trabalho estudamos propriedades termodinâmicas de um gás de elétrons confinado em uma superfície bidimensional cilíndrica sob a ação de um campo magnético perpendicular ao eixo do cilindro. Observamos que o campo magnético aplicado desta forma produz efeito similar ao produzido por um campo magnético não-homogêneo em um sistema plano. Calculamos o espectro de energia nesse sistema para diferentes valores de curvatura e simetria do campo com a superfície. Mostramos que as propriedades físicas desses sistemas estão fortemente ligadas a essa simetria do campo magnético através do cálculo da densidade de estados, potencial químico e calor específico do sistema. Investigamos como a curvatura de um filme semicondutor afeta suas propriedades eletrônicas e de transporte. Estudamos como o potencial efetivo induzido pelas deformações de curvatura periódicas no filme modificam sua estrutura de bandas induzindo o confinamento eletrônico. Para parâmetros fixos de curvatura, tal confinamento pode ser ajustado através de um campo elétrico externo, de modo que certas características da estrutura de bandas tais como emph{gaps} de energia e curvaturas das bandas podem ser controladas por um parâmetro externo. Também mostramos que, para alguns valores de curvatura e campo elétrico, é possível obter bandas de Dirac para filmes semicondutores com curvatura Gaussiana. Além disso, usamos um método de propagação de pacotes de onda para demonstrar que as curvaturas são responsáveis por significantes transições entre sub-bandas, especialmente para valores moderados de curvatura.

O yacon (Smallanthus sonchifolius) é uma raiz de origem andina, considerada como um alimento funcional por apresentar em sua composição frutoligossacarídeos (FOS) e compostos fenólicos. Os FOS são polímeros de frutose com grau de polimerização de 3-10 e têm sido designados como prebióticos e fibras alimentares por sua não digestibilidade pelas enzimas do trato digestivo humano e por estimulando seletivamente o crescimento e a atividade de bactérias intestinais promotoras de saúde. Além da ação prebiótica, as raízes de yacon são ricas em compostos fenólicos com propriedades antioxidantes, que protegem o corpo humano dos processos oxidativos. Entretanto, a presença desses compostos torna as raízes suscetíveis à reação de escurecimento enzimático causado pela peroxidase e polifenoloxidase. Diante disso, inicialmente, foi estudada a cinética da inativação térmica e parâmetros termodinâmicos durante o branqueamento dessas enzimas e da enzima inulinase no suco de yacon. O suco de yacon, previamente acidificado com 1% de ácido cítrico foi branqueado com diferentes combinações de tempo-temperatura na faixa de 0-10minutos e 80-100 ºC. O comportamento cinético das três enzimas indicou a presença de duas isoenzimas com diferentes estabilidades térmicas, seguindo o modelo bifásico. A análise cinética demonstrou ainda, a alta resistência térmica das enzimas avaliadas, sendo que a inulinase foi a mais resistente ao calor. A análise termodinâmica indicou que a adição do ácido cítrico ao suco de yacon, provavelmente, causou a desnaturação da maior parte das enzimas que posteriormente foram agregadas durante o branqueamento. Posteriormente, o suco de yacon foi microencapsulado por atomização a fim de avaliar o uso da polidextrose como material de parede através da comparação com a goma arábica que é um dos encapsulantes mais utilizados em alimentos. Os efeitos da concentração dos agentes encapsulantes e da temperatura de secagem no teor de compostos fenólicos totais, atividade antioxidante, frutoligossacarídeos, umidade, atividade de água, solubilidade, higroscopicidade, cor e morfologia foram investigados. Os resultados indicaram que a polidextrose apresentou bom desempenho no microencapsulamento de componentes bioativos do suco de yacon, apresentando alta retenção dos compostos fenólicos e da atividade antioxidante. Em todos os tratamentos avaliados teve comportamento muito similar à goma arábica apresentando boas características, tais como baixa umidade, atividade de água e higroscopicidade e elevada solubilidade. Posteriormente, a cinética e termodinâmica de degradação dos compostos fenólicos e a cinética da degradação da diferença total de cor dessas microcápsulas foram avaliadas sob condições de cinética acelerada de armazenamento, com umidade relativa de 75 e 90% e temperaturas de 35 e 45 ºC. As microcápsulas foram atomizadas na temperatura de 140 ºC com goma arábica e polidextrose na proporção de 10% e armazenadas nessas condições por 35 dias. A degradação dos compostos fenólicos e da diferença total de cor das microcápsulas exibiram cinética de primeira ordem. Em relação à degradação dos compostos fenólicos, para todas as condições de umidade e temperatura, as microcápsulas com goma arábica foram mais estáveis do que as encapsuladas com polidextrose, apresentando maiores tempos de meia vida. Entretanto, os valores dos parâmetros termodinâmicos tiveram valores similares, indicando que a degradação dos fenóis ocorreu de forma similar nas microcápsulas independente do material de parede utilizado. As constantes de velocidades da degradação da diferença total de cor das microcápsulas não apresentaram diferença significativa com o aumento da temperatura e/ou da umidade relativa. Paralelamente, foi avaliada a estabilidade do bagaço de yacon desidratado através das isotermas de sorção e análise termodinâmica. O bagaço é o subproduto do processo de extração do suco, tem baixa atividade de água e potencial para uso em formulações alimentícias devido ao teor de FOS que permanece mesmo após a secagem. Os dados de umidade de equilíbrio de bagaço de yacon desidratado em pó foram determinados nas temperaturas de 20, 30, 40 e 50 ºC e o modelo de Halsey ajustou adequadamente os dados de sorção. As isotermas obtidas foram do tipo III, características de produtos contendo açúcares. / Yacon (Smallanthus sonchifolius) is a root of Andean origin, considered to be a functional food as it presents fructooligosaccharides (FOS) and phenolic compounds in its composition. FOS are fructose polymers with a polymerization degree of 3–10 units and have been referred to as prebiotics and dietary fibers because they are not digestible by the enzymes of the human digestive tract and they selectively stimulate the growth and activity of of health promoting bacteria. Other than their prebiotic action, yacon roots are rich on phenolic compounds with antioxidant properties, which protect the human body from oxidative processes. However, the presence of such compounds makes the roots susceptible to enzymatic browning reaction caused by peroxidase and polyphenoloxidase. Thereby, initially, a study was conducted on the kinetics of thermal inactivation and thermodynamic parameters during blanching of these enzymes as well as inulinase enzyme on yacon juice. The yacon juice, previously acidified with 1% citric acid was blanched with different time-temperature combinations in the ranges of 0-10 minutes and 80-100 °C. The kinetic behavior of the three enzymes indicated the presence of two isoenzymes with different thermal stabilities, following the biphasic model. Furthermore, the kinetic analysis showed high thermal resistance for the evaluated enzymes, where in inulinase was the most heat resistant. Thermodynamic analysis indicated that the adding of citric acid to the yacon juice, probably, caused the denaturation of the most of the enzymes that were subsequently aggregated during blanching. Afterwards, yacon juice was microencapsulated by spray drying with the aim of evaluating the use of polydextrose as wall material through in comparison to gum arabic, which is one of the more often used encapsulants in food. The effects of the concentration of the encapsulating agents and drying temperature in the content of total phenolic compounds, antioxidant activity, fructooligosaccharides, moisture, water activity, solubility, hygroscopicity, color, and morphology were investigated. The results indicated that polydextrose presented a good performance in the encapsulation of yacon juice, presenting high retention of phenolic compounds and antioxidant activity. On all the evaluated treatments, a behavior similar to arabic gum was observed, presenting good characteristics, such as low moisture content, water activity and hygroscopicity and high solubility. Hereafter, the kinetics and thermodynamics of the degradation of phenolic compounds and the kinetics of the degradation of the total color difference of these microcapsules were evaluated under accelerated storage kinetics conditions, with relative humidity of 75 and 90% and temperatures between 35 and 45 °C. The spray drying process was performed under a temperature of 140°C with arabic gum and polydextrose in a 10% concentration and stored under such conditions for 35 days. Degradation of phenolic compounds and total color of microcapsules showed first order kinetics. As of phenolic compound degradation, for all the conditions of relative humidity and temperature the microcapsules with arabic gum were more stable than the ones encapsulated with polydextrose, presenting longer half-lives. Nevertheless, values for the thermodynamic parameters were similar, indicating that the degradation of the phenols occurred in a similar way in the microcapsules, regardless of the wall material used. The kinetic analysis for total color difference of the microcapsules showed that the increase in temperature and/or relative humidity caused no significant difference on the the rate constants. Meantime, the stability of dehydrated yacon bagasse was evaluated by use of sorption isotherms and thermodynamic analysis. The bagasse is a byproduct of the juice extraction process, with low water activity and potential for usage in food formulations due to residual FOS content, even after drying. Equilibrium moisture data for powdered dehydrated yacon bagasse was determined under temperatures of 20, 30, 40, and 50°C and the Halsey model suitably adjusted to the sorption data. The isotherms thus obtained were class III isotherms, typical of sugar rich products.

A microestrutura típica dos aços inoxidáveis duplex (AID) e superduplex (AISD) proporciona uma excelente combinação de resistência à corrosão e propriedades mecânicas. Como resultado, os AID e AISD possuem aplicações na indústria do óleo e gás, papel e celulose, química, petroquímica e geração de energia. Neste trabalho, foi realizado um estudo com o objetivo de analisar a influência de diferentes frações volumétricas das fases ferrita (d) e austenita (g) nas propriedades mecânicas do aço UNS-S32760. Inicialmente foi realizado um estudo termodinâmico-computacional, a fim de acompanhar a evolução das fases em termos de quantidade e composição química no intervalo de temperaturas compreendido entre 1050°C e 1150°C. Após as simulações termodinâmicas, foi realizada a caracterização mecânica e metalúrgica do aço em estudo. Assim, tendo por base as simulações termodinâmicas e objetivando-se analisar a evolução das fases ferrita e austenita, foram realizados tratamentos isotérmicos em diferentes tempos e temperaturas. Para tanto, fez-se uso (i) do software de simulação termodinâmica FactSage v. 6.4, (ii) técnicas metalográficas e DRX e, (iii) de uma máquina de ensaios universal. Os resultados mostraram que as frações volumétricas das fases ferrita e austenita são função do tempo e temperatura empregados e indicaram, também, forte correlação entre a morfologia e distribuição das fases e as propriedades mecânicas do aço inoxidável superduplex UNS-S32760. / The typical microstructure of duplex (DSS) and superduplex (SDSS) stainless steels provides an excellent combination of corrosion resistance and mechanical properties. As a result, DSS and SDSS have applications in the oil and gas industry, pulp and paper, chemical, petrochemical and power generation. In this work, a study was conducted in order to analyze the influence of different volume fractions of ferrite and austenite phases on the mechanical properties of UNS-S32760 steel. Initially a computational thermodynamic study was conducted in order to follow the phase evolution in terms of amount and chemical composition in the temperature range between 1050°C and 1150°C. After the thermodynamic simulation, the mechanical and metallurgical characterization of the steel under study were carried out. Thus, based on the thermodynamic simulations and aiming to study the development of ferrite and austenite phases, isothermal treatments were performed at several time span and temperature. Consequently, (i) the thermodynamic simulation software FactSage v. 6.4, (ii) metallographic techniques and XRD and, (iii) a universal testing machine were use. The results showed that the volume fraction of ferrite and austenite phases are a function of the time and temperature and also indicated a strong correlation between morphology and phase distribution and the mechanical properties of superduplex stainless steel UNS-S32760.