[pt] Os processos de formação e de dissociação de hidratos são de grande interesse nas áreas ambiental e energética. Especificamente para a indústria de petróleo e gás, o hidrato aparece como um empecilho à garantia de escoamento, alavancando ainda mais a necessidade urgente de ampliar o conhecimento sobre seus fenômenos. Neste trabalho, uma nova abordagem para observar e compreender a cinética e as propriedades mecânicas de hidratos por meio da reologia interfacial é apresentada. O conhecido anel du Nouy é empregado com uma nova célula de latão projetada para permitir o necessário gerenciamento da temperatura de teste. Ciclopentano é utilizado como formador de hidrato. Com a nova geometria interfacial, diferentes temperaturas e protocolos de contato água/ciclopentano são explorados. A importância de primeiro provocar o contato do CP com cristais de gelo a fim de iniciar a formação de hidrato é de particular interesse. Assim, time sweeps são realizados em duas etapas: uma para a formação de gelo e outra para os formação de hidrato. Foi determinado que os hidratos de ciclopentano são detectados em temperaturas Tf menor ou igual a 6 graus Celsius. Uma interessante discussão a respeito do estado de metaestabilidade dos hidratos é, então, apresentada. Depois que os hidratos preenchem completamente a interface água/ciclopentano, strain sweeps são realizados para examinar a fragilidade dos filmes de hidrato, medindo os módulos interfaciais elástico e viscoso (G e G). As propriedades mecânicas desses filmes demonstraram uma forte dependência da temperatura (Tf ): o tempo de indução (tc), medido a partir do primeiro contato do ciclopentano com gelo, bem como o módulo elástico (G) e a deformação de escoamento (γy) aumentam conforme Tf é aumentada. / [en] Hydrate formation and dissociation processes are of major interest in environmental and energy fields. Specifically for the oil and gas industry, hydrate appears as an issue regarding flow assurance, pushing even more the urgent need for expanding the knowledge on hydrate phenomena. In the current work, a new approach to observe and understand the kinetics and mechanical properties of hydrates by interfacial rheology is presented. The standard du Nouy ring is employed with a novel brass cell designed to permit the necessary temperature management. Cyclopentane is used as hydrate former. With the new interfacial geometry, different temperature and water/cyclopentane contact protocols are explored. The importance of first contacting CP against ice crystals in order to initiate hydrate formation is of particular interest. Thus, time sweeps are performed in two stages: one for ice formation and another for hydrate formation. It was determined that cyclopentane hydrates only arise at temperatures Tf less than or equal to 6 celsius degree. A worthwhile discussion regarding the hydrate metastability state is then presented. After hydrates completely populate the water/cyclopentane interface, strain sweeps of the interfacial elastic and viscous moduli (G and G) are conducted to examine the fragility of the hydrate films. The mechanical properties of hydrate films demonstrated high dependence on temperature (Tf): the induction time (tc), measured from the moment when cyclopentane first contacts ice, as well as the elastic modulus (G) and the yield strain (γy) increase as Tf is increased.

En raison de la demande de miniaturisation croissante dans l’industrie microélectronique, il est nécessaire de développer des circuits imprimés multicouches (PCB, Printed Circuit Board) présentant une densité d’interconnections de plus en plus élevée. Avec leurs bonnes propriétés physico-chimiques et mécaniques et un relatif faible coût, les matériaux composites à base de résine époxy sont des matériaux de premier choix pour ce type d’application. Cependant, la réduction de la taille des connexions électriques de cuivre (largeur < 1 µm), implique que l’adhésion cuivre/époxy soit améliorée. Dans la littérature, des études ont montré que le taux de réticulation des résines epoxy est un paramètre clé, contrôlant la résistance chimique de la résine epoxy (vis-à-vis des procédés industriels d’impression de cuivre par voie chimique) et les propriétés d’adhésion du cuivre sur le substrat composite.L’objectif de cette thèse est d’étudier de façon approfondie la cinétique de réticulation d’un composite époxy/silice (ABF) utilisé en production de masse dans l’industrie microélectronique afin de proposer un protocole de fabrication des circuits imprimés en fonction du taux de réticulation.Le comportement rhéologique du matériau composite en fonction du taux de réticulation a été étudié par analyse mécanique dynamique (DMA). L’influence du taux de réticulation sur les processus de gélification et de vitrification est présentée et une analyse du comportement viscoélastique de la résine epoxy près de la transition vitreuse est discutée. Le modèle WLF est utilisé pour décrire la dynamique de réseau du polymère. La cinétique de réticulation du composite a été étudiée in situ en spectroscopie proche-infrarouge (NIR) et en calorimétrie différentielle à balayage (DSC) en modes isotherme et non-isotherme. L’analyse iso-conversionnelle a permis de déterminer l’énergie d’activation de la réaction de réticulation. Cependant, une modélisation plus approfondie de la cinétique de réticulation a été nécessaire en raison d’une contribution de diffusion s’ajoutant à la contribution chimique de la réaction. Cette étude a montré que les cinétiques de réticulation peuvent être décrites par le modèle auto-catalytique d’ordre n combiné aux modèles de Rabinowitch et WLF-modifié, modèles tenant compte de la contribution de diffusion. Ce modèle a permis de prédire le comportement du matériau dans une large gamme temps/température et d’établir le diagramme Température-Temps-Transformation du matériau .Compte tenu de l’importance du taux de réticulation sur les propriétés d’adhésion des connexions électriques de cuivre, une méthode de mesure du taux de réticulation sur des PCB industriels a été développée. La spectroscopie infrarouge en réflexion diffuse (DRIFTS) s’est avérée être une technique d’analyse parfaitement adaptée. L’influence du taux de réticulation sur l’étape de “desmear” du procédé de fabrication a également été étudiée. Cette étape, constituée d’une phase de gonflement de la résine epoxy (swelling) suivie d’une attaque oxydante au permanganate et d’une étape de réduction, est déterminante quant à la rugosité de surface obtenue et donc l’adhésion du cuivre sur le substrat composite. Une méthode originale a été développée pour déterminer le profil de diffusion de l’agent de gonflement (sweller) au sein du matériau, méthode alliant microtomie et analyse chromatographique. L’effet des conditions de “swelling” sur la rugosité finale du matériau a été déterminé par microscopie à force atomique (AFM). Des tests d’adhésion du cuivre ont également été réalisés afin d’étudier l’influence du taux de réticulation de la résine epoxy et de la rugosité de surface du composite sur la force d’adhésion. Finalement, une bonne adhésion du cuivre (environ 4 N/cm) pour des surfaces de faible rugosité (< 10 nm). / Due to the increasing miniaturization in microelectronics the manufacturing of densely interconnected multilayer printed-circuit boards (PCB) is needed. With their well-balanced physico-chemical and mechanical properties and low cost, epoxy-based composites are insulating materials of prime choice. However, to achieve interconnections at a lower scale (copper line width down to ca. 1 µm), the adhesion between the composite substrate and the copper interconnections must be enhanced. Previous studies showed that the degree of curing of the epoxy matrix (i.e. conversion of crosslinking reaction) is one key-parameter, driving the matrix chemical and mechanical resistance (during the PCP manufacturing process) and the composite/copper line adhesion properties.In this work we present and discuss an in-depth study of the curing kinetics of an epoxy/silica composite (ABF) relevant to the microelectronics industry. The final objective is to propose a process protocol of the PCB manufacturing as function of the degree of curing.The rheological behaviour of the composite material is investigated by dynamic mechanical analysis (DMA). The gelation and vitrification mechanisms are presented as a function of the degree of curing. The viscoelastic behavior of the epoxy matrix near the glass-transition is studied and is shown to be well-described by the WLF model.The curing kinetics of the epoxy composite are studied by in situ near-infrared (NIR) spectroscopy and both isothermal and non-isothermal differential scanning calorimetry (DSC). Iso-conversional analyses are performed to determine the apparent activation energy of the curing reaction. Due to a non-negligible contribution of the diffusion part in the curing reaction, further modelling was needed to achieve a complete description of the curing kinetics. This study showed that the curing kinetic is well-described by the nth-order autocatalytic fitting model in combination with the Rabinowitch/modified-WLF models, taking into account the diffusion contribution. This model is used to predict the material behaviour in a wide time/temperature range and to propose a Temperature-Time-Transformation diagram of the material.Due to the influence of the degree of curing on the adhesion of copper electrical lines, an experimental method for the measurement of the degree of curing of industrial PCB was developed. Diffuse-reflectance infrared spectroscopy (DRIFTS) is found to be a versatile and accurate technique. The influence of the degree of curing on the “desmear” step of the PCB manufacturing process is studied as well. The “desmear” step proceeds in the swelling of the epoxy matrix and the subsequent permanganate etching and reduction reactions. The “desmear” step is quite important regarding the composite surface roughness and, as a consequence, the adhesion of the copper lines. An original method for the determination of the diffusion profile of the sweller through the depth of the material was developed using microtomy and chromatography. The effect of swelling experimental parameters on the final roughness of the composite is determined by atomic force microscopy (AFM). Adhesion tests of copper lines on the composite substrate are performed to study the influence of the initial degree of curing and the roughness on the peel strength. Good adhesion of copper (about 4 N/cm) is achieved for a low substrate roughness (< 10 nm).

La fracture des matériaux, omniprésente aussi bien en science des matériaux qu’en géologie, implique souvent des événements soudains et imprévisibles, sans précurseurs détectables macroscopiquement. Une compréhension approfondie des mécanismes microscopiques conduisant in fine à la rupture est requise, mais les expériences restent rares. La détection de la dynamique microscopique dans les échantillons cisaillés est expérimentalement très difficile, car elle nécessite de combiner sensibilité mécanique, qualité optique et exigences strictes sur l’encombrement. Dans ce travail, nous présentons l'une des premières tentatives réussies de mesure des précurseurs microscopiques de fracture dans des matériaux mous modèles, grâce à des mesures de la plasticité microscopique à l'aide d'un nouvel instrument, couplant une cellule de cisaillement à contrainte contrôlée à un appareil de diffusion de lumière statique et dynamique (DLS) à petits angles. Dans un premier temps, nous montrons théoriquement, numériquement et expérimentalement comment la DLS, une technique très puissante difficile à utiliser pour un échantillon sous cisaillement, peut être utilisée comme outil de mesure de la dynamique microscopique dans les systèmes mous sous cisaillement. Pour un solide parfait et un fluide visqueux simple, le champ de déplacement résultant d'une déformation de cisaillement est purement affine. Nous montrons comment les déplacements affines et non affines, qui sont présents dans de nombreuses situations d’intérêt (matériaux élastiquement hétérogènes ou en raison de réarrangements plastiques) peuvent être évalués séparément par DLS et discutons de l'effet des non-idéalités dans des expériences typiques.Ce travail est centré sur un gel colloïdal fractal modèle, dont nous caractérisons la rhéologie linéaire en loi de puissance. Nous montrons que celle-ci est décrite par un modèle phénoménologique Fractional Maxwell (FMM), et discutons la relation possible entre FMM et la structure microscopique du gel.Sous une contrainte de cisaillement constante (expérience de fluage), le gel colloïdal présente une déformation rapide élastique suivie d'un fluage lent en loi de puissance, puis, après plusieurs heures par une accélération du taux de cisaillement, entraînant la rupture retardée du gel. Nos expériences montrent que le premier régime en loi de puissance, bien décrit par la viscoélasticité linéaire, correspond à l'échelle microscopique à une dynamique partiellement nonaffine, mais entièrement réversible. Lorsque la viscoélasticité dévie de la linéarité, une accélération nette, localisée dans le temps de la dynamique non-affine, est observée. Ces réarrangements rapides précèdent la fracture macroscopique du gel de plusieurs heures: ce sont des précurseurs dynamiques de la fracture qui permettent de prédire l’évolution du gel bien avant toute mesure rhéologique.Pour obtenir une image plus complète de la fracture, nous étudions l'apparition de l'irréversibilité lors d’une perturbation cyclique répétée plusieurs fois (expérience de fatigue). En suivant l'évolution stroboscopique du système en fonction de la déformation cumulée, on constate que, au-delà du régime linéaire, le taux de relaxation augmente brusquement, signature de plasticité. Si la contrainte appliquée est suffisamment grande, le gel à long terme montre une rupture retardée, en analogie avec celle observée en fluage. Les différences et similitudes entre les deux mécanismes de fracture sont discutées.Enfin, la généralité des résultats obtenus sur les gels colloïdaux est vérifiée en étudiant comme second système modèle un verre colloïdal, dont la mise en écoulement sous contrainte oscillante est un processus progressif, pour lequel deux modes de relaxation contribuent à la dynamique observée. Les analogies qualitatives trouvées avec des systèmes similaires (par ex. des émulsions concentrées) suggèrent qu'une image unifiée pourrait être obtenue, motivant des recherches futures. / Material failure is ubiquitous, with implications from geology to everyday life and material science. It often involves sudden, unpredictable events, with little or no macroscopically detectable precursors. A deeper understanding of the microscopic mechanisms eventually leading to failure is clearly required, but experiments remain scarce. The detection of microscopic dynamics in samples under shear is experimentally very challenging, because it requires to combine the highest mechanical sensitivity to strict requirements on the geometry of the whole setup and on the quality of the optical interfaces. In this work we present one of the first successful attempts to measure microscopic failure precursors in model soft solids. Here, microscopic plasticity under shear is observed using a novel setup, coupling a custom-made stress controlled shear cell to small angle static and dynamic light scattering (DLS).DLS is a very powerful technique, but its application to materials under shear is not trivial. In a first step we show a theoretical, numerical and experimental investigation of how DLS may be used as a tool to measure the microscopic dynamics in soft systems under shear. In ideal solids and simple viscous fluids, the displacement field resulting from an applied shear deformation is purely affine. Additional non-affine displacements arise in many situations of great interest, for example in elastically heterogeneous materials or due to plastic rearrangements. We show how affine and non-affine displacements can be separately resolved by DLS, and discuss the effect of several non-idealities in typical experiments.As a model system, this work mainly focuses on a fractal colloidal gel. We thoroughly characterize the linear power-law rheology of the gel, we show that it is very accurately described by the phenomenological Fractional Maxwell (FM) model, and we discuss the possible relationship between the FM model and the microscopic structure of the gel.Under a constant shear stress (creep experiment), the colloidal gel exhibits a fast, elastic deformation followed by a slow sublinear power-law creep, which is eventually interrupted after several hours by an upturn in the shear rate, leading to the delayed failure of the material. Our experiments show that the first power-law regime, nicely described by linear viscoelasticity, corresponds at the microscopic scale to partially nonaffine, yet fully reversible dynamics. Upon deviation from the linear viscoelasticity, a sharp acceleration, localized in time of the nonaffine dynamics is observed. These faster rearrangements precede the macroscopic failure of the gel by thousands of seconds: they thus are dynamic precursors of failure that allow one to predict the fate of the gel well before any rheological measurement.To obtain a more comprehensive picture of material failure, we next address the onset of irreversibility under a cyclic perturbation repeated many times (fatigue experiment). By following the stroboscopic evolution of the system as a function of the cumulated deformation, we observe that as soon as the shear amplitude is increased beyond the linear regime the relaxation rate increases abruptly, indicating that irreversible plasticity is at play. If a large enough stress amplitude is applied, the system on the long run displays delayed fatigue failure, with reminiscences of the one observed in creep. Differences and similarities between the two failure mechanisms are discussed.Finally, the generality of the results obtained on colloidal gels is checked by investigating as second model system a soft colloidal glass. In this case, our experiments indicate that oscillatory yielding is a gradual process, where two relaxation modes contribute to the observed dynamics. Qualitative analogies found with similar systems (e.g. concentrated emulsions) suggest that a general picture might be obtained with our study, which motivates ongoing and future investigations.

Cette thèse s’inscrit dans le projet ASCoPE qui vise à développer les connaissances scientifiques et technologiques nécessaires à la conception et à la réalisation d’un pilote de production d’acier par réduction électrochimique de particules d’hématite en suspension dans un milieu alcalin à 110°C, en vue de proposer un procédé industriel fiable et écologique, comme alternative au procédé classique reposant sur le charbon. Le mélange considéré contient une suspension d’hématite à 12% en volume dans une solution aqueuse de soude à 50% en masse. Cette thèse a pour objectif l’étude de la sédimentation et de la rhéologie des suspensions d’hématite et le comportement hydrodynamique des particules d’hématite dans une cellule inclinée et de quantifier l’éventuel phénomène d’impact sur la cathode / This thesis aims to develop scientific and technological knowledge needed to design a pilot production of steel by electrochemical reduction of hematite particles suspended in an alkaline medium at 110°C in order to provide a reliable and environmentally friendly industrial process, as an alternative to the conventional process based on coal. The mixture considered contains a suspension of hematite of 12% by volume in an aqueous sodium hydroxide solution of 50% by weight. This thesis seeks to study the sedimentation and rheology of hematite suspensions and the hydrodynamic behavior of hematite particles in inclined cell and to quantify the possible phenomeno impact on the cathode

In this work differential scanning calorimetry, dynamic mechanical analysis, Fourier-Transformed Infrared Spectroscopy [FT-IR] and polarized light microscopy will be employed to characterize polymeric systems. The first chapter broadly covers polymer synthesis and important characterization methods. In the second chapter, a polyamide (PA12) will be sintered via a novel additive manufacturing (AM) technology developed here at USF termed LAPS (Large Area Projection Sintering). LAPS uses extended sintering timespans to ensure complete melting and densification of the polymer powder over the entire two-dimensional area of the part’s footprint. Further, it allows for the printed layer to crystallize and shrink in its entirety as the temperature falls below the crystallization temperature prior to the next layer being added. The printed parts (termed coupons) will be assayed by DSC and polarized light microscopy to determine sintering efficacy. Additionally, the parts will be compared to coupons printed with conventional methods to show that the USF AM technology shows superior elongation at break (EaB), with comparable ultimate tensile strength (UTS) and Young’s Modulus to laser sintered coupons. This is notable as conventional AM methods produce parts which usually compromise between EaB and modulus. The EaB of LAPS-printed parts is comparable to injection molding (IM) grade PA12, which is remarkable as IM grade PA12 powder normally has higher molecular weight and limited crystallinity. The reduced crystallinity of IM grade PA12 parts is thought to be due to the high shear rates during injection and fast cooling rates post-fabrication. Further, the USF LAPS parts show minimal or no detectable porosity. Porosity is an artifact of the sintering process which conventional techniques like laser sintering (LS) have little ability to mitigate, as higher energy wattages simply burn and degrade the polymer surface with insufficient time available for heat transfer and bulk melt flow. Porosity is documented as one of the leading causes of part failure and decreased mechanical properties in the literature, and as such the USF AM technology is in the process of being patented as of March, 2018. Chapters three through six will explore a phenomenon first noticed by clinicians at the James A. Haley Veterans Hospital. They observed that starch-thickened drinks for patients suffering from dysphagia became dangerously thinned down upon addition of the osmotic drug polyethylene glycol (PEG) 3350, marketed as Miralax®. Starch-based hydrocolloids are common thickeners used for patients with dysphagia, and so any incompatibility with such a ubiquitous drug as PEG 3350 poses an immediate danger. Patients with the disorder can suffer increased rates of aspiration-related pneumonia, incurring up to nearly a 60% fatality rate within a year. Chances for aspiration greatly increase for food items which are too inviscid to safely swallow. Rheology and FT-IR spectroscopy will be used to show that the breakdown of the starch network in aqueous solution is dependent upon the molecular weight of PEG. As the molecular weight of PEG is reduced to that of a small molecule (~300MW) from its large drug form (3350MW), the structure stabilizes and can resist shearing forces in a steady shear rheological experiment. Spectroscopy will show that PEG molecular weight also influences syneresis and the crystallinity of the starch hydrocolloid solutions. It is postulated that the molecular weight of PEG influences its miscibility in starch solutions, and its ability to interrupt the hydrogen bonding and entanglements which maintain the elastic framework which allow starch thickeners to impart viscosity and resist shearing forces. When this framework collapses, absorbed water is expelled as evidenced as a biphasic separation where water collects on top of the starch suspension. This was the phenomenon observed by the clinicians at the Veterans’ Hospital.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-21T11:22:50Z No. of bitstreams: 1 MARCO TÚLLIO LIMA DUARTE - TESE (PPGEP) 2018.pdf: 2250276 bytes, checksum: fbe9c7f829118eade9f7ed9fba1f9644 (MD5) / Made available in DSpace on 2018-08-21T11:22:50Z (GMT). No. of bitstreams: 1 MARCO TÚLLIO LIMA DUARTE - TESE (PPGEP) 2018.pdf: 2250276 bytes, checksum: fbe9c7f829118eade9f7ed9fba1f9644 (MD5) Previous issue date: 2018-02 / A lichia (Litchi chinensis) é um fruto nativo da Ásia, sendo considerada a rainha das frutas. No Brasil, sua introdução se deu como planta ornamental e somente a partir da década de 70, teve seu consumo ampliado. Devido ao seu elevado valor comercial, curto período de safra e alta perecibilidade, uma das estratégias de ampliação da sua oferta é a sua desidratação e posterior uso do pó em bebidas lácteas probióticas. Dessa forma, objetivou-se no presente estudo a produção de lichia em pó através da liofilização, avaliando a estabilidade do pó durante o armazenamento e a elaboração de uma bebida láctea probiótica. Foram elaboradas três formulações de maltodextrina, nas concentrações de 15, 20 e 25%. Essas formulações foram previamente caracterizadas, juntamente com a polpa integral, foram avaliados seus comportamentos reológicos e em seguida, liofilizadas na temperatura de –40 °C durante 48 h. Após a caracterização dos pós, a melhor amostra foi submetida a análises de isotermas de adsorção de água, nas temperaturas de 30 e 40°C, analisada em microscopia eletrônica de varredura e armazenada em embalagens laminadas por 60 dias, nas temperaturas de 20, 30 e 40°C, quando foram monitoradas a cada 10 dias suas características, físicas, químicas e físicoquímicas. Adicionalmente, foram processadas bebidas lácteas fermentadas isentas de pó de lichia e nas concentrações de 7, 9 e 11% do pó, que foram caracterizadas quanto aos parâmetros físicos, químicos e físico-químicos. Os resultados obtidos revelaram que as polpas formuladas e desidratadas sofreram alterações quanto aos parâmetros avaliados em todas as amostras, em função da concentração da maltodextrina. A polpa integral e as diferentes formulações exibiram comportamento reológico típico de polpas de frutas, classificando-se como fluido não-newtoniano, de caráter pseudoplástico, cujo melhor ajuste matemático foi com o modelo de Mizrahi-Berk. O processo de liofilização refletiu em alterações dos parâmetros analisados, tendo o pó adicionado de 25% de maltodextrina exibido as melhores características dentre amostras avaliadas. A análise das isotermas de adsorção de água foram determinadas como tipo III e o melhor modelo matemático para descrição dos dados experimentais foi o de GAB, por exibir maiores valores de R2 e menores índices de erros médios relativos. Quanto à análise da microscopia eletrônica, foi constatado que o pó da lichia exibiu estruturas amorfas e aglomerado de partículas, com rugosidades acentuadas e grande porosidade. Durante o período de armazenamento, a maioria dos parâmetros físicos, químicos e físicoquímicos foram alterados, principalmente em função da temperatura de exposição e as bebidas lácteas probióticas demonstraram diferenças significativas em função da elevação da concentração do pó de lichia adicionado como saborizante. / The lychee (Litchi chinensis) is a fruit native to Asia, being considered the queen of the fruit. In Brazil, its introduction was given as an ornamental plant and only from the decade of 70, had its consumption expanded. Due to its high commercial value, short harvest period and high perishability, one of the strategies to expand their offer is your dehydration and subsequent use of powder in probiotic dairy drinks. Thus, the objective of the present study verified the production of lychee powder by lyophilization, evaluating the stability of powder during storage and prepares a probiotic milk drink. In this way, were drawn up three formulations, added maltodextrin, at concentrations of 15, 20 and 25%. These formulations were previously characterized, along with the integral pulp, evaluated their rheological behavior and then freeze at a temperature of - 40 °C for 48 h. The powders obtained were subsequently characterized and the best sample, subjected to analyzes of adsorption isotherms of water at temperatures of 30 and 40 °C, analyzed in scanning electron microscopy and stored in laminated packaging by 60 days at temperatures of 20, 30 and 40 °C, when were monitored every 10 days, its characteristics, physical, chemical and physico-chemical properties. In addition, were processed fermented dairy drinks free of powder of lychee and at concentrations of 7, 9 and 11% of powder, which were characterized according to the physical, chemical and physico-chemical properties. The results obtained showed that the dehydrated pulps formulated and suffered changes regarding the parameters evaluated in all samples, depending on the concentration of maltodextrin. The integral pulp and the different formulations exhibited rheological behavior typical of fruit pulps, classifying it as non- Newtonian fluid, pseudoplastic character, whose best fit was with the mathematical model of Mizrahi-Berk. The lyophilization process reflected in changes of the parameters analyzed, taking the powder added to 25%maltodextrin displayed the best characteristics among samples. The analysis of adsorption isotherms of water were determined as type III and the best mathematical model for description of the experimental data was the GAB, to display larger values of R2 and lower rates of errors average. Regarding the analysis of electronic microscopy, it was noticed that the powder of the lychee exhibited amorphous structures and particleboard, with pronounced roughness and high porosity. During the storage period, most of the physical, chemical and physico-chemical parameters were altered, mainly in function of the temperature of exposure and the probiotic dairy drinks have demonstrated significant differences depending on the elevation of the concentration of powder of lychee added as flavor.

Objetivos: Desenvolver e caracterizar hidrogéis de quitosana contendo capsaicinóides nanoencapsulados, bem como analisar o efeito das nanocápsulas e do veículo nos perfis de liberação dos capsaicinóides. Metodologia: As nanocápsulas foram obtidas (método de deposição interfacial do polímero préformado) utilizando Eudragit® RS100 e triglicerídeos do ácido cáprico/caprílico como parede polimérica e núcleo oleoso, respectivamente, e foram caracterizadas. Para determinação do teor e da taxa de associação da capsaicina e dihidrocapsaicina às nanocápsulas utilizou-se metodologia validada por CLAE-UV. As nanocápsulas contendo capsaicinóides foram incorporadas em hidrogel de quitosana. Para tanto, determinaram-se previamente as características reológicas e o hidrogel ideal para uso tópico. Através dos estudos de liberação in vitro, utilizando método de saco de diálise, foram obtidos os perfis de liberação dos fármacos a partir das nanocápsulas e destas incorporadas no veículo semissólido. Resultados e Discussão: As nanocápsulas apresentaram diâmetro médio de partícula de 153 ± 7nm (PDI < 0,2), potencial zeta de + 9,62 ± 1,48 mV, pH de 5,7 ± 0,1 e uma leve tendência à sedimentação, típica de suspensões. A nanoencapsulação dos capsaicinóides não provocou alterações nas características da formulação. O teor e a taxa de associação foram próximos a 100% para ambos capsaicinóides, considerando concentração de 0,5mg/mL de capsaicinoides na formulação. Foi possível obter um hidrogel de quitosana contendo nanocápsulas adequado para uso tópico. Previamente, observou-se uma grande influência da concentração de quitosana na consistência dos hidrogéis e um comportamento reológico pseudoplástico que não foi alterado pela adição das nanocápsulas. Observou-se uma liberação controlada devido à nanoencapsulação, de modo que dihidrocapsaicina foi liberada mais lentamente do que a capsaicina. Pode-se observar um retardo na liberação da capsaicina, quando as nanocápsulas foram incorporadas no hidrogel. Conclusões: Nanocápsulas estáveis e capazes de controlar a liberação dos capsaicinóides foram obtidas, sendo que tanto o núcleo oleoso quanto o polímero são responsáveis pelo controle da liberação. A formulação semissólida contendo nanocápsulas, obtida a partir do polímero quitosana, manteve a liberação controlada observada e apresentou adequadas características para aplicação tópica. / Purpose: To develop and characterize chitosan hydrogels containing nanoencapsulated capsaicin and dihydrocapsaicin, as well as to analyze the effect of the nanocapsulation and the vehicle on the in vitro release of the capsaicinoids. Methodology: Nanocapsules were obtained (interfacial deposition of the pre-formed polymer method) using Eudragit® RS100 and capric/caprylic triglycerids as the polymeric shell and oily core, respectively, and they were characterized. An HPLCUV validated method was used to determine the drug content and drug encapsulation efficiency. The nanocapsules containing capsaicinoids were incorporated in a chitosan hydrogel. Previously, the rheological properties and the most suitable hydrogel aiming the topical delivery were determined. By means of in vitro release experiments (dialyses bags), the release profiles of the capsaicinoids from the nanocapsules and the gel containing nanocapsules were obtained. Results and Discussion: The nanocapsule formulation presented an average diameter of 153 ± 7nm (PDI < 0.2), the zeta potential was +9.62 ± 1.48 mV, and the pH 5.7± 0.1. A slight tendency to sedimentation was observed, typical of suspensions. The drug encapsulation did not alter the formulation properties. The drug content and encapsulation efficiency were nearly 100% for both capsaicinoids, considering a drug amout of 0.5mg/mL of capsaicinoids in the formulation. A chitosan hydrogel containing nanocapsules were successfully obtanined. The chitosan concentration significantly influenced the consistence of the formulations, and the pseudoplastic behavior did not change after the nanocapsule incorporation. controlled release was observed due to nanoencapsulation, in a way that capsaicin released faster than dihydrocapsaicin. The release of capsaicin from the hydrogel containing nanocapsules presented a delay in comparison with the release from the nanocapsule suspension. Conclusions: Stable nanocapsules capable of controlling the capsaicinoids release were obtained. Both the oily core and the polymeric shell are responsible for the controlled release. The semi-solid formulation containing nanocapsules obtained with the polymer chitosan maintained the controlled release and presented suitable properties for cutaneous applications.

O processo de microfabricação por coextrusão (MFCX) foi estudado a fim de obter compósitos de zirconato titanato de chumbo (PZT), por meio da fabricação de fibras. O princípio desta técnica é a redução dimensional de um pré-formato cilíndrico formado pelos materiais já nas posições e proporções desejadas ao longo da secção transversal em filamentos mais finos, através da passagem por um molde. Tais componentes devem possuir o mesmo comportamento reológico para que possam fluir juntos, fazendo com que o pré-formato sofra apenas uma redução da secção transversal ao passar pela boquilha. Entre tais componentes, o material principal é uma suspensão concentrada de pó de PZT e polietileno de baixa densidade (PEBD). Este fornece a característica termoplástica para a mistura e auxilia na resistência mecânica a verde. Existe ainda, o material provisório, o qual já havia sido estudado e foi trocado de negro de fumo (NF) para celulose microcristalina (MCC), uma vez que com o uso de NF, um resíduo inorgânico foi verificado após a etapa de retirada do ligante o qual poderia influenciar na microestrutura e nas propriedades piezoelétricas do PZT, causando queda na polarização obtida. Para caracterizar a reologia das misturas, foram usados pré-formatos cilíndricos formados por metades de diferentes materiais com secção transversal semicircular, tendo como composição padrão 58 vol. % de PZT + PEBD. Já os materiais provisórios foram estudados nas seguintes composições: 25 vol. % de NF + PEBD, 31 vol. % de MCC + PEBD e 41 vol. % de MCC + ácido esteárico (AE) + PEBD. Os filamentos obtidos após a passagem pelo molde foram caracterizados e posteriormente comparados entre si, a fim de verificar a influência do material fugitivo e dos aditivos na microestrutura. A capacidade do pré-formato de manter o equilíbrio das dimensões e proporções após a coextrusão também foi verificada por meio de análise de imagem. Verificou-se que as misturas de MCC + PEBD e PZT + PEBD não foram capazes de fluir concomitantemente mesmo quando ambas apresentavam a mesma viscosidade. Assim, a reologia foi estudada considerando não apenas a viscosidade, mas também as propriedades de deslizamento na parede do molde para este sistema. Depois de modificações na composição e parâmetros do processo, foi obtida uma equivalência adequada entre os materiais, concluindo que a coextrusão de dois materiais compondo um pré-formato de seção transversal complexa pode ser bem-sucedida quando as mesmas velocidades de deslizamento na parede e as mesmas viscosidades corrigidas puderem ser encontradas para a mesma taxa de cisalhamento. / The process of microfabrication by coextrusion (MFCX) was investigated to obtain composites of lead zirconate titanate (PZT), through the fabrication of PZT fibers. The principle of this technique is the reduction of a preform formed of concentrated suspensions in the positions and proportions desired, into filaments thinner after passing through a die. Such materials must have the same rheological behavior so they can flow together, making the preform to suffer only a reduction in the cross section to pass through the capillary. The main material was a concentrated suspension of PZT powder and low density polyethylene (LDPE), which provides the thermoplastic characteristic for the mixture and improves the mechanical strength at green state. In the other hand, the fugitive material was changed from carbon black (CB) into microcrystalline cellulose (MCC), once with the use of CB, an inorganic residue was found after the step of debinding. Furthermore, the CB impurities could influence the piezoelectric properties of PZT, causing a drop in the polarization measured. The rheological characterization employed preforms with cross section geometry of a half moon, with a standard composition of 58 vol. % PZT. Meanwhile, the fugitive materials were studied using the following compositions: 25 vol. % CB + LDPE, 31 vol. % MCC + LDPE and 41% vol. MCC + stearic acid (ST) + LDPE. The filaments obtained were characterized and then compared to verify the influence of the fugitive material and the additives on the microstructure. The ability of the preform to maintain the balance of the dimensions and proportions after co-extrusion was also verified by image analysis. It was found that mixtures of MCC + LDPE and CB + LDPE were not able to flow simultaneously. Thus, the rheology was studied considering not only the viscosity but also the properties of slip on the wall of the capillary die. After changing the composition and process parameters, a good match between the materials could be obtained, which allowed the coextrusion in the shape of half moon, getting a constant and well defined reduction of the diameter.

A distribuição de massa molar (DMM) e seus parâmetros são de fundamental importância na caracterização dos polímeros. Por este motivo, o desenvolvimento de técnicas que permitam a determinação da DMM de forma mais rápida e a menor custo é de grande importância prática. Os principais objetivos deste trabalho foram a implementação de alguns dos modelos baseados da teoria da reptação dupla propostos na literatura para descrever o mecanismo de relaxação das cadeias poliméricas, a avaliação dessas implementações e a análise de dois passos fundamentais na obtenção da DMM a partir de dados reológicos que são a metodologia de cálculo do espectro de relaxação baseado no modelo de Maxwell e a estratégia para a avaliação numérica das integrais que aparecem nos modelos de relaxação. Foi resolvido o problema denominado problema inverso, ou seja, a determinação da DMM a partir de dados reológicos usando um modelo de relaxação especificado e uma função de distribuição imposta. Foi usada a função Exponencial Generalizada (GEX) para representar a probabilidade de distribuição, sendo consideradas duas abordagens: i) cálculo explícito do espectro de relaxação e ii) aproximações paramétricas de Schwarzl, que evitam a necessidade do cálculo explícito do espectro de relaxação. A metodologia de determinação da DMM foi aplicada para amostras de polietileno e foram estimadas distribuições com boa representação dos dados experimentais do GPC, ao considerarem-se amostras com polidispersões inferiores a 10. Com relação a metodologia de cálculo do espectro de relaxação, foi realizado um estudo comparativo da aplicação de espectros de relaxação discreto e contínuo, com o objetivo de estabelecer critérios para especificação do número ótimo de modos de Maxwell a serem considerados. Ao efetuar-se a comparação entre as técnicas, verificou-se o espectro discreto apresenta como um sistema melhor condicionado, permitindo assim obter maior confiabilidade dos parâmetros estimados. Também é proposta uma modificação da metodologia de determinação da DMM, em que é aplicada a quadratura de Gauss-Hermite para a resolução numérica da integral dos modelos de relaxação. / The molecular weight distribution (MWD) and its parameters are of the fundamental importance in the characterization of polymers. Therefore, the development of techniques for faster and less time consuming determination of the MWD is of great practical relevance. The goals of this work were the implementation of some of the relaxation models from double reptation theory proposed in the literature, the evaluation of these implementations and the analysis of two key points in the recovery of the MWD from rheological data which are the methodology for calculation of the relaxation spectrum based on the Maxwell model and the numeric strategy for the evaluation of the integrals appearing in the relaxation models. The inverse problem, i.e., the determination of the MWD from rheological data using a specified relaxation model and an imposed distribution function, was solved. In the analysis of the inverse problem, the Generalized Exponential (GEX) was used as distribution function and two approaches were considered: i) explicit calculation of the relaxation spectrum and ii) use of the parametric method proposed by Schwarzl to avoid the explicit calculation of the relaxation spectrum. In the test of commercial samples of polyethylene with polidispersity less than 10, the application of this methodology led to MWD curves which provided good fit of the experimental SEC data. Regarding the methodology for calculation of the relaxation spectrum, a comparison between the performance of discrete and continuous relaxation spectrum was performed and some possible a criteria to determine the appropriate number of relaxation modes of Maxwell to be used were evaluated. It was found that the technique of discrete spectrum leads to better conditioned systems and, consequently, greater reliability of the estimated parameters. With relation to the numeric strategy for the evaluation of the integrals appearing in the relaxation models, the use of Gauss-Hermite quadrature using a new change of variables was proposed.

No presente trabalho, avaliou-se os efeitos individuais e combinados de nove enzimas comerciais sobre as propriedades reológicas de massa das farinhas de trigo, com o objetivo de identificar seus efeitos sinérgicos ou antagônicos e as suas concentrações ótimas, como alternativa para substituição de oxidantes químicos no tratamento de farinhas. α-Amilases de origem fúngica (AMY-F), bacteriana (AMY-B) e maltogênica (AMY-M), xilanases fúngica (XYL-F) e bacteriana (XYL-B), glucose oxidase (GOX), lacase (LAC), lipase (LIP) e transglutaminase (TG) foram testadas em dois tipos de farinha: uma farinha forte padrão (farinha A) e uma farinha fraca comum (farinha B). Inicialmente, as enzimas foram adicionadas individualmente na farinha onde, seus efeitos sobre Falling Number (FN), farinografia e alveografia, foram avaliados variando-se suas concentrações de 25 - 833 U.kg-1, a fim de se identificar as faixas de concentração ideais de cada uma delas. Identificou-se que as α-amilases afetaram principalmente as propriedades farinográficas, reduzindo a capacidade de absorção de água (WA) e tempo de estabilidade (ST) das massas. Para o ajuste de FN, AMY-B (150 U.kg-1) foi mais eficiente que AMY-F (583 U.kg-1) e AMY-M (583 U.kg-1). As xilanases melhoraram o valor de W (10-4 J) e razão P/L, sendo que em todos os testes XYL-B foi mais eficiente do que XYL-F. Na concentração de 25 U.kg-1, GOX e LAC melhoraram o ST, razão P/L e valor de W; no entanto, aumentaram o tempo de desenvolvimento (DT) das massas. LIP (150 U.kg-1) promoveu a melhora no W e DT, enquanto que TG não apresentou efeitos significativos na maioria dos parâmetros avaliados. A partir disso, os efeitos combinados das enzimas foram avaliados através de dois planejamentos experimentais sequenciais. Para farinha A, a combinação enzimática ótima foi AMY-B (166 U.kg-1), AMY-M (133 U.kg-1), XYL-B (150 U.kg-1), GOX (8 U. kg-1) e LIP (150 U.kg-1). Identificou-se um efeito sinérgico entre XYL-B e GOX na melhoria do W e razão P/L. Para a farinha B, a combinação enzimática ótima foi AMY-B (150 U.kg-1), LIP (150 U.kg-1), GOX (100 U.kg-1) e LAC (200 U.kg-1), sendo que GOX e LAC apresentaram um efeito cooperativo, quando usadas em concentrações opostas. As combinações enzimáticas foram mais eficientes do que a azodicarbonamida, cujo efeito, mesmo na concentração máxima (40 ppm) permitida pela legislação, não melhorou os parâmetros reológicos das massas. Foi demonstrado que é possível a substituição de oxidantes químicos por enzimas para o tratamento de farinhas, a fim de melhorar a reologia das massas, mesmo para uma farinha fraca, tornando-a adequada para panificação. / In the present work, it was evaluated the individual and combined effects of nine commercial enzymes on the rheological properties of dough wheat flour, aiming to identify synergistic and antagonist effects between the enzymes and their optimal concentrations as substitutes of chemical oxidants. Fungal (AMY-F), bacterial (AMY-B) and maltogenic (AMY-M) -amylases, fungal (XYL-F) and bacterial (XYL-B) xylanases, glucose oxidase (GOX), laccase (LAC), lipase (LIP) and transglutaminase (TG) were tested in two types of flour: standard strong flour (flour A) and common weak flour (flour B). Initially, Falling Number, farinography and alveography analysis were carried out varying the enzymes concentrations from 25 to 833 U.kg-1, to identify the ideal ranges of each of them to improve the rheological characteristics of dough wheat flour. It was identified that α-amylases affected mainly the farinographic properties, reducing the water absorption (WA) and stability time (ST). AMY-B was the most effective enzyme for setting the FN, requiring 150 U.kg-1, while for AMY-F and AMY-M it was necessary 583 U.kg-1. In all tests, XYL-B was more efficient than XYL-F, but both improved the W (10-4 J) value and P/L ratio. At 25 U.kg-1, GOX and LAC had important improves on the ST, P/L ratio and W value, however increased undesirably the development time (DT). LIP (150 U.kg 1) promoted the improvement in W value and DT, while TG had not significant effects on most of the evaluated parameters. After that, the combined effects of enzymes were evaluated through two sequential experimental designs. For flour A, the optimal combination of enzymes was AMY-B (166 U.kg-1), AMY-M (133 U.kg-1), XYL-B (150 U.kg-1), GOX (8 U.kg-1) and LIP (150 U.kg-1). It was identified a synergistic effect between XYL-B and GOX to improvement of W value (10-4 J) and the P/L ratio. For the flour B, the optimal combination of enzymes was AMY-B (150 U.kg-1), LIP (150 U.kg-1), GOX (100 U.kg-1) and LAC (200 U.kg-1). GOX and LAC presented a cooperative effect, when they were used at opposite concentrations. The enzymes mixtures were compared with chemical oxidant azodicarbonamide, and, even at the maximum concentration (40 ppm) allowed by Brazilian Health Surveillance Agency, the enzyme mixture was more effective. It was demonstrated that it is possible to perform the complete substitution of chemical oxidants by enzymes in order to adequate and improve the rheological parameters of dough wheat flours, even for a weak flour, making it suitable for bakery.