Ce travail constitue une approche innovante mettant en complémentarité diverses techniques de caractérisation physicochimique, électrique et structurale. Menées sur un polymère époxyde, ces études ont pour principal objectif la compréhension des phénomènes et propriétés diélectriques associés aux charges d’espace, ainsi que le suivi de leur évolution dans le temps ou suite à l’application de contraintes extérieures. Les mesures de spectroscopie d’impédance et de courant de dépolarisation thermo-stimulé (CDTS), ont mis en évidence des processus de relaxations dipolaires et interfaciales. L’origine de ces phénomènes a pu être expliquée à partir des analyses physico-chimiques et structurales. Tout d’abord à l’aide des mesures de fluorescence X qui ont révélé la présence de deux types d’impuretés, pouvant créer des états énergétiques plus ou moins profonds dans la bande interdite. Ensuite, par des mesures en réflectométrie X qui ont mis en évidence plusieurs structures ordonnées au sein d’une matrice amorphe. Cette hétérogénéité structurale explique les mécanismes de piégeage et d’accumulation des charges d’espaces aux interfaces. De même, l’ordre local favorisant la mobilité des charges, ces résultats donnent une première réponse quant à la valeur relativement élevée de la conductivité électrique du polymère, telle qu’elle a pu être déterminée à partir des mesures des caractéristiques courant-tension. Des études de vieillissement accéléré ont également été menées. Les différents recuits appliqués ont contribué à la création de charges qui sont piégées dans des niveaux énergétiques de plus en plus profonds. Cela s’est traduit par une diminution de la quantité de charges qui relaxent par activation thermique ainsi que par une diminution de la conductivité électrique des échantillons. Ces changements de propriétés électriques ont été corrélés aux changements structuraux qui se sont produits au sein du polymère, et dont la principale manifestation est la disparition progressive des structures ordonnées. Cette disparition de l’ordre local a aussi été observée en l’absence de contraintes thermiques (vieillissement naturel), où il a été montré que le comportement superficiel et en volume des échantillons n’était pas identique. / This work constitutes an innovative approach in epoxy based polymer characterization, where complementary physico-chemical, electric and structural techniques are used. The main objective of these studies is to understand both dielectric phenomena and properties associated to the space charges, as well as to follow-up their evolution in time or after the application of external constraints.Impedance spectroscopy and thermo-stimulated depolarization current (TSDC), measurements have highlighted dipolar and interfacial relaxations processes. Origin of these phenomena has been explained from physico-chemical and structural analyses. First, X-ray fluorescence measurements revealed the presence of two types of impurities, which are able to create deep energetic levels in the forbidden energy band. Then, X ray reflectometry measurements highlighted several periodic structures within an amorphous matrix. This structural heterogeneity explains the mechanisms of trapping and accumulation of space charges at the interfaces and gives a first reply as for the relatively high value of the polymer electric conductivity, calculated from current-voltage measurements.Accelerated ageing studies have been also carried out. They have shown that annealing creates charges which are trapped in increasingly deep energetic levels. Consequently, both the quantity of released charges and annealed samples conductivities have decreased.These electric properties changes have been correlated with the structural changes occurring within the polymer, and whose principal manifestation is the progressive disappearance of the ordered structures. This disappearance of the local periodicity has also been observed in the absence of thermal constraints (natural ageing), where it was shown that samples surface’s behavior is different from the bulk.

Pouco ainda se sabe das respostas do orégano frente às condições brasileiras de cultivo agrícola. Esta dissertação tem por objetivo verificar as respostas do orégano em produção de biomassa e óleo essencial frente ao déficit hídrico ocasionado por diferentes potenciais matriciais da água no solo. Em casa de vegetação, foram realizados dois experimentos em vasos de 15 L. O primeiro ensaio foi realizado na primavera/verão de 2014/2015 e o segundo ensaio no outono/inverno de 2015, em um delineamento em blocos casualizados em fatorial 4 X 3 + 1 composto por quatro potenciais mátricos da água no solo (-60,8; -91,2; - 121,2 e -152,0 kPa) adotados em três fases do cultivo (ciclo todo, fase vegetativa e fase de pré-florescimento) e o tratamento adicional (-19,7 kPa equivalente a capacidade de campo), com 6 repetições, totalizando 78 parcelas. Aos 96 dias após o transplantio das mudas foram realizadas as colheitas e a avaliação das plantas cultivadas, por meio da determinação da biomassa fresca e seca, teor e rendimento de óleo essencial e produtividade da água em função da biomassa seca e óleo essencial. O potencial mátrico -60,8 kPa adotado no manejo da irrigação durante todo o cultivo do orégano resultou no maior teor e rendimento de óleo essencial, já o potencial mátrico -91,2 kPa adotado no manejo da irrigação durante o préflorescimento do orégano resultou na melhor média de biomassa seca. O potencial mátrico -60,8 kPa adotado no manejo da irrigação durante o pré-florescimento do orégano resultou na melhor média de biomassa fresca. A maior produtividade da água em função do óleo essencial foi alcançada manejando a irrigação do orégano a -60,8 kPa durante todo ciclo de cultivo, a maior produtividade da água em função da biomassa seca foi obtida manejando a irrigação do orégano a -91,2 kPa durante todo ciclo de cultivo. A melhor estação sazonal para cultivo do orégano tendo por foco a extração de óleo essencial foi à primavera/verão e ambas estações sazonais são recomendadas para o cultivo do orégano tendo por foco a produção de biomassa seca e fresca. / Little is known about the responses of oregano against the brazilian conditions of agricultural cultivation. This dissertation aims to verify the oregano responses in biomass and essential oil production against water deficit caused by different matric potentials of water in the soil. At the greenhouse, two experiments were conducted in 15L pots. The first trial was conducted in the spring / summer 2014/2015 and the second during the autumn / winter 2015, in a randomized block design in a factorial 4 x 3 + 1 consisting of four potential matric of water in the soil (-60, 8; -91.2; -121.2 and -152.0 kPa) adopted in three different stages of cultivation (the whole cycle, vegetative phase and pre-flowering) and the additional treatment (- 19.7 kPa equivalent to the field capacity), with 6 repetitions, totaling 78 plots. At 96 days after transplanting the seedlings, plants were harvested and evaluated by determining the weight of fresh and dried biomass, content and yield of essential oil and water productivity according to the dried biomass and essential oil. The matric potential of -60.8 kPa adopted in the management of irrigation throughout the oregano cultivation resulted in higher content and essential oil yield, while the matric potential of -91.2 kPa adopted in the management of irrigation during the preflowering oregano resulted in the best average of dry biomass. The matric potential of -60.8 kPa adopted in the management of irrigation during the oregano pre-flowering resulted in a better fresh biomass average. The highest yield of water in function of essential oil was achieved during oregano irrigation with -60.8 kPa throughout the growing season while the highest water productivity in function of dry biomass was obtained managing oregano irrigation to -91,2 kPa throughout the crop cycle. The best season for seasonal oregano cultivation focusing on essential oil extraction was the spring / summer and both seasonal stations are recommended for oregano cultivation focusing on the production of fresh and dry biomass.

Neste trabalho, cerâmicas de BaTiO3 foram preparadas pelo método de Pechini com o propósito de estudar as suas propriedades dielétricas, incluindo as anomalias dielétricas de origem interfacial nestes ferroelétricos. Após calcinação das soluções precursoras a 600 oC por 2h, os pós compactados foram sinterizados a várias temperaturas entre 1150 e 1450 oC. Subseqüentemente, foram realizadas caracterizações (micro)estruturais aplicando as técnicas de microscopia eletrônica de varredura e difração de raios X, além de estudos dielétricos utilizando a técnica de espectroscopia de impedância. Destas caracterizações, verificou-se a obtenção de materiais cerâmicos com tamanhos de grãos variando entre 0,8 e 37 micrometros ao aumentar a temperatura de sinterização. Os resultados de dinâmica térmica de densificação indicam a contribuição de dois mecanismos independentes: (i) sinterização com participação de fase líquida, induzindo altas densidades dos materiais a partir de ~1300 oC (perto do ponto eutético), e (ii) sinterização via reação de estado sólido, implicando alta sinterabilidade mesmo abaixo dos 1300 oC, em se tratando de pós nanométricos, ou seja, com alta densidade de defeitos e, portanto, processos de difusão iônica intensificados. Por outro lado, a resposta dielétrica dos grãos evidenciou o cumprimento da lei de Curie-Weiss, típica de ferroelétricos, enquanto um fenômeno de anomalia dielétrica (não cumprimento desta lei) foi observado para as respostas totais destes materiais em altas temperaturas e baixas freqüências. A análise dos resultados de espectroscopia de impedância via circuito equivalente, sendo considerado o modelo de camadas (grãos e contornos de grãos) em série, revelou a predominância das propriedades dielétricas das interfaces intergranulares como a causa desta anomalia. Considerando a relação entre propriedades macroscópicas e microscópicas no modelo, a variação da intensidade da anomalia é discutida em função do tamanho dos grãos, sendo este parâmetro uma medida (função inversa) da densidade das interfaces intergranulares. Em geral, este trabalho revela uma excelente correlação entre microestruturas, circuito equivalente e propriedades dielétricas exibidas por estes materiais eletrocerâmicos. / BaTiO3 ceramics were prepared in this work, following the Pechinis method, with the purpose of studying their dielectric properties, including especially the occurrence and characteristics of dielectric anomalies associated to internal interfaces, as often found in ferroelectrics. After calcination of the precursor solutions at 600 oC for 2h, the synthesized green compacts were sintered at several temperatures from 1150 to 1450 oC. Subsequently, (micro)structural characterizations were carried out by applying scanning electron microscopy and X-ray diffraction techniques, followed by dielectric measurements using the impedance spectroscopy technique. From these characterizations, the production of ceramic bodies with average grain sizes varying from 0.8 to 37 micrometer was verified when increasing the sintering temperature. The results of thermal dynamics of densification indicate the contribution of two independent mechanisms, namely (i) liquid phase-assisted sintering, inducing high materials density from ~1300 oC (close to the eutectic point) above, and (ii) solid-state sintering, implying high sinterability even below 1300 oC, as dealing with nanoparticles-sized powders, meaning high density of surface defects and, thus, enhanced ionic diffusion processes. On the other hand, while the dielectric response of the grains satisfied the Curie-Weiss law, typical of ferroelectrics, a dielectric anomaly (departure from this law) phenomenon was observed for the total dielectric response of these materials towards higher temperatures and lower frequencies. The analysis of the results from impedance spectroscopy via equivalent circuit, involving consideration of the series layer (grains and grain boundaries) model, revealed that the predominance of the dielectric properties from the intergranular interfaces is responsible for occurrence of this anomaly. Considering the relation between macroscopic and microscopic properties holding in this model, the variation of the anomaly strength is here discussed in terms of the value of average grain size in these ceramics, a microstructural parameter that represents a measure (inverse function) of the density of the intergranular interfaces. In general, the present study reveals a really good correlation between microstructures, equivalent circuit and dielectric properties exhibited by these electroceramic materials.

Continuous-flow microwave heating is an alternative processing technology that can bring advantages to the pasteurization of food products, particularly, fruit-based beverages. This work aimed to study the continuous-flow microwave thermal processing of cloudy apple juice. Dielectric and electric properties of cloudy apple juices, obtained from different varieties and from an industrial plant, were determined from 500 to 3000 MHz and temperatures between 10 °C and 90 °C. At these frequencies, apple variety showed little influence and the permittivity decreased almost linearly with temperature. Inactivation kinetics of pathogen microorganisms (Escherichia coli O157:H7 and Listeria monocytogenes) and enzymes (polyphenol oxidase, peroxidase and pectin methylesterase) were studied and modeled to evaluate non-thermal effects of microwave radiation. For both processing technologies, it was possible to achieve a 5-log10 reduction of E. coli and L. monocytogenes, as recommended by the FDA. Microwave processing in comparison to conventional heating enhanced the microorganism inactivation in 18 out of 28 experiments. Predicted enzyme inactivation curves for pasteurization at 70 °C and 80 °C of the cloudy apple juice showed that pectin methylesterase has the highest thermal resistance and that there was no significant evidence of non-thermal microwave effects. A pilot scale unit used for pasteurizing fruit juices was evaluated and the process was modeled and simulated to determine the average time-temperature history. Mean residence times and dispersion parameters were obtained from internal volume measurements and residence time distribution experiments. Thermal processing experiments using water provided heat transfer coefficients as functions of Reynolds number and also microwave power absorption. Mathematical modeling was used to determine the temperature distribution along the product path and results were validated. Results showed that focused microwave heating provided the necessary temperature increase in a very short time, with a lethality contribution of only 0.7% as compared to 59-68% when using the conventional heat exchanger, which configures over-processing and can decrease product quality. Fresh cloudy apple juice was subjected to continuous flow microwave assisted pasteurization in a pilot scale unit at three processing temperatures (70 °C, 80 °C and 90 °C), two flow rate levels and two heating systems (conventional and focused microwave). Good results were obtained for polyphenol oxidase and peroxidase inactivation, but not for pectin methylesterase, which showed to be the most resistant enzyme. A comparative evaluation on quality changes was performed in cloudy apple juice samples pasteurized in the continuous-flow unit. Profile of volatiles of the microwave pasteurized apple juice was more similar to the nonpasteurized juice, in comparison with the conventionally pasteurized juice. However, total organic acids and total soluble sugar contents were not significantly different between both processing technologies. There was an increase of phenolic contents during processing of cloudy apple juice, possibly due to the extraction of phenolic compounds present in suspension of material. Furthermore, it was observed the same trend of antioxidant capacity by DPPH and ORAC methods. In conclusion, this PhD work presents the potential of the microwave-assisted pasteurization in cloudy apple juice regarding enzymatic, microbiological and quality aspects. / Aquecimento de micro-ondas de fluxo contínuo é uma tecnologia de processamento alternativa que pode proporcionar vantagens para a pasteurização de produtos alimentícios, particularmente, bebidas à base de frutas. Este trabalho teve como objetivo estudar o processamento térmico de micro-ondas de fluxo contínuo em suco de maçã não clarificado. As propriedades dielétricas e elétricas dos sucos de maçã não clarificados, obtidos de diferentes variedades de maçãs e de uma planta industrial, foram determinadas entre 500 e 3000 MHz e temperaturas entre 10 °C e 90 ° C. Nessas frequências, a variedade da maçã apresentou pouca influência e a permissividade elétrica diminuiu quase linearmente com a temperatura. Cinéticas de inativação de microrganismos patogênicos (Escherichia coli O157: H7 e Listeria monocytogenes) e enzimas (polifenol oxidase, peroxidase e pectina metilesterase) foram estudadas e modeladas a fim de avaliar os efeitos não térmicos da radiação de micro-ondas. Para ambas tecnologias de processamento foi possível obter uma redução de 5-log10 de E. coli e L. monocytogenes, como recomendado pelo FDA. O processamento de micro-ondas em comparação com o aquecimento convencional aumentou a inativação dos micro-organismos em 18 dos 28 experimentos. As curvas de inativação enzimática preditas para pasteurização a 70 ° C e 80 ° C do suco de maçã mostraram que a pectina metilesterase possui a maior resistência térmica e que não houve evidência de efeitos não térmicos. Uma unidade de escala piloto usada para pasteurizar sucos de frutas foi avaliada e o processo foi modelado e simulado para determinar o histórico de tempo-temperatura. Os tempos médios de residência e os parâmetros de dispersão foram obtidos a partir de experimentos de distribuição do tempo de residência e volumes. Experimentos do processamento térmico utilizando água, como produto alimentício, forneceram coeficientes de transferência de calor em função do número de Reynolds e absorção de energia de micro-ondas. A modelagem matemática foi utilizada para determinar a distribuição de temperatura do percurso do produto, e posteriormente, foram validados. Os resultados mostraram que o aquecimento por microondas focalizadas proporcionou o aumento necessário da temperatura em um tempo curto, com uma contribuição de letalidade de apenas 0,7% em comparação a 59-68%, quando usado somente o trocador de calor convencional, o que configura sobre processamento, podendo diminuir a qualidade do produto. O suco de maçã fresco não clarificado foi submetido à pasteurização por micro-ondas em fluxo contínuo em uma unidade de escala piloto em três temperaturas de processamento (70 ° C, 80 ° C e 90 ° C), dois níveis de vazão e dois sistemas de aquecimento (convencional e micro-ondas). Resultados positivos foram obtidos para polifenol oxidase e peroxidase, mas não para a pectina metilesterase demonstrando ser a enzima mais resistente. Uma avaliação comparativa das mudanças de qualidade foi realizada em amostras de suco de maçã pasteurizado na unidade de fluxo contínuo. O perfil de voláteis do suco de maçã pasteurizado por microondas foi mais semelhante ao suco não pasteurizado em comparação ao suco pasteurizado convencionalmente. Entretanto, ácidos orgânicos totais e açúcares solúveis totais não foram significativamente diferentes no processamento por estas duas tecnologias. Houve um aumento de compostos fenólicos durante o processamento do suco de maçã não clarificado, possivelmente devido a extração de compostos fenólicos presentes no material em suspensão. Além disso, foi observado a mesma tendência na atividade antioxidante determinada pelos métodos de DPPH e ORAC. Em conclusão, este trabalho de doutorado apresenta o potencial da pasteurização por micro-ondas em suco de maçã não clarificado quanto aos aspectos enzimáticos, microbiológicos e de qualidade.

O aquecimento por micro-ondas (MO) é uma tecnologia emergente para o processamento térmico contínuo de alimentos líquidos. A taxa d aquecimento e a profundidade de penetração das MO dependem das propriedades dielétricas (PD) do alimento (permissividade elétrica relativa e fator de perda dielétrica ). As PD de água de coco verde e de sucos de frutas cítricas (laranja, limão e tangerina) foram estudadas empregando a técnica de cabo coaxial. As medições foram realizadas em 101 frequências na faixa de 500 MHz até 3000 MHz e em temperaturas entre 0 °C e 90 °C, o que permitiu estudar o efeito da frequência e da temperatura. A profundidade de penetração foi calculada com uma expressão derivada das equações de Maxwell para eletromagnetismo. O trabalho experimental começou com as PD de: água de coco verde simulada, água destilada, solução de açúcares e sais da água de coco verde e água de coco verde natural. Resultados foram comparados para avaliar a contribuição de cada componente (água, açúcares e sais). PD de sucos de diferentes variedades de laranjas, tangerinas e limões, assim como misturas de sucos de duas variedades de laranja, foram também avaliadas. A condutividade elétrica das amostras foi medida nas diferentes temperaturas e o seu efeito sobre o fator de perda foi analisado. Os resultados foram comparados nas frequências comerciais de 915 MHz e 2450 MHz. O comportamento dielétrico das amostras estudadas foi caracterizado por dois mecanismos principais: a condução iônica de sais dissolvidos e a rotação dipolar da molécula de água, os quais têm predominância variável dependendo da frequência e da temperatura. A permissividade elétrica relativa de todas as amostras decresceu com o incremento da temperatura e da frequência, enquanto que o comportamento do fator de perda com a temperatura e frequência foi determinado pela composição. Os sais apresentaram maior efeito que os açúcares sobre as PD da água de coco verde. A profundidade de penetração foi maior na frequência de 915 MHz, associada com o aumento no comprimento de onda. Correlações polinomiais foram ajustadas nas frequências comerciais para representar a dependência com a temperatura. / Microwave (MW) heating is an emergent technology for thermal processing of liquid food products. Heating rate and MW penetration depth depending on dielectric properties (DP) of food material (relative electrical permittivity () and dielectric loss factor ()). DP for green coconut water (GCW) and citrus fruits juices (orange, tangerine and lemon) were studied by open-ended coaxial line probe technique. The measurements were carried out for frequencies between 500 MHz and 3000 MHz at 101 points in this range and temperatures from 0 °C to 90 °C, which allowed studying temperature and frequency effect. The power penetration depth was calculated using an expression derived from the Maxwell equations for electromagnetism. Experimental work started with DP measurement for: simulated (GCW), distilled water, sugars and salts solutions of (GCW) and natural (GCW). Results were compared in order to evaluate the each component contribution (water, sugars and salts). DP for juices from different orange, tangerine and lemon varieties as well as mixtures of orange juice from two varieties, were also evaluated. Electrical conductivity was measured and its effect on dielectric loss factor was analyzed. Obtained results were compared at commercial frequencies of 915 MHz and 2450 MHz. Dielectric behavior of studied samples was characterized by two main mechanisms: ionic conduction of dissolved salts and dipole rotation of water molecules, which presented variable predominance, depending on frequency and temperature. Relative electrical permittivity decreased with increase on both temperature and frequency for all tested samples, whereas dielectric loss factor behavior with temperature and frequency was determined by composition. Salts showed higher effect than sugars on dielectric properties of GCW. Penetration depth was higher at 915 MHz, associated to increasing wave length. Polynomial correlations for DP were adjusted at commercial frequencies in order to illustrate the temperature dependence.

Neste trabalho, foram determinadas as propriedades dielétricas e a condutividade elétrica de quatro tipos leite (leite humano e 3 tipos de leite vaca - cru, integral e semi-desnatado) e de três fórmulas infantis (FIs) empregando a técnica de cabo coaxial de ponta aberta. As medições das propriedades dielétricas foram realizadas na faixa de frequência de (500 a 3000) MHz e em temperaturas de (5 a 90) ºC. O comportamento dielétrico de todos os tipos de leite e das FIs foi caracterizado por dois mecanismos principais (condução iônica e rotação dipolar), que se mostraram dependentes da frequência e da temperatura. Também foi estudada a inativação da enzima fosfatase alcalina (ALP), presente em leite de vaca e humano, utilizando um reator de micro-ondas focalizadas em processo térmico descontínuo. Durante o processamento, por meio de um sensor de fibra óptica, em contato direto com o leite, foram obtidos os históricos de temperatura dos quais os parâmetros cinéticos D e z foram calculados no intervalo de temperatura de (50 a 80) ºC e tempos de (15, 30, 45, 60, 180 e 300) s. A inativação térmica da ALP obedeceu a cinética de primeira ordem e os parâmetros cinéticos determinados foram: z = 4,4 ºC e D70ºC = 1,1 s para o leite humano e z = 7,4 ºC e D70ºC = 44,3 s para o leite de vaca tipo B. Os resultados desse estudo mostraram que o tratamento térmico assistido por micro-ondas, na condição ótima de 60 ºC por 30 s, foi eficiente na inativação de micro-organismos patogênicos (Staphylococcus aureus e Salmonella) e na preservação do perfil de ácidos graxos em leite humano. Além disso, o tratamento térmico assistido por microondas resultou em menores perdas de proteínas, como as imunoglobulinas e lactoferrina, quando comparado ao processamento térmico convencional (Holder), utilizado nos Bancos de Leite Humano (BLH), demonstrando que pode ser considerado uma tecnologia alternativa para o processamento de alimentos líquidos. / In this work, the dielectric properties and electrical conductivity of four types of milk (human milk and 3 types of cow milk - raw, whole and low-fat) and three infant formulae (IFs) were measured using the open-ended coaxial method. The measurements of the dielectric properties were performed at frequency range from (500 to 3000) MHz and temperatures from (5 to 90) ºC. The dielectric behavior of all types of milk and IFs was characterized by two main mechanisms (ion conduction and dipole rotation), which showed dependency in relation to frequency and temperature. The inactivation of alkaline phosphatase (ALP), present in cow and human milk, was also studied using a microwave reactor focused on a batch process. During the processing, by means of a fiber optic sensor, the temperature histories were obtained from which the kinetic parameters D and z were calculated at temperature range from (50 to 80) °C and times from (15, 30, 45, 60, 180 and 300) s. The thermal inactivation of the ALP followed the first-order kinetics and the kinetic parameters determined were: z = 4.4 °C and D70°C = 1.1 s for human milk and z = 7.4 °C and D70 °C = 44.3 s for the type B cow\'s milk. The results of this study showed that microwave-assisted heating, under optimum condition (60 ºC for 30 s), was efficient for inactivation pathogenic microorganisms (Staphylococcus aureus and Salmonella) and preservation of fatty acids profile in human milk. In addition, microwave-assisted heating resulted in lower losses of important proteins, such as immunoglobulins and lactoferrin, compared to conventional thermal processing (Holder), used in Human Milk Banks (BLH), demonstrating that it can be considered an alternative technology for the processing of liquid foods.

Ce travail vise à étudier l'intérêt duchauffage micro-ondes pour l'inactivation desenzymes dans les jus de fruit, à travers desapproches numériques et aussi expérimentales.En premier lieu, une étude sur les propriétésdiélectriques des jus de fruits modèles est menée,démontrant leur forte sensibilité à la température,à la fréquence et à la composition du produit. Dansune seconde partie, l'inactivation de la peroxydaseest étudiée par chauffage conventionnel et lesdonnées sont ajustées par un modèle cinétique dupremier ordre. Dans la troisième et principalepartie de ce travail, un modèle tridimensionnel,résolu par éléments finis, est proposé pour simulerle chauffage par micro-ondes du jus, en couplantélectromagnétisme, transfert de chaleur etécoulement, avec la cinétique d'inactivation de laperoxydase précédemment déterminée.Cette simulation permet de prédire la distributionspatiale de la température, le profil d’écoulementet l'inactivation de la peroxydase. L’accord entre lemodèle et les expériences est très satisfaisant, cequi confirme la pertinence de l’approche. Dans ladernière partie, les réactivations de la peroxydaseaprès chauffage conventionnel et micro-ondessont évaluées et comparées. Enfin, l’éventuelleexistence d’effets non thermiques des microondesest discutée via des expériencesadditionnelles. En conclusion, ces travauxmontrent tout l’intérêt de la simulation numériquecomme outil de compréhension du processusmultiphysique du chauffage par micro-ondes pourl’inactivation des enzymes, ce qui peut êtreparticulièrement intéressant pour la conception etl’optimisation de traitements micro-ondes. / This work aims at studying the use ofmicrowave heating for enzyme inactivation in fruitjuices by means of numerical and experimentalapproaches. In the first part, a study on thedielectric properties of model fruit juices isconducted, evidencing their high dependence onthe temperature, frequency and composition of theproduct. Then in the second part, the inactivation ofperoxidase is studied using conventional heatingand the data are fitted by a first order kinetic model.In the third and main part of this work, a threedimensionalfinite element model is developed tosimulate the microwave heating of juices, couplingelectromagnetics, heat transfer and fluid flow aswell as the peroxidase inactivation kineticspreviously determined.As a result, spatial temperature distribution, flowpattern and peroxidase inactivation are obtained.The model is experimentally validated and goodagreement is observed, confirming the relevanceof the approach. Finally, in the last part, thepotential peroxidase reactivations afterconventional and microwave heating areassessed and compared. Also, the possibleexistence of non-thermal effects of microwaves isdiscussed thanks to additional experimentations.In conclusion, this work shows the large interest ofcomputer simulation as a tool for understandingthe multiphysics process of microwave heating forenzyme inactivation, which can be particularlyinteresting for further design of optimizedmicrowave processing.

In the presented thesis, lead-free Ba(Ti0.8Zr0.2)O3-(Ba0.7Ca0.3)TiO3 (BZT-BCT) thin films were deposited on Pt/TiO2/SiO2/Si substrates using chemical solution deposition method and then the effect of process parameters were investigated to obtain optimum parameters of these lead-free thin films. The phase was selected near to the morphotropic phase boundary (MPH) to increase the number of polarization directions where rhombohedral and tetragonal phases exist together. In this study, the effect of sintering temperatures on microstructure, dielectric and ferroelectric properties were studied systematically. Among the various high-quality BZT-BCT thin films with uniform thickness, the optimum dielectric and ferroelectric responses were observed for films annealed at 800 oC for 1 h sintering time. The thickness was kept constant for all measurements as 500 nm (triple layered films). Therefore, the average grain sizes were found around 60 nm for samples sintered at 700,750 and 800 oC. BZT-BCT thin films sintered at 800 oC showed effective remnant polarization and coercive field values of 2.9 &micro / C/cm2 and 49.4 kV/cm, together with a high dielectric constant and low loss tangent of 365.6 and 3.52 %, respectively, at a frequency of 600 kHz due to pure perovskite phase showing full crystallization and minimum surface porosity obtained at this temperature.

Conventionally discrete passive components like capacitors, resistors, and inductors are surface-mounted on top of the printed circuit boards (PCBs). To match the ever increasing demands of miniaturization, cost reduction, and high performance in microelectronic industry, a promising approach is to integrate passive components into the board during PCB manufacture. Because they are embedded inside multilayer PCBs, such components are called embedded passives. This work focuses on the materials design, development and processing of polymer-based dielectric nanocomposites for embedded capacitor applications. The methodology of this approach is to combine the advantages of the polymer and the filler to satisfy the electric, dielectric, mechanical, fabrication, and reliability requirements for embedded capacitors. Restrained by poor adhesion and poor thermal stress reliability at high filler loadings, currently polymer-ceramic composites can only achieve a dielectric constant of less than 50. In order to increase the dielectric constant to above 50, effects of high-k polymer matrix, bimodal fillers, and dispersing agent are systematically investigated. Surface functionalization of nanofiller particles and modification of epoxy matrix with a secondary rubberized epoxy to form sea-island structure are proposed to enhance the dielectric constant, adhesion and high-temperature thermal stress reliability of high-k composites. To obtain photodefinable high-k composites, fundamental understanding of the photopolymerization of the novel epoxy-ceramic composite photoresist is addressed. While the properties of high-k composites largely depend on the polymer matrix, the fillers can also drastically affect the material properties. Carbon black- and carbon nanotubes-filled ultrahigh-k polymer composites are investigated as the candidate materials for embedded capacitors. Dielectric composites based on percolation typically show a high dielectric constant, and a high dielectric loss which is not desirable for high frequency applications. To achieve a reproducible low-loss percolative composite, a novel low-cost core-shell particle filled high-k percolative composite is developed. The nanoscale insulating shells allow the electrons in the metallic core to tunnel through it, and thereby the composites exhibit a high dielectric constant as a percolation system; on the other hand, the insulating oxide layer restricts the electron transfer between filler particles, thus leading to a low loss as in a polymer-ceramic system.

This thesis deals with the investigations on the dielectric properties of polycrystalline ceramics having uncommon substitutions in barium titanate and other related phases of BaTiO3-CaTiO3, MgTiO3-CaTiO3 and MgTiO3-BaTiO3 systems. After presenting a brief introduction on the ceramic materials studied in terms of their crystal structures, electrical properties, nonstoichiometry and microstructural characteristics. The thesis describes the synthesis of the ceramics and the methodology of different techniques utilized in characterizing the samples. Barium calcium titanate was synthesized through novel wet chemical techniques and the dielectric properties of calcium substituted barium titanate do not reveal multi-site occupancy whereas they are predominantly influenced by the A/B cationic ratio. The role of transition metals of the 3d series from vanadium (Z=23) to zinc (Z=30) in modifying the crystallographic phase content, microstructure and the dielectric properties of BaTiO3 ceramics containing 10 at% impurities were studied. All the transition metals brought about the phase conversion to hexagonal BaTiO3, although no systematics could be arrived at relating the hexagonal content to the 3d electronic configuration of the impurities. The relaxor dielectrics arising from the titanate solid solution with uncommon substitution and its interconversion to normal ferroelectrics is studied. The effects of cationic substitutions of iron and niobium for titanium in BaTiO3 pervoskite lattice in crystal symmetry and dielectric properties were investigated. The above dielectric characteristics are comparable in a converse way to those of the well known Pb(Mg1/3Nb2/3)O3-PbTiO3 system wherein the relaxor behaviour occurs within the lower lead titanate compositional limits. The modification in -T characteristics of positive temperature coefficient in resistance (PTCR) by the addition of segregative additives such as B2O3, Al2O3 etc in BaTiO3 and its conversion to grain boundary layer capacitance is studied. The presence of Al-related hole centers at the grain boundary regions resulted in charge redistribution across the modified phase transition temperatures due to symmetry-related vibronic interactions, which result in broad PTCR characteristics extending to higher temperatures. The processing of high permittivity ceramics by the manipulation of microstructural features in semiconducting BaTiO3 is studied wherein the grain boundary layer effect superimposed with the contributions from the barrier layers formed during electroding related to microstructure is proposed to be responsible for the unusual high permittivity in semiconducting BaTiO3. The influence of Mg2+ as a substituent in modifying the crystallographic phase contents, microstructure and the dielectric properties of (Ba1-xMgx)TiO3 ceramics, (x ranging from zero to 1.0 ) is studied. The results point to the dual occupancy of Mg2+ both in A and B sublattice and the role of oxygen vacancy as well as (Ti3+ –VO) defects in stabilization of hexagonal phase to lower temperatures. The microwave dielectrics of the BaMg6Ti6O19 phase formed in the compositional range of x=0.4 to 0.7 was investigated for suitable application in microwave dielectrics. Extensive miscibility between the ilmenite-type MgTiO3 and perovskite-type CaTiO3 over a wide compositional range is brought about by the simultaneous equivalent substitution of Al3+ and La3+. The resulting Mg1-(x+y)CaxLay)(Ti1-yAly)O3 ceramics exhibit improved microwave dielectric properties by way of high permittivity, low TCK and high quality factor. The elemental distribution reveals the complexity in the Mg/Ca distribution and its correlation with the solid state miscibility as well as dielectric properties. Microwave dielectric property of Mg4Al2Ti9O25 which is detected as secondary phase is studied in detail.