Nesta pesquisa é feita uma análise da interação do campo eletromagnético gerado por microcomputadores portáteis com o corpo humano, operando na faixa de radiocomunicações WI-FI, através da avaliação da taxa de absorção especifica (SAR). Os modelos de corpo humano heterogêneos utilizados são de um adulto de 34 anos e duas crianças de 6 e 11 anos os quais foram analisados em varias situações típicas de exposição à presença de um microcomputador portátil. Nas simulações dos cenários para avaliar a dosimetria foi utilizada a versão comercial do programa chamado SEMCAD X que é baseado no Método das Diferenças Finitas no Domínio no Tempo (FDTD). Da análise das simulações do modelo de corpo inteiro, o único resultado que ultrapassou a recomendação do (FCC, 1997) para 1 g de tecido foi na situação em que o microcomputador portátil, com a antena dipolo na parte posterior do teclado, está no colo do modelo de 34 anos. Numa segunda etapa, é feito um estudo teórico experimental da intensidade do campo elétrico gerado por dispositivos geradores de sinais Wi-Fi comerciais. Analisa-se à propagação de ondas eletromagnéticas através de paredes, utilizando uma antena monocone não ressonante e de banda larga, mediante o estudo e análise da sua taxa de onda estacionária. As medidas visam avaliar que projetando uma parede com uma espessura determinada consegue a propagação dos campos eletromagnéticos evitando reflexões e pontos quentes que possam produzir uma taxa de absorção maior no corpo humano presente nestes ambientes, além de caracterizar as propriedades dielétricas destas paredes. / This research analyses the interaction of the electromagnetic field generated by portable computers with the human body, operating in the range of radio Wi-Fi, by evaluating the specific absorption rate (SAR). The heterogeneous human body models used were those of a 34 years old adult and two children aged 6 and 11, were analyzed under various standard conditions of exposure to the presence of a portable microcomputer. The commercial version of SEMCAD X which is based on the Finite Difference Method in the Time Domain (FDTD) method was used in the simulations of the scenarios, to evaluate the dosimetry. The analysis of the simulation of the whole body model, the only result that exceeded the recommendation of the (FCC, 1997) for 1g of tissue was the simulation in which the dipole antenna on the back of the keyboard of the laptop resting on the lap of the 34-year old model. In the second stage, a theoretical experimental study was made of the intensity of the electric field created from Wi-Fi band signals generating devices. Subsequently, an analysis is made of the propagation of the electromagnetic waves through walls, using a non-resonant broadband monocone antenna by analyzing its voltage standing wave ratio (VSWR). The measures aim to assess that designing a wall with a given thickness, propagation of electromagnetic waves can be achieved, thus avoiding reflections and hot spots that can lead to higher SAR in the human body present in these environments, moreover to characterize the dielectric properties of these walls.

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.

Ce travail de thèse a contribué au développement d'un outil numérique multi-échelle capable de restituer l'aspect visuel de revêtements de peinture de carrosserie automobile à partir des caractéristiques physico-chimiques et des propriétés diélectriques des différents constituants de base ; l'objectif est la prédiction et la complète maîtrise de l'aspect visuel des matériaux. Dans cette étude, des nanoparticules d'hématite (variété α-Fe2O3), d'oxyde et d'hydroxyde de nickel de différentes formes et tailles ont été synthétisées par un procédé hydrothermal. Les particularités de ces particules en termes de morphologie, de taille et de structure ont été soulignées car elles sont susceptibles d'affecter ses propriétés diélectriques, et donc la couleur obtenue. La réponse diélectrique des particules a été mesurée par spectroscopie de pertes d'énergie des électrons (EELS). Dans un revêtement de peinture, les pigments, qui interagissent les uns avec les autres pour former des floculats, modifient la diffusion de la lumière et donc la couleur perçue. Au cours d'une deuxième phase, des revêtements de peinture « modèles », constitués de particules d'hématite dispersées dans une résine polymère, ont été élaborés. L'auto-organisation spatiale de ces nanoparticules au sein du revêtement a été décrite à partir d'images 2D enregistrées à différentes échelles d'observation. Sur la base des mesures diélectriques locales réalisées sur les nanoparticules et peintures « modèles » synthétisées dans le présent travail, des modèles aléatoires de matériaux hétérogènes ont alors été établis par le Centre de Morphologie Mathématique, pour générer une « microstructure diélectrique» 3D de ces revêtements. Sur la base de ces modèles morphologiques, les propriétés diélectriques effectives des revêtements ont été prédites; les fonctions diélectriques alors obtenues sont en bon accord avec les mesures macroscopiques réalisées par ellipsométrie. / This work contributed to the development of a multi-scale numerical tool able to reproduce the visual appearance of coatings for motor vehicle bodywork from the physico-chemical characteristics and dielectric properties of various base constituents; the goal is the prediction and complete control of the visual appearance of materials. In this study, hematite nanoparticles (the α-Fe2O3 variety), nickel oxides and hydroxides of different shapes and sizes were synthesised using a hydrothermal process. The characteristics of these particles in terms of morphology, size and structure have been particularly emphasised since they are likely to affect the overall dielectric properties of the coating, and therefore the color obtained. The dielectric response of the particles was measured by electron energy loss spectroscopy (EELS). In a coating of automobile paint, pigments which interact with each other to form flocs alter the light scattering and therefore the perceived color. During a second phase, model paint coatings consisting of hematite particles dispersed in a polymer resin were developed. The volume self-organisation of nanoparticles in the coating has been described from 2D images recorded at different scales of observation. Based on our local measurements of the dielectric function at different scales of the nanoparticules and model paint that were synthetized in the present work, random models of heterogeneous materials were then established by a partner within the consortium to generate a "dielectric 3D microstructure" of these coatings. Based on these morphological models, effective dielectric properties of the coatings were predicted, and then satisfactorily compared with macroscopic measurements from ellipsometry.

High quality and accurate computational data was obtained through first principle quantum mechanical calculations originated from density functional theory without the inclusion of empirical data (ab initio). The support of the computing facility NGS allows us to carry out our research involving large scale atomistic simulations. The data we recently obtained clearly shows piezoelectricity in GaAs and InAs are proved to be non linear in relation to a general strain.The high order fitting equation obtained through the parameterization procedure allowed us to directly evaluate higher order piezoelectric coefficients. By comparing with other linear and non linear models and also experimental data, we reached the conclusion that the validity of our model is correct in the limitation of small shear strain, particularly in case of (111) grown semiconductors. Such limitation however is not restricted under pseudomorphic growth in (001) direction where typically shear strain is small.We further validate our model through elasticity theory to demonstrate the sign of the polarization is found to be opposite to bulk values for an InAs semiconductor layer grown in the (001) direction of growth and subject to 6-7% of lattice mismatch. This is additionally supported with experimental evidence (optical absorption spectra).Furthermore our model provides a direct way in evaluating the polarization for any crystal structure described on the atomic level. This is mainly beneficial to researchers who use molecular dynamics and empirical methods for predicting bandstructure.The fundamental performance for semiconductor devices can be improved through the use of the small polarization created from strain and is likely to bring advantages in future photovoltaics devices.

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.

[EN] Sustainability is nowadays an investment for the future of any economic activity. The current situation of crisis has had an adverse impact in most industries, including the agri-food sector. However, this industry has been relatively the least affected when compared with other industrial sectors. This is mainly attributed to the fact that food products continue to be basic for consumers despite the economic downturn. Therefore, the agri-food sector is a key element in the European economy and can play a crucial role in the achievement of the objectives set in the EU's strategy for 2020: ensuring a sustainable framework of growth of a more competitive economy. The European agri-food industry has focused on energy efficiency and on reducing greenhouse gases emissions, along with better management of their resources as a way to improve its industrial competitiveness. In this sense, the search for solutions to transform the by-products generated in high value-added ingredients, is a priority. In this context, the juice industry, as fundamental sub-sector within the food sector, and large waste generator, must exploit the opportunity to transform their by-products into useful and profitable products for society. This transformation presents some difficulties which impede the profitability of the process. These difficulties are associated with the by-product, such as its compositional variability and its seasonality, and current techniques of transformation as the high energy cost in dehydration processes. This thesis represents an innovative and sustainable solution for overcoming the disadvantages associated with the high costs of stabilization, turning this by-products into high value-added ingredients, from both, nutritional and technological, points of view. The aim is to develop a microwave coupled with hot air drying technique allowing maximizing profits by using the following strategy: reducing time and operational costs, producing a new ingredient rich in dietary fiber, with interesting technological properties for the development of healthy foods, studying the proposed comprehensive process and analyzing the new generated by-products. The methodological approach of the thesis been focused, on the one hand, on studying phenomena that govern the internal transport of water and energy through the orange peel during its dehydration applying thermodynamics. On the other hand, the energy consumption of the drying process, the technological and sensory properties of the fiber obtained and its potential use as a fat substitute have been compared with the conventional hot air drying method. Finally, the integrated process, including both the combined drying technique and the pretreatments needed for colour and bitter compounds extraction, is proposed as a new route of valorization, in which the new by-products obtained, polyphenols and carotenoid rich extracts, are analysed. This study has analyzed the microwave coupled with hot air process, developing tools that allow the adequate upscaling of the drying operation by adapting it to the best standards of quality of the final product. A monitoring system that ensures these standards has been designed. The quality and the energy consumption of the dietary fiber production process has been improved. The properties associated with its inclusion in food matrices have been optimized. An innovative and sustainable process for the stabilization of industrial by-products and for their further conversion into dietary fiber and other bioactive compounds, applying microwave coupled with hot air drying, has been developed. / [ES] La sostenibilidad es una de las apuestas de futuro en cualquier actividad económica. La situación de crisis ha tenido un impacto adverso en la mayoría de las industrias, incluyendo las de ámbito agroalimentario. Sin embargo, ésta ha sido relativamente la menos afectada cuando se compara con otros sectores industriales. Esto se atribuye al hecho de que los productos alimenticios continúan siendo básicos para los consumidores a pesar de la desaceleración económica. Por lo tanto, esta industria es un pilar fundamental en la economía europea y puede jugar un papel crucial en la consecución de los objetivos marcados en la Estrategia de la UE para 2020: asegurar un marco sostenible de crecimiento de una economía más competitiva. La industria agroalimentaria europea ha apostado por la eficiencia energética y la reducción de emisiones de gases invernadero, junto con una mejor gestión de sus recursos como vía para la mejora de su competitividad industrial. La búsqueda de soluciones para transformar los subproductos generados en ingredientes de alto valor añadido, es una de las prioridades. En este contexto, la industria productora de zumos, como subsector fundamental dentro del sector alimentario, y gran generador de residuos, tiene la oportunidad de transformar sus subproductos en productos útiles y rentables para la sociedad. Esta transformación presenta algunas dificultades que impiden la rentabilidad del proceso. Estas dificultades están asociadas al subproducto, como su variabilidad composicional o su estacionalidad, y a las técnicas actuales de transformación como el elevado coste energético en procesos de deshidratación. Esta tesis se plantea como una solución innovadora y sostenible para, más allá de superar los inconvenientes asociados a los altos costes de estabilización, transformar este subproducto en un ingrediente de alto valor añadido, tanto nutricional como tecnológico. Para ello se propone desarrollar una técnica de secado combinado por aire caliente y microondas que permita maximizar beneficios mediante la siguiente estrategia: reducir el tiempo y el coste energético de la operación, produciendo un nuevo ingrediente rico en fibra dietética con propiedades tecnológicas de interés para el desarrollo de alimentos más saludables, estudiando el proceso integral propuesto y analizando los nuevos subproductos generados. El enfoque metodológico de la tesis ha estado dirigido, por una parte, a estudiar los fenómenos que gobiernan el transporte interno de agua y energía a través de la piel de naranja durante su deshidratación, aplicando termodinámica. Por otra parte, el consumo energético del proceso de secado, las propiedades tecnológicas y sensoriales de la fibra obtenida y su potencial uso como ingrediente sustituto de grasa, se han comparado con el método de secado convencional por aire caliente. Finalmente, el proceso integrado, incluyendo tanto el secado combinado como las etapas previas de extracción de color y compuestos amargos, se propone como una nueva ruta de valorización, en la que se analizan posibles subproductos de interés tales como extractos ricos en polifenoles y carotenoides. En este estudio se ha analizado el proceso combinado de secado con aire caliente y microondas, desarrollando herramientas que permiten dimensionar adecuadamente la operación de secado adaptándola a los estándares óptimos de calidad del producto final. Se ha diseñado un sistema de monitorización que asegure dichos estándares. Se ha mejorado el proceso de obtención de fibra alimentaria respecto a su calidad y a su gasto energético. Se han optimizado las propiedades asociadas a su inclusión en matrices alimentarias. Se ha desarrollado un proceso innovador y sostenible para la estabilización de subproductos vegetales de origen industrial y para su posterior conversión en fibra dietética y otros compuestos bioactivos, aplicando la tecnología de secado por aire caliente y / [CAT] La sostenibilitat és una de les apostes de futur en qualsevol activitat econòmica. L'actual situació de crisi ha tingut un impacte advers en la majoria de les indústries, incloent les d'àmbit agroalimentari. No obstant això, la indústria agroalimentària ha sigut relativament la menys afectada quan es compara amb altres sectors industrials. Açò s'atribuïx principalment al fet de que els productes alimentaris continuen sent bàsics per als consumidors a pesar de la desacceleració econòmica. Per tant, esta indústria és un pilar fonamental en l'economia europea i pot jugar un paper crucial en la consecució dels objectius marcats en l'Estratègia de la UE per a 2020: assegurar un marc sostenible de creixement d'una economia més competitiva. La indústria agroalimentària europea ha apostat per l'eficiència energètica i la reducció d'emissions de gasos d'efecte hivernacle, junt amb una millor gestió dels seus recursos com a via per a la millora del seu vaig competirtu En este sentit, la busca de solucions per a transformar els subproductes generats en ingredients d'alt valor afegit, és una de les prioritats. En este context, la indústria productora de sucs, com subsector fonamental dins del sector alimentari, i gran generador de residus, té el deure i l'oportunitat de transformar els seus subproductes en productes útils i rendibles per a la societat. Esta transformació presenta algunes dificultats que impedixen la rendibilitat del procés. Estes dificultats estan associades al subproducte, com la seua variabilitat composicional o la seua estacionalitat, i a les tècniques actuals de transformació com l'elevat cost energètic en processos de deshidratació. Esta tesi es planteja com una solució innovadora i sostenible per a, més enllà de superar els inconvenients associats als alts costos d'estabilització, transformar este subproducte en un ingredient d'alt valor afegit, tant nutricional com tecnològic. Per a això es proposa desenvolupar una tècnica de'assecat combinat per aire calent i microones que permeta maximitzar beneficis per mitjà de l'estratègia següent: reduir el temps i el cost energètic de l'operació, produint un nou ingredient ric en fibra dietètica amb propietats tecnològiques d'interés per al desenvolupament d'aliments més saludables, estudiant el procés integral proposat i analitzant els nous subproductes generats. L'enfocament metodològic de la tesi ha estat dirigit, d'una banda, a estudiar els fenòmens que governen el transport intern d'aigua i energia a través de la pell de taronja durant la seua deshidratació, aplicant termodinàmica. D'altra banda, el consum energètic del procés de d'assecat, les propietats tecnològiques i sensorials de la fibra obtinguda i el seu potencial ús com a ingredient substitut de greix, s'han comparat amb el mètode d'assecat convencional per aire calent. Finalment, el procés integrat, incloent tant l'assecat combinat com les etapes prèvies d'extracció de color i compostos amargs, es proposa com una nova ruta de valoració, en la que s'analitzen possibles subproductes d'interés com ara extractes rics en polifenoles i carotenoides. En este estudi s'ha analitzat el procés combinat d'assecat amb aire calent i microones, desenvolupant ferramentes que permeten dimensionar adequadament l'operació d'assecat adaptant-la als estàndards òptims de qualitat del producte final. S'ha dissenyat un sistema de monitorització que assegure els dits estàndards. S'ha millorat el procés d'obtenció de fibra alimentaria respecte a la seua qualitat i al seu consum energètic. S'han optimitzat les propietats associades a la seua inclusió en matrius alimentàries. S'ha desenvolupat un procés innovador i sostenible per a l'estabilització de subproductes vegetals d'origen industrial i per a la seua posterior conversió en fibra dietètica i altres compostos bioactius, aplicant la tecnologia d'assecat por aire calent i microones. / Talens Vila, C. (2015). DESARROLLO DE TÉCNICAS COMBINADAS DE SECADO CON AIRE CALIENTE Y MICROONDAS EN LA PRODUCCIÓN DE FIBRA ALIMENTARIA A PARTIR DE SUBPRODUCTOS CÍTRICOS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/54114 / TESIS

"Il ya beaucoup de place vers le bas!", ait déclaré Richard Feynman dans son discours sur les nanotechnologies en 1959, ouvrant un nouveau monde de la science et de la technologie! L'idée d'utiliser des nanoparticules afin d'améliorer les propriétés diélectriques des polymères qui étaient déjà en cours d'utilisation a suscité l'intérêt des chercheurs dans les deux dernières décennies. Nanocharges tels que la silice, l'alumine, l dioxyde de titan, etc, mais aussi des particules plus grosses comme les argiles ou les nanotubes de carbone ont été mélangés avec les polymères «classiques» afin d'améliorer les propriétés du polyéthylène, des résines époxy, de polypropylène, etc.De nos jours, le rendement de conversion d'énergie de générateurs électriques est limitée par des problèmes thermiques et électriques, limitations étant surtout liées à la qualité des rubans isolants appliqués sur les barres en cuivre. En conséquence, des rubans isolants innovants basés sur des de matériaux nanostructurés ont été envisagés pour augmenter le rendement énergétique des alternateurs et le but de ce travail est d'étudier ces matériaux innovants et de comparer leurs propriétés avec celles des matériaux déjà utilisés, afin d'aider à choisir le meilleur matériau composite pour les futurs rubans. Après une brève introduction sur le contexte de ce travail, on a présenté bref état de l'art les propriétés des polymères époxy, avec un débat sur les propriétés électriques de la matrice polymère choisie (résine époxyde), ses propriétés chimiques et thermiques. Ensuite, les nanocharges choisies et leurs propriétés spécifiques sont présentés, en discutant les différentes étapes du procédé de fabrication, aussi qu'un débat sur les phénomènes qui apparaissent à l'échelle nanométrique et leur éventuelle influence sur les propriétés du matériau composite fini.Différents groupes de matériaux composites à base d'époxy remplis de silice nanométrique, argile organique ou de nitrure de bore sont analysés dans ce travail. Afin de caractériser et interpréter leurs propriétés, plusieurs outils ont été utilisés: la microscopie imagerie, la caractérisation thermique ainsi que les méthodes d'investigation à fort ou faible champ électrique. Leur caractéristiques sont ressemblés et différents observations sur des propriétés «générales» ou «spécifiques» des matériaux composites ont été observés et discutés par rapport à l'influence du type de charge utilisée, de son traitement ou de son poids total sont débattues.Enfin, un modèle numérique basé sure une généralisation de la loi des mélanges sera utilisée afin de prédire la réponse diélectrique des matériaux composites ainsi que les paramètres (taille, permittivité) de l'interphase, «l'ingrédient« magique du mélange matrice de remplissage. Le modèle présenté nous a permis de donner un lien entre les différents matériaux et de valider les résultats obtenus expérimentalement. Une approche par éléments finis est utilisée.Ce manuscrit s'achève par des conclusions sur le travail présenté et il laisse entrevoir les perspectives dans l'analyse complexe des polymères nanocomposites . / “There's plenty of room of the bottom!” said Richard Feynman in his talk on top-down nanotechnology in 1959, bringing into the spot light a new world of science and technology ! The idea of using nanoparticles in order to improve the dielectric properties of the polymers that were already in use attracted the interest of researchers for the last two decades. Nanofillers such as silica, alumina, titania etc, but also larger particles such as clays or carbon nanotubes were mixed with the “classic” polymers in order to improve the properties of polyethylene, epoxy resins, polypropylene etc. Since nowadays the energy conversion efficiency of electrical generators is restricted by thermal and electrical issues, these limitations can be related to the electrical insulator tapes themselves. Thus, innovative insulating tapes based on nanostructured material scenarios to address the energy saving concern are intended and the purpose of this work is to investigate these innovative materials and to compare their properties with those of the materials already in use, in order to help choosing the best composite material for the future tapes.This works begins with a state of the art regarding the properties of epoxy polymers. Their chemical, thermal and dielectric properties are presented. Afterwards, the chosen fillers and their specific properties are presented. The influence of the chosen fillers as well as different steps of the nanocomposite materials manufacturing process are presented and the discussion ends with a debate on the phenomena appearing at the nanometric scale and their possible influence on the properties of the finite composite material .Different materials groups of epoxy based composites filled with nanometric silica, organoclay or boron nitride are analyzed afterwards. In order to characterize and interpret their properties, several tools were used: imaging microscopy, thermal characterization as well as high and low electric field investigation methods. A debate trying to distinguish between so called “general” or “specific” behavior of the composite materials with respect to the normal, unfilled polymer is also presented. The influence of the type of filler, its treatment or its weight total percentage will be are chosen as comparison criteria. Finally, a numerical model based on Finite Element Method approximation was used in order to predict the dielectric response of the composite materials as well as the specific parameters (size, permittivity) of the interphase, the magic “ingredient” of the matrix-filler mix. The presented model allowed us to give a connection between the different materials and validate the experimentally obtained results. This manuscript ends with conclusions on the presented work and suggests possible future works in the complex analysis of polymer nanocomposites.

Ces travaux de thèse consistent à élaborer des nanocomposites Polyaniline/hexaferrite pour l’absorption des micro-ondes. L’idée principale est la mise en œuvre de matériaux composites à base de polymères conducteurs intrinsèques telle la Polyaniline que nous avons dopée avec différents types d’acides (HCl, CSA, NSA et TSA…) et l’hexaferrite de baryum de type magnétoplombite (M) stœchiométrique ou substitué. Au niveau de l’hexaferrite de baryum, la substitution du Fe3+ s’est faite par les ions Al3+, Bi3+, Cr3+ et Mn3+.L’hexaferrite de baryum et les hexaferrites substitués par les différents ions cités ci-dessus ont été synthétisés par voie hydrothermale dynamique en faisant varier divers paramètres au cours de la synthèse (pH, température, temps, rapport [OH-]/[NO3-]…).L’élaboration des composites Polyaniline/hexaferrite (pur ou substitués) a été effectuée par polymérisation oxydative en utilisant plusieurs techniques de synthèse : la polymérisation chimique en solution (en tenant compte de la nature de l’acide utilisé) avec ou sans agitation (Aqueous-Based Polymerization with or without stirring) et la polymérisation oxydative par voie solide (Solid-Based Polymerization). L’optimisation de ces différentes techniques de synthèse après caractérisations physicochimiques (DRX, FTIR, ATG, MEB, EDX), diélectriques (ε’, ε’’, σdc) et magnétiques (Mr, Ms, Hc, Tc, µ’, µ’’) des échantillons, a montré que la polymérisation par voie solide se trouve la méthode la plus facile, économique et respectueuse de l’environnement. Elle est aussi adaptée à la production du composite Pani/BaFe12O19 avec de bonnes propriétés structurales, physiques et magnétiques. L’étude de la substitution du Fe3+ dans le BaFe12O19 par Al3+, Bi3+, Cr3+ et Mn3+ a montré une forte dépendance des propriétés structurales et magnétiques avec la distribution de ces ions dans la maille cristalline hexagonale. En effet, les ions Al3+, Cr3+ et Mn3+ ont une tendance à occuper les sites tétraédriques, alors que le Bi3+ occupe les sites octaédriques. Une augmentation de Hc associée à la taille des cristallites a été observée pour les particules substituées avec l'Al et le Cr alors qu’une modification de l'anisotropie magnetocristalline (fort terme d'ordre supérieur) a été mise en évidence pour les substitutions Bi et Mn, dû à leur grand rayon ionique. L’incorporation des hexaferrites substitués dans la Polyaniline pour obtenir des composites Pani/BaMeFe11O19, où Me = Al, Bi, Cr et Mn, révèle une variation des propriétés électromagnétiques dans la gamme de fréquences allant de 1 à 18 GHz. En effet, ces variations sont dues à la formation de dipôles entre l’ion de substitution et les cations O2- dans le ferrite qui sont responsables de la résonance ferromagnétique, de l'anisotropie magnétocristalline et des interactions avec la matrice polymérique. Le composite Pani/BaFe12O19 présente des absorptions dans la bande X qui se déplacent vers la bande Ku avec la substitution du fer confirmant / This thesis deals with the formulation of Polyaniline/hexaferrite nanocomposite for absorbing electromagnetic waves. The main idea is the process of composite materials based on polymers intrinsic conductors such as polyaniline that we doped with different types of acids (HCl, CSA, NSA, and ... TSA) and barium hexaferrite with magnetoplumbite structure with or without substitution according to desired stoichiometries. In the barium hexaferrite, the substitution of Fe 3+ is made by Al3+, Bi3+, Cr3+ and Mn3+ ions.The barium hexaferrite and its substitutions by different ions mentioned above were synthesized dynamic hydrothermal method by varying various parameters during the synthesis (pH, temperature, time, ratio [OH-]/[NO3-] ...).The elaboration of polyaniline/hexaferrite composite (pure or substituted) was carried out by oxidative polymerization using various synthesis techniques: Aqueous-Based Polymerisation with or without agitation (taking into account the nature of the acid used) (ABP) and Solid-Based Polymerization (SBP). The optimization of these various synthesis techniques after physicochemical (XRD, FTIR, TGA, SEM, EDX), dielectric (ε ', ε' ', σdc) and magnetic (Mr, Ms, Hc, Tc, µ', µ'') characterizations of the samples showed that the solid route is the easiest method, economical and environmentally friendly. It is also suitable for the production of composite Pani/BaFe12O19 with good structural, physical and magnetic properties.The study of the substitution of Fe 3+ in the BaFe12O19 by Al3+, Bi3+, Cr3+ and Mn3+ showed a strong dependence of the structural and magnetic properties with the distribution of these ions in the hexagonal crystal lattice. In fact, Al3+, Cr3+ and Mn3+ ions tend to occupy the tetrahedral sites, while the Bi3+ favoured the octahedral sites. An increase in Hc associated with the small crystallite size observed for particles substituted with Al and Cr and the enhancement magnetocristalline anisotropy (strong higher order term) for Bi and Mn due to their high ionic radius.The incorporation of the substituted hexaferrite in the polyaniline to obtain Pani/BaMeFe11O19 composite, where Me = Al, Bi, Cr and Mn, reveals a variation in electromagnetic properties in the frequency range from 1 to 18 GHz. In fact, these variations are due to the formation of dipoles between the substituting ion and surrounding O2- cations in the ferrite which are responsible for the ferromagnetic resonance, the magnetocrystalline anisotropy and the exchange interaction with the polymer. The composite Pani/BaFe12O19 shows absorption bands at the X-band that shift to the Ku-band with the substitution of iron, confirming the potential of these materials for microwave applications.

The diploma thesis is focused on the preparation of test samples of paint-filled micronized mica and analysis of electrical properties of insulating material values in different environmental conditions. For this purpose, it was created five sets of composite paint primers with different ratio of mica. Samples were gradually exposed to the environment relative humidity of 0%, 33%, 55%, 65% and 75%. For each environment with a defined moisture characteristics were observed in samples exposed to the temperature of 20 to 50 ° C. The diploma paper analyzed the influence of the mass implementation of mica in each set of samples and placed on the surface structure of samples.

Le contrôle des chaussées neuves en génie civil est primordial pour assurer sa bonne miseen oeuvre et lui conférer une durée de vie optimale. Dans cet objectif, divers paramètresphysiques nécessitent d'être scrupuleusement calibrés et contrôlés afin d'éviter une dégradation précoce de la chaussée et des problèmes de sécurité pour les conducteurs qui l'empruntent. De plus, les coûts associés à la mise en place et à la maintenance des chaussées sont considérables. Parmi les propriétés qui requièrent une attention particulière, la compacité, qui est indicative de la quantité d'air en volume dans la chaussée, est celle qui nous intéresse dans cette étude. Actuellement, seulement deux méthodes en laboratoire (en Europe) sont considérées comme des méthodes normalisées pour déterminer la compacité. Néanmoins, ces techniques sont destructives et/ou nucléaires ce qui est un frein majeur à leur utilisation. Durant ces deux dernières décennies, de nouvelles techniques électromagnétiques (non nucléaires et non destructives) ont émergé et ont prouvé leur forte utilité dans le domaine de la géophysique et du génie civil et plus particulièrement pour la détermination de la compacité. Cependant, ces nouvelles techniques nécessitent de prendre un certain nombre de précautions pour déterminer la compacité. Tout d'abord, elles permettent de mesurer la permittivité diélectrique du matériau en question. Ainsi pour déterminer la compacité, il est nécessaire d'utiliser des lois de mélange électromagnétiques. L'utilisation de ces modèles requiert une connaissance précise des constituants qui composent la chaussée ainsi que de leurs propriétés (masse volumique et permittivité diélectrique). La première partie de ce travail démontre la pertinence d'utiliser un radar à sauts de fréquences pour déterminer la compacité. L'étude de plusieurs lois de mélange électromagnétiques a été réalisée et les modèles présentant les meilleurs résultats ont été sélectionnés. Cependant, ces techniques font face de nos jours à un problème majeur. En effet, l'utilisation de matériaux recyclés est de plus en plus fréquente pour la construction de nouvelles chaussées ce qui rend la détermination de la compacité encore plus difficile par des méthodes électromagnétiques. Par conséquent, plusieurs méthodologies ont été développées, et sont proposées pour déterminer la compacité d'une nouvelle autoroute qui comporte des matériaux recyclés. La seconde partie de ces travaux de recherche porte sur la caractérisation diélectrique de plusieurs roches qui sont les éléments principaux d'une chaussée. Cette caractérisation est validée de basses à hautes fréquences mais aussi en fonction de la température. Les résultats montrent que à haute fréquence, la permittivité est principalement dépendante de la densité et de la composition chimique de la roche. En revanche, lorsque la fréquence d'investigation diminue et que la température varie, d'autres phénomènes apparaissent et changent dramatiquement le comportement diélectrique de la roche. Il a également été montré que l'eau joue un rôle majeur dans le comportement diélectrique à basse fréquence de la roche. Ces phénomènes se répercutent à "haute fréquence" par de très faibles variations qui pourraient expliquer les déviations obtenues par les méthodes électromagnétiques capacitives qui fonctionnent dans la région du MHz et qui sont également utilisées pour le contrôle de la compacité des chaussées neuves. / The control of new paved road is primordial to ensure its quality as well as its lifetime. Thus, several physical properties need to be well calibrated and controlled in order to avoid early degradations and safety issues for the drivers. Furthermore, the coast associated to the road building and the road maintenance is significant which makes the implementation of asphalt pavement according to the standard even more important. Among the properties that need attentions, the compactness which is indicative of the air void concentration in the asphalt pavement is the one we are interested in. Currently, only two methods in laboratory (in Europe) are considered as standards to assess the compactness. Nevertheless, these techniques are either nuclear or destructive which is a major hindrance. In the past two decades, new electromagnetic (EM) techniques have emerged and proved their great utility for geophysics or civil engineering applications and more importantly for the compactness assessment. However, these non-destructive and non-nuclear methods require many special precautions for the compactness assessment. First of all, they allow to measure the dielectric permittivity of the investigated material. Then to figure out the compactness, the use of EM mixing models is required. This leads to the accurate knowledge of every components constituting the asphalt pavement and their related properties (density and permittivity). The first main part of this work spotlights the relevance of using a step frequency radar for the compactness assessment. The study of several EM mixing models is performed to select the most appropriate ones. Nowadays, one of the challenges to address for these techniques is that the use of recycled materials is more and more commonly implemented for new roads building. Indeed, as the knowledge of the component properties is required, this makes the compactness assessment even more difficult. As a consequence, several methods have been developed and are proposed to assess the compactness of a new paved highway containing recycled asphalt pavement. The second main part of this research is the dielectric characterization of many rocks which are the main component of the asphalt pavement. This characterization is validated from low to high frequencies and also as a function of the temperature. The results show at high frequency that the permittivity is mainly dependent on the density and the chemical composition of the rock. However, as the frequency decreases and the temperature varies, this is not longer true and additional phenomena appear and drastically change the dielectric behavior of the rock. Also, it has been shown that the water plays a major role on the dielectric behavior at low frequency. This phenomena are reflected partially by small variations at "high frequency" that could explained the deviations obtained for capacitive techniques which work in the MHz region and which are used also for the compactness assessment.