Ce travail de doctorat consiste à valoriser les coproduits issus des industries d’agrumes par des technologies innovantes. Le pressage des agrumes produit des millions de tonnes de déchets par an dans le monde. Ces déchets (peaux, pulpes et pépins) sont généralement dédiés à l’alimentation animale ou bien éliminés par compostage ou incinération. Cependant leur contenu en molécules bioactives conduit à plusieurs voies de valorisation. Vu que les peaux constituent à peu près la moitié de la masse des déchets d’agrumes, les études ont été faites sur la valorisation des peaux de différents types d’agrumes. Les méthodes conventionnelles généralement utilisées pour l’extraction des molécules d’intérêt (extraction solide-liquide, hydrodistillation) présentent plusieurs désavantages tels que l’utilisation des solvants coûteux et toxiques, les longues durées d’extraction et la consommation élevée en énergie. Pour cette raison plusieurs technologies innovantes non thermiques telles que les Champs Electriques Pulsés (CEP), les Décharges Électriques de Haute Tension (DEHT) et les ultrasons (US) et thermiques comme les microondes (MO) et les infrarouges (IR) ont été testées dans ce travail de thèse, pour la valorisation des coproduits d’agrumes. Les agrumes entiers (oranges, pomelos, citrons) sont traités par les CEP à une intensité de 3 kV/cm et l’extraction du jus d’agrumes et des polyphénols a été réalisée par pressage. L’étude de la perméabilisation cellulaire induite par les CEP a été réalisée par plusieurs méthodes et a montré que les degrés d’endommagement diffèrent selon le type d’agrumes traités. L’électroporation des cellules, induite par les CEP a permis d’augmenter les rendements en jus après pressage et d’améliorer le passage des polyphénols des peaux d’agrumes dans le jus. Ce qui explique la possibilité d’obtention d’un jus riche en polyphénols en traitant les agrumes par les CEP avant leur pressage. Parmi les solvants testés pour l’extraction des polyphénols à partir des peaux d’agrumes, l’eau est le moins efficace. L’ajout de 20% de glycérol dans l’eau a modifié la polarité du milieu et a amélioré l’extraction des polyphénols. L’utilisation d’un mélange enzymatique a favorisé la libération des polyphénols piégés dans les polysaccharides. Les solvants eutectiques profonds préparés, ont été aussi efficaces que les mélanges hydro éthanoliques. Pour améliorer d’avantages l’extraction dans les différents solvants verts ou dans le mélange enzymatique, les peaux d’agrumes ont été prétraitées par les DEHT dans l’eau. L’effet mécanique des DEHT, capable de fragmenter les peaux a permis d’améliorer l’extraction des polyphénols 6 dans les différents solvants. L’intensification de l’extraction des polyphénols a été aussi réalisée par les IR et les US. L’extraction des polyphénols par les IR a été optimisée en ayant recours à la méthodologie de surface de réponse. Le chauffage par les IR n’a pas altéré les polyphénols extraits qui ont gardé des activités antifongiques et anti-mycotoxinogènes importantes. Le prétraitement des peaux d’agrumes par les IR sans solvant a fragilisé les structures cellulaires, ce qui a permis d’augmenter la diffusion des polyphénols durant le traitement avec les US. / This work consists of the valorization of citrus by-products with innovative technologies. Citrus pressing produces millions of tons of waste per year worldwide. This waste (peels, pulps and seeds) is generally dedicated to animal feed or eliminated by composting or incineration. However its content in bioactive molecules leads to several ways of valorization. Since peels present about half of the citrus waste mass, studies have been focused on the valorization of citrus peels by the extraction of bioactive compounds. Conventional methods generally used for the extraction of bioactive compounds (solid-liquid extraction, hydrodistillation) have several disadvantages such as the use of expensive and toxic solvents, long extraction times and high energy consumption. For this reason, several innovative non-thermal technologies such as Pulsed Electric Fields (PEF), High Voltage Electrical Discharges (HVED) and Ultrasounds (US) and thermal treatments such as microwaves (MO) and infrared (IR) have been tested for the valorization of citrus by-products. Whole citrus fruits (oranges, pomelos, lemons) were PEF treated at an intensity of 3 kV/cm, then citrus juice and polyphenols were extracted by pressing. The study of the PEF-induced cell permeabilization was conducted by several methods and showed that the degree of damage varied according to the type of the treated fruit. The electroporation of the cells induced by the PEF, allowed an increase the juice yields after pressing and improved the liberation of the polyphenols from the citrus peels into the juice. This explains the possibility of obtaining a juice rich in polyphenols by treating the whole fruits with PEF before pressing. Among the solvents tested for the extraction of polyphenols from citrus peels, water is the least effective. The addition of 20% glycerol to water changed the polarity of the medium and improved the extraction of the polyphenols. The use of an enzyme mixture enhanced the release of the polyphenols related to the polysaccharides. Deep eutectic solvents have been as effective as hydroethanolic mixtures. To improve the yields and the kinetics of extractions in the different green solvents and in the enzyme mixture, citrus peels were pretreated with HVED in water. The mechanical effect of HVED, based on the fragmentation of the peels has improved the extraction of polyphenols in the various solvents. The intensification of polyphenols extraction was also conducted by IR and US. The extraction of polyphenols by IR was optimized using the surface response methodology. IR heating did not alter the extracted polyphenols which have significant antifungal and anti-mycotoxinogenic activities. The pretreatment of citrus peels with IR weakened the cell structures, increasing thus the diffusion of polyphenols during US treatment.

In the aerospace industry, gas discharges have gained importance with the exploration of their performance and capabilities for flow control and combustion. Tunable properties of plasma make gas discharges efficient tools for various purposes. Since the scales of plasma and the available technology limit the knowledge gained from experimental studies, computational studies are essential to understand the results of experimental studies. The temporal and spatial scales of plasma also restrict the numerical studies. It is a necessity to use an idealized model, in which enough physics is captured, while the computational costs are acceptable.<br><br>In this work, numerical simulations of different low-pressure gas discharges are presented with a detailed analysis of the numerical approach. A one moment model is employed for DC glow discharges and nanosecond-pulse discharges. The cheap-est method regarding the modeling and simulation costs is chosen by checking the requirements of the fundamental processes of gas discharges. The verification of one-moment 1-D glow discharges with constant electron temperature variation is achieved by comparing other computational results.<br><br>The one moment model for pulse discharge simulation aims to capture the information from the experimental data for low-pressure argon discharges. Since the constant temperature assumption is crude, the local field approximation is investigated to obtain the data for electron temperature. It was observed that experimental data and computational data do not match because of the stagnant decay of electron number densities and temperatures. At the suggestion of the experimental group, water vapor was added as an impurity to the plasma chemistry. Although there was an improvement with the addition of water vapor, the results were still not in good agreement with experiment.<br><br>The applicability of the local field approximation was investigated, and non-local effects were included in the context of an averaged energy equation. A 0-D electron temperature equation was employed with the collision frequencies obtained from the local field approximation. It was observed that the shape of the decay profiles matched with the experimental data. The number densities; however, are less almost an order of magnitude.<br><br>As a final step, the two-moment model, one-moment model plus thermal electron energy equation, was solved to involve non-local effects. The two-moment model allows capturing of non-local effects and improves agreement with the experimental data. Overall, it was observed that non-local regions dominate low-pressure pulsed discharges. The local field approximation is not adequate to solve these types of discharges.

Dissertação(mestrado) - Universidade Federal do Rio Grande, Programa de Pós-Graduação em Engenharia Oceânica, Escola de Engenharia, 2005. / Submitted by Lilian M. Silva (lilianmadeirasilva@hotmail.com) on 2013-04-20T21:03:34Z No. of bitstreams: 1 Estudo para o desenvolvimento de um previsor descargas elétricas atmosféricas aplicado à região costeira do estado do Rio de Janeiro.pdf: 5929611 bytes, checksum: 6d12186a0ae17fe81eca3382c1b88f42 (MD5) / Approved for entry into archive by Bruna Vieira(bruninha_vieira@ibest.com.br) on 2013-06-04T16:31:08Z (GMT) No. of bitstreams: 1 Estudo para o desenvolvimento de um previsor descargas elétricas atmosféricas aplicado à região costeira do estado do Rio de Janeiro.pdf: 5929611 bytes, checksum: 6d12186a0ae17fe81eca3382c1b88f42 (MD5) / Made available in DSpace on 2013-06-04T16:31:08Z (GMT). No. of bitstreams: 1 Estudo para o desenvolvimento de um previsor descargas elétricas atmosféricas aplicado à região costeira do estado do Rio de Janeiro.pdf: 5929611 bytes, checksum: 6d12186a0ae17fe81eca3382c1b88f42 (MD5) Previous issue date: 2005 / The atmospheric dynamics evidently is very complex. There are many macro and micron scales processes and meteorological variables involved in the atmospheric physical phenomena. The storms with electrical dischargesare distinguished, among these phenomena, by the damage consequences to the human beings, directly or indirectly. Many researchers have pursued the possibility of forecasting the occurrence of a storm with electrical discharges, principally in the last three decades. However, there are not improvements in forecast performance, mainly due to phenomenon complexity. The main objective of the present dissertation was to accomplish a study to determine the viability or not of constructing a forecast system of atmospheric electrical discharges from artificial intelligence techniques, specifically artificial neural networks (NN). The base of the system was constituted of numerical simulations results of the atmospheric dynamics obtained from the mesoscale model MM5. It was identified meteorological variables (outputs of MM5) that would have some correlation with the electrical discharges. These variables act as input in the NN, which generate the forecast, consisting in the number of electrical discharges that will reach the ground some posterior time to the relative time of the simulated atmospheric fields. The region chosen for this study includes the state of Rio de Janeiro, the south of Espírito Santo, the southeast of Minas Gerais and the AtlanticOcean. Besides possessing a detection system of electrical discharges, this region contains the most important concentration of oil platforms of Brazil, being strategic to better know the atmospheric behavior in this place. Before developing the forecast system based on NN, some comparative tests were made using the MM5 simulation results and GOES infrared imagery, in order to survey the model prognostic capability. The forecast system showed reasonable results, indicating that the NN application may be a promising way to the electrical discharge forecast. However, it is necessary a better investigation, mainly with relation to the accomplishment of others tests with a bigger set of electrical discharges real data. / A dinâmica da atmosfera é evidentemente bastante complexa. Muitos são os processos físicos de macro e micro escalas e as variáveis meteorológicas envolvidos nos fenômenos atmosféricos. As tempestades com descargas elétricas destacam-se, dentre estes fenômenos, pelas conseqüências danosas causadas aos seres humanos, direta ou indiretamente. Diversos pesquisadores têm procurado investigar a possibilidade de prever a ocorrência de tempestades com descargas elétricas, principalmente nas úl timas três décadas, entretanto, progressos na performance da previsão ainda não foram alcançados devido à complexidade do fenômeno. O principal objetivo da presente dissertação foi realizar um estudo para determinar a viabilidade ou não de construir um sistema de previsão de descargas elétricas atmosféricas a partir de técnicas de inteligência artificial, mais precisamente redes neurais artificiais (RNA). A base do sistema constituiu-se de resultados de simulações numéricas da dinâmica atmosférica obtidos com o modelo de mesoescala MM5. Variáveis meteorológicas (saídas do MM5), que teriam alguma correlação com as descargas elétricas, foram identificadas e selecionadas como entradas na RNA, a qual gera a previsão, isto é, o número de descargas elétricas que atingirá o solo algum tempo posterior ao tempo relativo dos campos atmosféricos simulados. A região escolhida para este estudo, abrangendo o Estado do Rio de Janeiro, o sul do Estado do Espírito Santo, o sudeste do Estado de Minas Gerais e o Oceano Atlântico, além de possuir um sistema de detecção e monitoramento de descargas elétricas, contém a mais importante concentração de plataformas de petróleo do Brasil, sendo, portanto, estratégico conhecer melhor o seu comportamento atmosférico. Antes de desenvolver o sistema de previsão baseado em RNA, alguns testes comparativ os foram realizados usando resultados de simulação do MM5 e imagens infravermelhas de satélite geoestacionário, a fim de aferir a capacidade preditiva do modelo. O sistema de previsão apresentou resultados razoáveis, indicando que a aplicação da RNA é um cami nho promissor na previsão de descargas elétricas. Contudo, faz-se necessária uma mel hor investigação, principalmente quanto à realização de outros testes com um conjunto maior de dados reais de descargas elétricas.

Orientadores: José Pissolato Filho, Pierre Kaufmann / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-23T01:41:59Z (GMT). No. of bitstreams: 1 Duro_MagdaAparecidaSalgueiro_D.pdf: 3861523 bytes, checksum: f5896319d2a3653a7903f977210f3ac1 (MD5) Previous issue date: 2013 / Resumo: A atual dependência da sociedade aos diversos sistemas tecnológicos em funcionamento na Terra traz uma constante preocupação pela sua vulnerabilidade a fatores menos conhecidos. As possíveis falhas no fornecimento de energia elétrica podem ocasionar transtornos de grande impacto às comunidades podendo acarretar perdas financeiras expressivas. Diversos fatores podem ocasionar falhas nas linhas de transmissão, entre eles, os fatores climáticos. Nesse contexto, são pouco conhecidas as influências qualitativas de distintos fatores, destacando-se os efeitos do denominado clima espacial. Há indicações que o clima espacial influencia a alta atmosfera terrestre, com repercussão no clima bem como em sistemas de engenharia em operação na Terra. As redes de transmissão de alta tensão representam um grande circuito elétrico pouco acima do solo sujeito a uma série de sobrecargas temporárias de vários tipos, algumas das quais podem levar a falhas. Algumas destas falhas podem estar relacionadas ao ambiente geofísico. Neste trabalho foi analisada uma base de dados sem precedentes de falhas em linhas de transmissão por um longo período (nove anos) numa grande malha localizada no Estado de São Paulo (sudeste do Brasil). O período estudado (1998-2006) compreende uma significativa fração do ciclo de atividade solar 23. A concessionária responsável (ISA.CTEEP) pela operação das linhas estudadas classifica as falhas em noventa e cinco tipos distintos de causas possíveis, sendo que a maior parte está relacionada às descargas atmosféricas. Este estudo está relacionado aos desligamentos devido às descargas atmosféricas, em duas redes de alta voltagem da companhia, de 138 kV e de 440 kV. No período estudado, estes desligamentos correspondem a 1.957 (42,80%) num total de 4.572 para a linha de 138 kV e de 170 (22,28%) sobre 763 para a linha de 440 kV. Equivale a menos de um a cada dez mil do número total de descargas atmosféricas ocorridas na mesma área, o que demonstra alta resiliência das redes de potência em relação aos raios. Durante a época das chuvas, há uma maior concentração de desligamentos. Para todo o período estudado houve redução de 67% e 77% no número de desligamentos devido às descargas atmosféricas, para as linhas de 138 kV e 440 kV, respectivamente, havendo uma boa correspondência com a redução do número de manchas solares. Nenhuma correlação foi encontrada em relação às atividades geomagnéticas caracterizadas pelo índice planetário (Kp) e pelas grandes tempestades (Dst) tanto em longos quanto em curtos prazos. Uma explicação sugerida associa a diminuição da atividade solar ao aumento da condutividade na atmosfera causada pelo maior fluxo de raios cósmicos. Consequentemente poderá ocorrer uma redução do limiar de voltagem necessário para produzir descargas atmosféricas para provocar desligamentos nas redes de alta voltagem. O circuito elétrico global descrito pelo acoplamento ionosfera-terra (a eletrosfera) exerce um papel importante para explicar a redução dos desligamentos. Com o aumento da condutividade atmosférica as descargas são menos potentes, resultando em menor número de desligamentos com o decréscimo do ciclo solar / Abstract: The current society dependence on the operating technological systems on the Earth brings a permanent concern for their vulnerability to not well known factors. Possible failures in electricity supply can cause inconveniences with large impact to the communities, which may cause significant financial losses. Different factors can cause failures in the transmission networks, including, climate factors. In this context, the influences of various qualitative factors, especially the effects of space weather are not well known. There are indications that space weather affects the upper atmosphere, with repercussions on the climate as well as in engineering systems in operation on Earth. High-voltage transmission networks represent large electrical circuits just above the ground which are subjected to a number of transient overcharges of various kinds, some of which may lead to failures. Some failures might be related to anomalies of the geophysical environment. In the present study we analyze a database consisting in a one unprecedented long series of transmission grid failures (nine years) on high-voltage networks located in São Paulo state (southeastern Brazil). The studied period (1998-2006) includes an important fraction of the solar activity cycle 23. The company responsible by the power grid operator (ISA.CTEEP) classifies causes in ninety-five distinct failure classes to explain the transmission grid shut downs. Most of the failures were attributed to atmospheric discharges. We have studied the failures attributed to atmospheric discharge, in the two power grids of the company, 138 kV and 440 kV. The failures attributed to atmospheric discharge correspond to 1.957 (42.80%) for a total 4.572 at 138 kV and to 170 (22.8%) out of 763 at 440 kV. They correspond to less than one ten thousandth of the actual number of atmospheric discharges recorded in the same area, demonstrating the grid's high resilience to breakdowns due to lightning. A clear concentration of failures in the region's thunderstorm season has been found. A significant 67% and 77% reduction in the number of failure rates has been found for the 138 and 440 kV grids, respectively, for the period studied, in good correspondence with the decay in the sunspot numbers. No obvious correlation was found between power failures and geomagnetic activity, represented by (Kp) the planetary index or major geomagnetic storms (Dst) in the period, either on short or on long time scales. One suggested explanation associates the decrease in solar activity to the increased conductivity in the atmosphere caused by increase cosmic ray flux. Consequently there may be a reduction in the threshold voltage necessary to produce discharge atmospheric to cause failures in high-voltage grids. The global electric circuit described by the ionosphere-ground coupling (the electrosphere), plays an important role in explaining the reduction the failures. With increase in conductivity atmospheric discharges are less potent, resulting in fewer failures with the decreasing solar cycle / Doutorado / Energia Eletrica / Doutor em Engenharia Elétrica

<div>Developments in modern electronics drive device design to smaller scale and higher electric fields and currents. Device size reductions to microscale and smaller have invalidated the assumption of avalanche formation for the traditional Paschen’s law for predicting gas breakdown. Under these conditions, the stronger electric fields induce field emission driven microscale gas breakdown; however, these theories often rely upon semi-empirical models to account for surface effects and the dependence of gas ionization on electric field, making them difficult to use for predicting device behavior a priori.</div><div>This dissertation hypothesizes that one may predict a priori how to tune emission physics and breakdown conditions for various electrode conditions (sharpness and surface roughness), gap size, and pressure. Specifically, it focuses on experiments to demonstrate the implications of surface roughness and emitter shape on gas breakdown for microscale and nanoscale devices at atmospheric pressure and simulations to extend traditional semi-empirical representations of the ionization coefficient to the relevant electric fields for these operating conditions.</div><div>First, this dissertation reports the effect of multiple discharges for 1 μm, 5 μm, and 10 μm gaps at atmospheric pressure. Multiple breakdown events create circular craters to 40 μm deep with crater depth more pronounced for smaller gap sizes and greater cathode surface roughness. Theoretical models of microscale breakdown using this modified effective gap distance agree well with the experimental results.</div><div>We next investigated the implications of gap distance and protrusion sharpness for nanoscale devices made of gold and titanium layered onto silicon wafers electrically isolated with SiO2 for gas breakdown and electron emission at atmospheric pressure. At lower voltages, the emitted current followed the Fowler-Nordheim (FN) law for field emission (FE). For either a 28 nm or 450 nm gap, gas breakdown occurred directly from FE, as observed for microscale gaps. For a 125 nm gap, emission current begins to transition toward the Mott-Gurney law for space-charge limited emission (SCLE) with collisions prior to undergoing breakdown. Thus, depending upon the conditions, gas breakdown may directly transition from either SCLE or FE for submicroscale gaps.</div><div>Applying microscale gas breakdown theories to predict this experimental behavior requires appropriately accounting for all physical parameters in the model. One critical parameter in these theories is the ionization coefficient, which has been determined semi-empirically with fitting parameters tabulated in the literature. Because these models fail at the strong electric fields relevant to the experiments reported above, we performed particle-in-cell simulations to calculate the ionization coefficient for argon and helium at various gap distances, pressures, and applied voltages to derive more comprehensive semi-empirical relationships to incorporate into breakdown theories.</div><div>In summary, this dissertation provides the first comprehensive assessment of the implications of surface roughness on microscale gas breakdown, the transition in gas breakdown and electron emission mechanisms at nanoscale, and the extension of semi-empirical laws for ionization coefficient. These results will be valuable in developing theories to predict electron emission and gas breakdown conditions for guiding nanoscale device design.</div>

<p>Multiple industry applications, including combustion, flow control, and medicine, have leveraged nanosecond pulsed plasma (NPP) discharges to create plasma generated reactive species (PGRS). The PGRS are essential to induce plasma-assisted mechanisms, but the rate of generation and permanence of these species remains complex. Many of the mechanisms surrounding plasma discharge have been discovered through experiments, but a consistent challenge of time scales limits the plasma measurements. Thus, a well-constructed model with experimental research will help elucidate complex plasma physics. The motivation of this work is to construct a feasible physical model within the additional numerical times scale limitations and computational resources. This thesis summarizes the development of a one-moment fluid model for NPP discharges, which are applied due to their efficacy in generating ionized and excited species from vacuum to atmospheric pressure. </p><p>From a pulsed power perspective, the influence of pulse parameters, such as electric field intensity, pulse shape and repetition rate, are critical; however, the effects of these parameters on PGRS remain incompletely characterized. Here, we assess the influence of pulse conditions on the electric field and PGRS computationally by coupling a quasi-one-dimensional model for a parallel plate geometry, with a Boltzmann solver (BOLSIG+) used to improve plasma species characterization. We first consider a low-pressure gas discharge (3 Torr) using a five-species model for argon. <a>We then extend to a 23 species model with a reduced set of reactions for air chemistry remaining at low pressure.</a> The foundations of a single NPP is first discussed to build upon the analysis of repeating pulses. Because many applications use multiple electric pulses (EPs) the need to examine EP parameters is necessary to optimize ionization and PGRS formation. </p><p>The major goal of this study is to understand how the delivered EP parameters scale with the generated species in the plasma. Beginning with a similar scaling study done by Paschen we examine the effects of scaling pressure and gap length when the product remains constant for the two models. This then leads to our study on the relationship of pulsed power for different voltages and pulse widths of EPs. By fixing the energy delivered to the gap for a single pulse we determine that the electron and ion number densities both increased with decreasing pulse duration; however, the rate of this increase of number densities appeared to reach a limit for 3 ns. These results suggest the feasibly of achieving comparable outputs using less expensive pulse generators with higher pulse duration and lower peak voltage. Lastly, we study these outcomes when increasing the number of pulses and discuss the effects of pulse repetition and the electron temperature.</p><p>Future work will extend this parametric study to different geometries (i.e. pin-to-plate, and pin-to pin) and ultimately incorporate this model into a high-fidelity computational fluid dynamics (CFD) model that may be compared to spectroscopic results under quiescent and flowing conditions will be discussed.<br></p>

<p> In the past two decades, great interest in weakly ionized plasmas sustained by high voltage nanosecond pulsed plasmas at high repetition rates has emerged. For such plasmas, the electron number density does not significantly decay between pulses, unlike the electron temperature. Such conditions are favorable to reconfigurable plasma antennas where the low electron temperature may enable the reduction of the Johnson–Nyquist thermal noise if an antenna is operated in the plasma afterglow. Moreover, it may be possible to sustain such conditions with RF pulses. Doing so could enable a plasma antenna that transmits the driving frequency when the pulse is applied and receives other frequencies with low thermal noise between pulses.</p> <p>To study nanosecond pulsed plasmas, experiments were performed in a parallel-plate electrode configuration in argon and nitrogen gas at a pressure of several Torr and repetition frequencies of 30-75 kHz. To measure the time-resolved electron number density in the afterglow of each pulse, a custom 58.1 GHz homodyne microwave interferometer was constructed. The voltage and current measurements were made using a back current shunt (BCS). Initial analysis of the measured electron density in both plasmas indicated that the electron thermalization was much faster than the electron decay. In the nitrogen plasma, dissociative recombination with cluster ions was the dominant electron loss mechanism. However, the dissociative recombination rates of the electrons in the argon plasma suggested the presence of molecular impurities, such as water vapor. Therefore, to better understand the recombination mechanisms in argon plasma with trace amounts (0.1% or less by volume) of water vapor under the experimental conditions, a 0-D kinetic model was developed and fit to the experimental data. The influence of trace amounts of water on the electron temperature and density decay was studied by solving electron energy and continuity equations. It was found that in pure argon, Ar⁺ ions dominate while the electrons are very slow to thermalize and recombine. Including trace amounts of water impurities drastically reduces the time for electrons to thermalize and increases their rate of recombination. </p> <p>In addition to large quasi-steady electron number densities and low electron temperature in the plasma afterglow, plasmas sustained by nanosecond pulses use a lower power budget than those sustained by RF or DC supplies. The efficiency of the power budget can be characterized by measuring the ionization cost per electron, defined as the ratio of the energy deposited in a pulse to the total number of electrons created. This was experimentally determined in air and argon plasmas at 2-10 Torr sustained by 1-7 kV nanosecond pulses at repetition frequencies of 0.1-30 kHz. The number of electrons were determined from the measured electron density through microwave interferometry and assuming a plasma volume equivalent to the volume between electrodes. The energy deposited was calculated from voltage and current measurements using both a BCS as well as high frequency resistive voltage divider and fast current transformer (FCT). It was found that the ionization cost in all conditions was within a factor of three of Stoletov’s point (the theoretical minimum ionization cost) and two orders of magnitude less than RF plasma.</p><p> </p><p>Having shown that it is possible to generate high electron density, low electron temperature plasmas with nanosecond pulses, it was necessary to now create a plasma antenna prototype. Initially, commercial fluorescent light bulbs were used and ignited using surface wave excitation at various RF frequencies and powers. The S₁₁ of the antenna response was measured by a VNA through a novel coupling circuit, while the deposited power was measured using a bi-directional coupler. Next, a custom plasma antenna was created in which the pressure and gas composition could be varied. In addition to the S₁₁ and deposited power, the antenna gain, and the electron number density were also measured for a pure argon plasma antenna at pressures of 0.3-1 Torr. Varying the applied power shifts the antenna resonance frequency while increasing the excitation frequency caused an increase in measured electron density for the same deposited power. Initial tests using direct electrode excitation of a twin-tube integrated compact fluorescent light bulb with nanosecond pulses have successfully been achieved. Future efforts include designing the proper circuitry to time-gate out the large pulse voltage to facilitate safe antenna measurements in the plasma afterglow.<br></p>

Ce projet de thèse est dédié à l’étude de l’intensification de l’extraction des polymères d’hémicelluloses à partir du bois d’épicéa par l’application de prétraitements physicochimiques : microondes (MO), décharges électriques de hautes tension (DEHT) et explosion à la vapeur (STEX). L’extraction des hémicelluloses est souvent réalisée par autohydrolyse ou par des traitements chimiques. Dans ce travail de thèse, nous avons étudié un procédé basé sur l’extraction des hémicelluloses en combinant des prétraitements physiques aux prétraitements chimiques et à l’autohydrolyse. Ce couplage a permis d’avoir des hémicelluloses avec des poids moléculaires moyens en masse (Mw) élevés allant jusqu’à 70 kDa, 66 kDa et 55 kDa lors des extractions en milieu basique par STEX, MO et DEHT respectivement. Les performances des prétraitements en termes de rendement d’extraction sont plus élevées que pour l’autohydrolyse seule pour les mêmes conditions de température et de temps d’extraction. La caractérisation des hémicelluloses extraites a révélé une sélectivité d’extraction en fonction du pH du milieu d’imprégnation. L’imprégnation en milieu neutre favorise la solubilisation des galactoglucomannanes (GGM) et l’imprégnation en milieu basique favorise la solubilisation des arabinoglucoronoxylanes (ARX). L’analyse du degré d’acétylation (DA) a montré que la STEX a permis d’extraire des acetyl-GGM avec des DA (~0,35) proches de celui des hémicelluloses à l’état natif. Les films élaborés à partir des hémicelluloses extraites présentent des barrières intéressantes vis à vis de l’oxygène (0,83 cm3.μm-1.jour-1.kPa au maximum) et du rayonnement UV. / This thesis project is specifically dedicated to the study of the intensification of the extraction of hemicellulose polymers from spruce wood by the application of physicochemical pretreatments: Microwave (MW), High Voltage Electrical Discharge (HVED) and Steam Explosion (STEX). Extraction of hemicelluloses is often carried out by an autohydrolysis or by chemical treatments. In this work, we have developed an original process for extracting hemicelluloses polymers by combining physical pretreatments (MW, HVED and STEX) with chemical pretreatments and autohydrolysis. This combination allowed us to recover hemicelluloses with average molecular weights (Mw) highs up to 70 kDa, 66 kDa and 55 kDa when STEX, MW and HVED were applied in basic medium respectively. The performance of the pretreatments in terms of extraction yield is higher than the autohydrolysis alone for the same extraction temperatures. The characterization of the extracted hemicelluloses revealed an extraction selectivity as a function of the pH of the medium of impregnation. Impregnation in neutral medium promotes the solubilization of galactoglucomannans (GGM) and impregnation in a basic medium promotes the solubilization of arabinoglucoronoxylans (ARX). The analysis of the degree of acetylation (AD) showed that STEX pretreatment allowed the extraction of acetyl-GGM with an AD of approximately 0.35 which is close to that in native hemicelluloses.The characterization of films made from extracted hemicelluloses showed that these films are good barrier to oxygen with oxygen permeability near to 0.83 cm3 μm-1 day-1 kPa-1 and to UV radiations.

Ce travail de thèse concerne l’utilisation des électrotechnologies pour une valorisation optimisée de la betterave à sucre conformément au concept de bioraffinerie. Les électro-technologies appliquées sont les champs électriques pulsés (CEP) et les décharges électriques de haute tension (DEHT). L’étude s’attache d’une part à l’optimisation d’un procédé alternatif pour l’extraction du sucre par pressage alcalin à froid assisté par CEP. D’autre part, elle propose des nouvelles voies pour la valorisation de deux coproduits de l’industrie betteravière qui sont les radicelles et la pulpe de betterave. Dans la première partie, le traitement électrique par CEP couplé au chaulage permet une meilleure désintégration du tissu betteravier. Il permet d’accélérer les cinétiques du pressage, d’améliorer le rendement ainsi que la qualité du jus et d’alléger la procédure de purification en aval de l’extraction. Une étude paramétrique d’optimisation a permis d’identifier le meilleur itinéraire d’application de ce nouveau procédé d’extraction. Les cossettes fraîches de betterave sont prétraitées par CEP à 600 V/cm pour 10 ms (Q = 2,7 Wh/kg). Les cossettes électroporées sont ensuite pressées à froid pour extraire 75 % du jus. Les cossettes pressées subissent un pressage alcalin avec 10 % du lait de chaux. Afin d’extraire le sucre résiduel dans le gâteau de pressage obtenu, deux étapes de pressage supplémentaires avec une étape intermédiaire d’hydratation sont nécessaires. Ce procédé optimisé permet de bien épuiser les cossettes en sucre (perte en sucre de 0,23 % et matière sèche de pulpes de 39 %) pendant une courte durée d’extraction (30 min) avec un faible soutirage (108 %) par rapport au procédé de diffusion. Il permet ainsi des économies significatives de matière et d’énergie surtout pour les étapes d’extraction du jus et de séchage de pulpes. Par rapport au procédé conventionnel, le gain énergétique s’élève à 91,96 × 106 kWh pour une usine traitant 10 000 t/j de betteraves pendant une campagne de 110 jours. De plus, le procédé proposé permet de simplifier la procédure de purification et de réduire de 50 à 60 % la quantité de chaux utilisée. Dans la deuxième partie de cette étude, deux procédés de transformation ont été proposés et optimisés à l’échelle laboratoire pour la valorisation des radicelles et de la pulpe de betterave à sucre. Les radicelles ont été utilisées pour produire du bioéthanol. Le jus brut de radicelles a été extrait par pressage à froid assisté par CEP. La production du bioéthanol a été achevée par fermentation alcoolique. Le prétraitement par CEP (450 V/cm, 10 ms) a permis d’accélérer la cinétique de pressage, d’augmenter le rendement en solutés (79,85 % vs. 16,8 %) et d’obtenir un jus plus concentré (10 % vs. 5,2 %). Le procédé optimisé permet de produire environ 41,75 L de bioéthanol par tonne de radicelles lorsque l’on applique un prétraitement par CEP contre seulement 8,2 L de bioéthanol sans prétraitement électrique confirmant ainsi le potentiel de ce nouveau schéma de valorisation. La pulpe de betterave déshydratée ayant une matière sèche de 92,8 % a été utilisée pour l’extraction de pectines. L’étude réalisée a montré que l’application d’un prétraitement par DEHT permet d’intensifier l’extraction des pectines. Le gain relatif de rendement en pectines est de 25,3 % pour une énergie consommée de 76,2 kJ/kg. Le schéma de bioraffinage proposé pourra aider au maintien de la filière betteravière en France après la suppression de système de quotas sucriers dans l’Union européen qui entrera en vigueur le 1er octobre 2017. / This work discusses the use of electrotechnologies for an optimized valorization of sugar beet according to the concept of biorefinery. The applied electrotechnologies are pulsed electric fields (PEF) and high-voltage electrical discharges (HVED). The study firstly aims at optimizing an alternative method for sugar extraction by PEF assisted cold alkaline pressing. On the other hand, it proposes new ways for valorizing two by-products of sugar beet industry, which are sugar beet tails and pulps. In the first part, PEF treatment combined with liming leads to a better disintegration of beet tissue. It permits accelerating of pressing kinetics, improvement of juice yield and quality, and reduction of subsequent purification procedure. A parametric optimization study identified the best application itinerary of the proposed extraction process. Fresh sugar beet cossettes are pretreated by PEF at 600 V/cm for 10 ms (Q = 2.7 Wh/kg). The electroporated cossettes are then pressed to extract 75% of intracellular juice. Compressed cossettes are subjected to an alkaline pressing with 10% lime milk. In order to extract the residual sucrose in the obtained press-cake, two additional steps of pressing with an intermediate hydration are required. This optimized process allows well exhausting the sugar cossettes (sugar loss of 0.23% and pulp dry matter of 39%) for a short extraction (30 min) and with low draft (108%) compared to diffusion method. Thus, it allows substantial saving in materials and energy especially for juice extraction and pulp drying. Compared to the conventional method, the energy saving amounted to 91.96 × 106 kWh for a sugar beet factory treating 10 000 tons per day for a campaign of 110 days. In addition, the proposed method simplifies the purification procedure of raw juice and reduces the used amount of lime from 50 to 60%. In the second part of this study, two processing methods were proposed and optimized at lab-scale for valorization of sugar beet tails and pulps. Sugar beet tails were used to produce bioethanol. Raw juice of beet tails was extracted by PEF assisted cold pressing. Bioethanol production was then done by alcoholic fermentation. Pretreatment of beet tails with PEF (450 V/cm, 10 ms) permits accelerating the pressing kinetics, increasing the yield of solutes (79.85% vs. 16.8%), and leads to a more concentrated juice (10% vs. 5.2%). The optimized process permits the production of about 41.75 L of bioethanol per ton of beet tails when PEF pretreatment is applied against only 8.2 L of bioethanol without PEF confirming the potential of this new valorization scheme. Dried beet pulp having a dry matter of 92.8% was used for pectin recovery. The present study showed that the application of HVED pretreatment leads to intensify pectin extraction. The relative gain of pectin yield is 25.3% with an energy consumption of 76.2 kJ/kg. The proposed biorefinery scheme could protect the sugar beet industry in France after the suppression of the sugar quota system in the European Union, which will take effect on 1st October 2017.

Ce travail de thèse concerne l'étude et l'évaluation de l'extraction et de la séparation de molécules d'intérêt à partir des résidus de colza. L'impact des différents traitements (broyage, champs électriques pulsés, décharges électriques de hautes tensions et ultrasons) sur l'amélioration de l'extraction des polyphénols et des protéines à partir des tiges de colza a été comparé. Ces traitements permettent d'endommager les membranes et/ou parois cellulaires de manière mécanique, électrique ou acoustique, facilitant ainsi la libération des composés intracellulaires vers le milieu extérieur. La cinétique d'extraction, le rendement en polyphenols totaux et en protéines et la consommation énergétique sont principalement étudiés. De plus, l'efficacité des traitements étudiés pour l'extraction des polyphénols et protéines, en fonction du degré de maturité de la plante a été étudiée. Les méthodes testées pour la séparation des extractibles (polyphénols et protéines) concernent la coagulation, la filtration membranaire ainsi que le couplage de ces deux méthodes afin de réduire la consommation de solvants organiques et la rétention des polyphénols au cours de séparation. La séparation des extractibles a été évaluée par le biais de l'analyse de pureté et du taux de rétention. Enfin, des effets positifs du traitement électrique sur l'étape de séparation des extractibles tels que l'augmentation du flux du perméat et la diminution du colmatage ont été remarqués. / This thesis work concerns the study and the evaluation of the extraction and the separation of valuable compounds from rapeseed residues. The impact of different treatments (grinding, pulsed electric fields, high voltage electrical discharges and ultrasound) on the enhancement of the extraction of polyphenols and proteins from rapeseed stems was compared. These treatments can damage cell membranes and 1 or cell walls mechanically, electrically or acoustically, thus facilitating the release of intracellular compounds to the surroundings. The extraction kinetics, yield of total polyphenols and proteins and energy consumption were mainly studied. In addition, influences of plant maturity on the efficiency of studied treatments for the extraction of polyphenols and proteins have been studied. The methods tested for the separation of extractives (polyphenols and proteins) include coagulation, membrane filtration and the combination of these two methods in order to reduce the consumption of organic solvents and the retention ofpolyphenols during separation. The separation of extractives was evaluated by means of analysis of purity and relative removal. Finally, positive effects of electrical treatment on the extractive separation step such as the increase ofpermeate flux and the decrease of membrane fouling have been observed.