Les besoins en électronique de puissance, de plus en plus exigeants, ont motivé des recherches à l'échelle mondiale sur d'autres matériaux tels que le diamant comme remplaçant du silicium. Nos travaux de recherche sont plus spécifiquement axés sur la définition et la qualification de matériaux polymères capables de garantir l'intégrité des fonctions physiques de modules de puissance en environnement sévère. L'étude concerne la durabilité de candidats polymères à retenir pour le boîtier dont l'objectif est de protéger l'interrupteur de l'environnement extérieur. Suite aux choix des différents polymères étudiés, variables dans leur chimie et leur morphologie (amorphe ou semi-cristallin), un premier objectif scientifique est alors de chercher les relations structures/propriétés permettant de contrôler le procédé de mise en forme des polyimides semi-cristallins et d'en déduire les conditions requises à l'obtention de performances optimisées. Un second objectif a concerné la tenue des différents matériaux sélectionnés en vieillissements isothermes thermo-oxydatifs. / Requirements in power electronics are more and more demanding about materials behavior in their operating conditions. This has motivated global scale researches about other materials replacing silicon such as diamond. This study is specifically focusing on the definition and qualification of polymer materials which could preserve physical functions of power modules in severe environments. This study focuses on the durability of several polymers used for the case. This later allows to protect the chip from external environment. The choice of different studied polymers which are dissimilar in chemistry and morphology (i.e. amorphous or semicrystalline) has been made in this study. Then, a first scientific goal was to search the structures/properties relations leading to the control of the manufacturing process of semicrystalline polyimides. A second goal concerned the mechanical strength evaluation of selected materials after thermo-oxidative isothermal ageing.

Nous nous sommes intéressés à l'optimisation de la dispersion des nanotubes de carbone (CNTs) dans une matrice semi-cristalline : le polyamide 6 (PA-6), et une matrice vitreuse : le poly(méthacrylate de méthyle) (PMMA). Nous avons réalisé des dispersions dans le PA-6 et le PMMA par voie fondu. Nous avons montré que la conductivité et le seuil de conductivité étaient nettement améliorés après un post traitement thermique, quelle que soit la matrice (PMMA ou PA-6). Dans le cas du PMMA, l'étude cinétique de la conductivité en fonction de la température nous a permis de préciser le mécanisme de formation de contacts entre CNTs observé dans le fondu. Une étude structurale et morphologique des composites de PA-6 a été réalisée. Nous montrons la disparition des sphérolites de PA et avons mis en évidence la croissance de lamelles trans-cristallines de PA-6 perpendiculairement à la surface des CNTs. Les CNTs ont aussi été dispersés à partir d'un pré-composite copolymère à blocs/nanotube. Le copolymère à blocs utilisé est un polystyrène-b-polybutadiène-b-polyméthacrylate de méthyle (SBM), les différences de compatibilité de chaque bloc avec les CNTs, la matrice ou le solvant sont utilisées pour stabiliser et disperser les CNTs. L'utilisation du SBM a permis d'améliorer l'état de dispersion dans les deux matrices pour deux méthodes de dispersion : par voie solvant et par voie fondu. Dans le PA-6, l'utilisation du SBM a également permis d'abaisser le seuil de conductivité, grâce à une localisation spécifique des CNTs. Ils sont localisés à l'interface PA-6/SBM pour les pré-composites réalisés par voie fondu et dans la matrice PA-6 pour les pré-composites réalisés par voie solvant.

O yacon é uma planta perene originária da região andina, cujas raízes têm recebido atenção devido ao alto teor de frutooligossacarídeos (FOS) prebióticos. Além de proporcionar benefícios à saúde, os FOS apresentam características interessantes como ingredientes alimentícios, sendo utilizados como substitutos do açúcar. Sua extração das raízes de yacon pode ser uma alternativa aos FOS de alto custo atualmente disponíveis comercialmente. O presente trabalho avaliou a tecnologia de separação por membranas para concentração e purificação dos FOS a partir de um extrato obtido da raiz de yacon, mediante o emprego de ultrafiltração (UF) e nanofiltração (NF), com e sem utilização de diafiltração (DF) descontínua. A UF teve como objetivo clarificar o extrato de yacon, removendo partículas em suspensão de alta massa molar e recolhendo os açúcares no permeado. Depois da UF, 63,75 % dos açúcares totais presentes na solução de alimentação inicial foram recuperados no permeado. A NF do permeado, obtido previamente por UF, foi realizada para remover os sais e açúcares simples e concentrar os FOS no retido. O emprego da DF não influenciou a retenção de FOS na NF (que aumentou de 68,78 % sem DF para 70,48 % com DF), mas diminuiu a retenção de glicose de 40,63 para 31,61 % e de frutose de 25,64 para 18,69 %, permitindo uma maior purificação dos FOS no retido. Após o processo combinado de UF-NF, 51,85 % dos FOS da solução inicial foram recuperados no retido da nanofiltração, alcançando pureza de 19,75%. A seguir, o retido obtido na nanofiltração associada à diafiltração foi liofilizado. Nesse produto liofilizado foram analisadas cor, atividade de água (aw), microestrutura – por meio de microscopia eletrônica de varredura acoplada a espectroscopia por energia dispersiva de raios-X (MEV-EDS) – e cristalinidade – através de difração de raios-X. O teor de açúcares do produto liofilizado foi 19,75 % de FOS, 36,66 % de glicose e 43,59 % de frutose, em massa, com aw de 0,284. A sua aparência externa foi a de um pó granulado e esbranquiçado, cujos parâmetros de cor, no sistema CIELAB, foram de 76,25±1,19, -1,03±0,09 e 1,02±0,03 para L*, a* e b* respectivamente. A amostra se mostrou altamente higroscópica e com tendência à aglomeração, confirmada pela visualização da formação de pontes entre partículas adjacentes nas imagens do MEV. Não foram identificados picos nos difratogramas de raios-X, indicando características amorfas. Entretanto, a alta higroscopicidade da amostra, que levou à formação de uma massa rígida e contínua, pode ter dificultado a correta difração de raios-X. / Yacon is a perennial plant originated from the Andean region which roots have been receiving increased attention due to their high content in prebiotic fructooligosaccharides (FOS). Apart from promoting many health benefits, FOS present interesting characteristics as food ingredient, being used as sugar substitute, and its extraction from yacon roots may be an alternative to the high costs FOS actually commercially available. The present work evaluated membrane technology for concentrating and purifying FOS from an extract obtained from yacon roots, combining a first ultrafiltration (UF) clarifying step with nanofiltration (NF), with and without association with discontinuous diafiltration (DF). UF aimed to remove large molecules such as proteins and suspended solids, yielding a saccharide-rich permeate. After UF, 63.75 % of total saccharides from the initial feed were recovered in the permeate, that was then subjected to NF in order to reduce glucose, fructose and salts content and concentrate the oligosaccharides in the retentate. DF did not largely influenced FOS retention in NF (it increased from 68.78 % without DF to 70.48 % with DF), but decreased glucose and fructose retentions, from 40.63 to 31.61 % and 25.64 to 18.69 %, respectively, allowing a greater purification of FOS in the retentate. After the combined UF-NF process, 51.85 % of FOS from the initial feed were recovered in the NF final retentate, with 19.75 % purity. After this, the final retentate of nanofiltration associated with diafiltration was lyophilized and the powder was subjected to analyses of color, water activity (aw), microstructure – by Scanning Electron Microscopy coupled to Energy-dispersive X-ray Spectroscopy (SEM-EDS) – and crystallinity – by X-ray diffraction. The obtained freeze-dried FOS-enriched saccharides powder, containing 19.75 % of FOS, 36.66 % of glucose and 43.59 % of fructose, in weight, was a whitish granulated powder, with aw of 0.284 and CIELAB color coordinates L*, a* and b* of 76.25±1.19, -1.03±0.09 and 1.02±0.03, respectively. It was highly hygroscopic and with agglomeration tendency, confirmed by the formation of bridges between particles on the SEM images. No peaks were identified at X-ray diffractograms, indicating its amorphous characteristics. However, the sample high hygrospicity and the formation of a rigid mass may have hindered a trustable X-ray analysis.

O yacon é uma planta perene originária da região andina, cujas raízes têm recebido atenção devido ao alto teor de frutooligossacarídeos (FOS) prebióticos. Além de proporcionar benefícios à saúde, os FOS apresentam características interessantes como ingredientes alimentícios, sendo utilizados como substitutos do açúcar. Sua extração das raízes de yacon pode ser uma alternativa aos FOS de alto custo atualmente disponíveis comercialmente. O presente trabalho avaliou a tecnologia de separação por membranas para concentração e purificação dos FOS a partir de um extrato obtido da raiz de yacon, mediante o emprego de ultrafiltração (UF) e nanofiltração (NF), com e sem utilização de diafiltração (DF) descontínua. A UF teve como objetivo clarificar o extrato de yacon, removendo partículas em suspensão de alta massa molar e recolhendo os açúcares no permeado. Depois da UF, 63,75 % dos açúcares totais presentes na solução de alimentação inicial foram recuperados no permeado. A NF do permeado, obtido previamente por UF, foi realizada para remover os sais e açúcares simples e concentrar os FOS no retido. O emprego da DF não influenciou a retenção de FOS na NF (que aumentou de 68,78 % sem DF para 70,48 % com DF), mas diminuiu a retenção de glicose de 40,63 para 31,61 % e de frutose de 25,64 para 18,69 %, permitindo uma maior purificação dos FOS no retido. Após o processo combinado de UF-NF, 51,85 % dos FOS da solução inicial foram recuperados no retido da nanofiltração, alcançando pureza de 19,75%. A seguir, o retido obtido na nanofiltração associada à diafiltração foi liofilizado. Nesse produto liofilizado foram analisadas cor, atividade de água (aw), microestrutura – por meio de microscopia eletrônica de varredura acoplada a espectroscopia por energia dispersiva de raios-X (MEV-EDS) – e cristalinidade – através de difração de raios-X. O teor de açúcares do produto liofilizado foi 19,75 % de FOS, 36,66 % de glicose e 43,59 % de frutose, em massa, com aw de 0,284. A sua aparência externa foi a de um pó granulado e esbranquiçado, cujos parâmetros de cor, no sistema CIELAB, foram de 76,25±1,19, -1,03±0,09 e 1,02±0,03 para L*, a* e b* respectivamente. A amostra se mostrou altamente higroscópica e com tendência à aglomeração, confirmada pela visualização da formação de pontes entre partículas adjacentes nas imagens do MEV. Não foram identificados picos nos difratogramas de raios-X, indicando características amorfas. Entretanto, a alta higroscopicidade da amostra, que levou à formação de uma massa rígida e contínua, pode ter dificultado a correta difração de raios-X. / Yacon is a perennial plant originated from the Andean region which roots have been receiving increased attention due to their high content in prebiotic fructooligosaccharides (FOS). Apart from promoting many health benefits, FOS present interesting characteristics as food ingredient, being used as sugar substitute, and its extraction from yacon roots may be an alternative to the high costs FOS actually commercially available. The present work evaluated membrane technology for concentrating and purifying FOS from an extract obtained from yacon roots, combining a first ultrafiltration (UF) clarifying step with nanofiltration (NF), with and without association with discontinuous diafiltration (DF). UF aimed to remove large molecules such as proteins and suspended solids, yielding a saccharide-rich permeate. After UF, 63.75 % of total saccharides from the initial feed were recovered in the permeate, that was then subjected to NF in order to reduce glucose, fructose and salts content and concentrate the oligosaccharides in the retentate. DF did not largely influenced FOS retention in NF (it increased from 68.78 % without DF to 70.48 % with DF), but decreased glucose and fructose retentions, from 40.63 to 31.61 % and 25.64 to 18.69 %, respectively, allowing a greater purification of FOS in the retentate. After the combined UF-NF process, 51.85 % of FOS from the initial feed were recovered in the NF final retentate, with 19.75 % purity. After this, the final retentate of nanofiltration associated with diafiltration was lyophilized and the powder was subjected to analyses of color, water activity (aw), microstructure – by Scanning Electron Microscopy coupled to Energy-dispersive X-ray Spectroscopy (SEM-EDS) – and crystallinity – by X-ray diffraction. The obtained freeze-dried FOS-enriched saccharides powder, containing 19.75 % of FOS, 36.66 % of glucose and 43.59 % of fructose, in weight, was a whitish granulated powder, with aw of 0.284 and CIELAB color coordinates L*, a* and b* of 76.25±1.19, -1.03±0.09 and 1.02±0.03, respectively. It was highly hygroscopic and with agglomeration tendency, confirmed by the formation of bridges between particles on the SEM images. No peaks were identified at X-ray diffractograms, indicating its amorphous characteristics. However, the sample high hygrospicity and the formation of a rigid mass may have hindered a trustable X-ray analysis.

O yacon é uma planta perene originária da região andina, cujas raízes têm recebido atenção devido ao alto teor de frutooligossacarídeos (FOS) prebióticos. Além de proporcionar benefícios à saúde, os FOS apresentam características interessantes como ingredientes alimentícios, sendo utilizados como substitutos do açúcar. Sua extração das raízes de yacon pode ser uma alternativa aos FOS de alto custo atualmente disponíveis comercialmente. O presente trabalho avaliou a tecnologia de separação por membranas para concentração e purificação dos FOS a partir de um extrato obtido da raiz de yacon, mediante o emprego de ultrafiltração (UF) e nanofiltração (NF), com e sem utilização de diafiltração (DF) descontínua. A UF teve como objetivo clarificar o extrato de yacon, removendo partículas em suspensão de alta massa molar e recolhendo os açúcares no permeado. Depois da UF, 63,75 % dos açúcares totais presentes na solução de alimentação inicial foram recuperados no permeado. A NF do permeado, obtido previamente por UF, foi realizada para remover os sais e açúcares simples e concentrar os FOS no retido. O emprego da DF não influenciou a retenção de FOS na NF (que aumentou de 68,78 % sem DF para 70,48 % com DF), mas diminuiu a retenção de glicose de 40,63 para 31,61 % e de frutose de 25,64 para 18,69 %, permitindo uma maior purificação dos FOS no retido. Após o processo combinado de UF-NF, 51,85 % dos FOS da solução inicial foram recuperados no retido da nanofiltração, alcançando pureza de 19,75%. A seguir, o retido obtido na nanofiltração associada à diafiltração foi liofilizado. Nesse produto liofilizado foram analisadas cor, atividade de água (aw), microestrutura – por meio de microscopia eletrônica de varredura acoplada a espectroscopia por energia dispersiva de raios-X (MEV-EDS) – e cristalinidade – através de difração de raios-X. O teor de açúcares do produto liofilizado foi 19,75 % de FOS, 36,66 % de glicose e 43,59 % de frutose, em massa, com aw de 0,284. A sua aparência externa foi a de um pó granulado e esbranquiçado, cujos parâmetros de cor, no sistema CIELAB, foram de 76,25±1,19, -1,03±0,09 e 1,02±0,03 para L*, a* e b* respectivamente. A amostra se mostrou altamente higroscópica e com tendência à aglomeração, confirmada pela visualização da formação de pontes entre partículas adjacentes nas imagens do MEV. Não foram identificados picos nos difratogramas de raios-X, indicando características amorfas. Entretanto, a alta higroscopicidade da amostra, que levou à formação de uma massa rígida e contínua, pode ter dificultado a correta difração de raios-X. / Yacon is a perennial plant originated from the Andean region which roots have been receiving increased attention due to their high content in prebiotic fructooligosaccharides (FOS). Apart from promoting many health benefits, FOS present interesting characteristics as food ingredient, being used as sugar substitute, and its extraction from yacon roots may be an alternative to the high costs FOS actually commercially available. The present work evaluated membrane technology for concentrating and purifying FOS from an extract obtained from yacon roots, combining a first ultrafiltration (UF) clarifying step with nanofiltration (NF), with and without association with discontinuous diafiltration (DF). UF aimed to remove large molecules such as proteins and suspended solids, yielding a saccharide-rich permeate. After UF, 63.75 % of total saccharides from the initial feed were recovered in the permeate, that was then subjected to NF in order to reduce glucose, fructose and salts content and concentrate the oligosaccharides in the retentate. DF did not largely influenced FOS retention in NF (it increased from 68.78 % without DF to 70.48 % with DF), but decreased glucose and fructose retentions, from 40.63 to 31.61 % and 25.64 to 18.69 %, respectively, allowing a greater purification of FOS in the retentate. After the combined UF-NF process, 51.85 % of FOS from the initial feed were recovered in the NF final retentate, with 19.75 % purity. After this, the final retentate of nanofiltration associated with diafiltration was lyophilized and the powder was subjected to analyses of color, water activity (aw), microstructure – by Scanning Electron Microscopy coupled to Energy-dispersive X-ray Spectroscopy (SEM-EDS) – and crystallinity – by X-ray diffraction. The obtained freeze-dried FOS-enriched saccharides powder, containing 19.75 % of FOS, 36.66 % of glucose and 43.59 % of fructose, in weight, was a whitish granulated powder, with aw of 0.284 and CIELAB color coordinates L*, a* and b* of 76.25±1.19, -1.03±0.09 and 1.02±0.03, respectively. It was highly hygroscopic and with agglomeration tendency, confirmed by the formation of bridges between particles on the SEM images. No peaks were identified at X-ray diffractograms, indicating its amorphous characteristics. However, the sample high hygrospicity and the formation of a rigid mass may have hindered a trustable X-ray analysis.

Ces travaux de thèse ont consisté à mener une étude approfondie des propriétés physico-chimiques duparylène C, qui est un polymère chloré, en lien avec ses propriétés électriques et diélectriques. Ces dernièresont cerné principalement le comportement de la constante diélectrique et des pertes diélectriques enfonction de la température (de l’azote jusqu’à 300 °C) sur une plage de fréquence étendue (10-4 Hz – 1 MHz).Les analyses par diffraction des rayons X ont montré que ce polymère présentait une structure cristalline a-monoclinique avec un taux de cristallinité de 45 % après élaboration. Ce taux est faiblement dépendant del’épaisseur pour des couches d’épaisseurs supérieures à 50 nm. Des recuits spécifiques appliqués sur leparylène C au dessus de la température de transition vitreuse ont permis de modifier le taux de cristallinité etdes valeurs de 30% à 75 % ont pu être obtenues. Une relation linéaire entre le taux de cristallinité et latempérature de recuit a été proposée. Les analyses diélectriques ont permis de mettre en évidence troismécanismes principaux de relaxation : La relaxation b, la relaxation g et la relaxation a. Par ailleurs, unmécanisme de polarisation interfaciale de type Maxwell-Wagner-Sillars (MWS) a été identifié à hautetempérature (au-delà de la transition vitreuse). La mobilité moléculaire des chaînes autour de la températurede transition vitreuse a été analysée en profondeur et les résultats (indice de fragilité, paramètresthermodynamiques…) ont été positionnés par rapport aux données de la littérature concernant d’autrespolymères. / This work of thesis consisted in undertaking a thorough study of the physicochemical properties of theparylene C, which is a chlorinated polymer, in relationship with its electric and dielectric properties. These lastdetermined mainly the behavior of the permittivity and the dielectric losses according to the temperature (ofnitrogen up to 300 °C) on a wide frequency range (10-4Hz – 1 MHz). The analyses by x-rays diffraction showedthat this polymer had a a - monoclinical crystalline structure with a rate of crystallinity of 45 %. This rate isslightly depending on the thickness for layers thicknesses higher than 50 nm. Specific annealing applied to theparylene C made it possible to modify the rate of crystallinity and values from 30% to 75 % of crystallinitycould be obtained. A linear relation between the rate of crystallinity and the temperature of annealing wasproposed. The dielectric analyses made it possible to highlight three principal mechanisms of relaxation: b, g,a. In addition, a mechanism of interfacial polarization (Maxwell-Wagner-Sillars) was identified at hightemperature (beyond the glass transition). The molecular mobility of the chains around the glass transitionwas analyzed in-depth and the results (index of fragility, thermodynamic parameters...) were positionedcompared to the data of the literature concerning of other polymers.

Les copolymères à blocs amphiphiles Polyéthylène-b-Polyéthylène glycol comportent un bloc hydrophile et un bloc hydrophobe, tous deux cristallisables. L’intérêt de cette thèse est de mieux comprendre le comportement de ces copolymères aux interfaces solides et liquides, via l’étude de la structure et de l’organisation des couches adsorbées. Des copolymères PE-b-PEG de différentes compositions ont été étudiés à l’état massique, mettant en évidence que le ratio PEG/PE ainsi que la longueur des blocs jouent un rôle significatif sur le taux de cristallinité, la morphologie et la croissance des structures cristallines. La caractérisation en films minces par spectroscopie PM-IRRAS et AFM a permis de déterminer quantitativement l’orientation des chaînes macromoléculaires de chaque bloc sur des substrats modèles hydrophiles et hydrophobes. L’adsorption des copolymères PE-b-PEG a par ailleurs été étudiée aux interfaces eau/air et eau/hexane par les méthodes de la goutte pendante et de la goutte oscillante. Les résultats, appuyés par des mesures de tailles de particules, ont montré que les copolymères sont capables de former des structures sphériques organisées à l’échelle nanométrique. L’influence de la composition du copolymère et de la nature des interfaces sur l’organisation des copolymères a ainsi permis d’élaborer des modèles d’adsorption des blocs aux interfaces. / Polyethylene-b-Polyethylene amphiphilic diblock copolymers are composed of one hydrophilic and one hydrophobic block, both able to crystallize. The aim of this thesis is to better understand the behaviour of PE-b-PEG copolymers at solid and liquid interfaces, via the study of the structure and the organization of adsorbed layers. The crystallinity of bulk PE-b-PEG copolymers with different composition was characterized, revealing that the ratio PEG/PE and the blocks length impact the crystallinity degree, the morphology and the growth of crystalline structures. Thin films characterization by PM-IRRAS spectrocopy and AFM allowed to determine quantitatively the macromolecular chains orientation on hydrophobic and hydrophilic substrates. PE-b-PEG copolymers adsorption at the water/air and water/hexane interfaces was studied thanks to the pendant drop and the oscillating drop techniques. These results, supported by particle size analysis, revealed that copolymers can organize as nanometric spherical structures. The influence of the copolymer composition and the type of interfaces on the organization then lead to the elaboration of adsorption models of PE and PEG blocks at solid and liquid interfaces.