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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
341

Dynamics in polymer blends and polymer-solvent blends close to the glass transition / Dynamique dans les mélanges de polymères et polymère-solvant à l'approche de la transition vitreuse

Julien, Grégoire 09 October 2014 (has links)
Dans ce travail, nous proposons un modèle qui décrit la dynamique dans les mélanges de polymères et polymère-solvant à l'approche de la transition vitreuse. Le modèle est résolu sur un réseau 2D sur des échelles de 10 nm à plusieurs microns. Ce modèle incorpore l'aspect hétérogène de la dynamique à l'échelle d'une hétérogénéité dynamique (3-5 nm). Dans le cas des mélanges de polymères, nous appliquons ce modèle afin d'étudier la séparation de phase lorsque le système est refroidi proche ou sous Tg, et le rajeunissement lorsque le système est réchauffé dans un état miscible et fondu. Pendant la séparation de phase, nous observons que des morphologies lentes se forment en coexistence avec des morphologies rapides. Pendant ce temps, la dynamique globale du système se ralentit et les domaines croissent comme le logarithme du temps. Lors de la réchauffe en revanche, nous observons que les domaines vitreux fondent plus vite que le temps nécessaire pour qu'ils se forment lors de la séparation de phase. Dans le cas des mélanges polymère-solvant, le système est en contact avec un réservoir de solvant et est en dessous de la température de transition vitreuse du polymère pur. L'activité du réservoir peut être changée afin de décrire le séchage ou le gonflement de films. Notre modèle permet de décrire la diffusion cas-II lorsqu'un polymère vitreux est plastifié par du solvant qui pénètre le système. Concernant le processus inverse de séchage, nous montrons que des films ayant des épaisseurs inférieures à 1 micron peuvent être séchés entièrement. Pour des films plus épais, en revanche, une croûte vitreuse se forme sur la surface libre du film / In this work, we propose a model for describing the dynamics in polymer blends or polymer-solvent blends close to and below Tg. The model is solved on a 2D lattice corresponding to spatial scales from 10 nm up to a few micrometers and incorporate the heterogeneous nature of the dynamics at the scale of a dynamic heterogeneity (3-5 nm). In case of polymer blends, we apply this model to study phase separation close to and below Tg upon cooling, and rejuvenation in miscible range upon heating. In the course of phase separation, we observe slow structures forming in coexistence with faster ones. In the same time, the global dynamics of the system slows down and domains grow like the logarithm of the time. During rejuvenation, we observe that morphologies melt much faster the elapsed time required to build them during aging. In the case of polymer-solvent blends, the system is put in contact with a solvent reservoir and is at temperatures far below the pure polymer glass transition. We consider situations where the activity of the solvent reservoir is varied in order to describe either films drying or swelling. Our model allows for explaining case-II diffusion in the context of the plasticisation of a glassy polymer by penetrating solvent during swelling. Regarding the process of film drying, we show that films up to 1 micrometer thick can be completely dried. When drying a thicker film, we show that a glassy crust may appear on the free surface, as shown experimentally
342

Morphology development and rheological properties of reactively compatibilized Polyamide 6 / High Density Polyethylene blends / Développement des morphologies et comportement rhéologique des mélanges Polyamide 6 / Polyethylene Haute Densité compatibilisés par voie réactive

Épinat, Chloé 18 December 2014 (has links)
L'enjeu de ce travail est de comprendre les paramètres contrôlant les mécanismes de développement des morphologies et notamment la formation des nanodispersions pour des mélanges binaires de polyamides 6 de différentes masses molaires et de polyéthylène haute densité greffé anhydride maléique, mis en oeuvre par extrusion réactive. Le choix stratégique des matériaux a permis de balayer une large gamme de rapports de viscosité ainsi que différentes architectures de copolymères formés à l'interface. Les mécanismes de nature rhéologique ont été isolés méthodiquement des mécanismes dus à la réaction à l'interface en étudiant, d'une part, des mélanges non compatibilisés PA6/PEHD, puis l'effet de la réaction de compatibilisation seule en condition statique. Différents mécanismes de rupture de gouttes basés sur des instabilités capillaires sont proposés selon le rapport de viscosité. L'observation de microstructures ordonnées de copolymères aux interfaces en condition statique démontre la déstabilisation de l'interface fortement relié à la symétrie des copolymères formés. Les propriétés rhéologiques des mélanges sont étudiées ensuite. Les mécanismes de relaxation observés sont discutés, en particulier ceux liés aux interfaces et aux interactions entre nodules, en lien avec les morphologies des mélanges. Dans les mélanges compatibilisés, le comportement type gel ou solide-élastique (forte augmentation de l'élasticité aux basses fréquences), pour les mélanges concentrés, suggère la création d'un réseau percolant d'interactions entre nodules voisins. Enfin, un modèle performant de prédiction de la composition à l'inversion de phase à partir du comportement rhéologique est proposé / The aim of this work is to understand the parameters that control the morphology development mechanisms, and especially, the formation of nanodispersions. This study deals with binary blends of polyamide 6 of different molecular weights and maleic anhydride grafted high density polyethylene, processed by reactive extrusion. The strategic choice of blend components allowed to cover a wide range of viscosity ratio and various copolymer architectures formed at the interface. Mechanisms controlled by classical rheological laws were methodically isolated from mechanisms specific to the compatibilization reaction at the interface by studying, on the one hand, uncompatibilized PA6/HDPE blends, and on the other hand, the effect of the compatibilization reaction in static condition. Different drop break-up mechanisms based on capillary instabilities are proposed depending on viscosity ratios. The observation of ordered microphase separated copolymer domains at the interfaces in static condition attests of the spontaneous interface destabilization, strongly related to the copolymer asymmetry. Blends rheological properties are then studied. The different relaxation mechanisms obtained are discussed, especially those related to the interfaces and interactions between droplets, relatively to blends morphologies. In compatibilized blends, gel-like or solid-elastic behavior (strong elasticity increase at low frequencies) for concentrated blends, suggest the creation of a percolating network of interactions between neighboring droplets. Finally, an efficient model for predicting the phase inversion composition from the rheological behavior is proposed
343

Estudo da degradação de polímeros e blendas aplicados à bovinocultura

Souza, Nelson Luis Gonçalves Dias de 18 May 2015 (has links)
Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-01-04T12:28:35Z No. of bitstreams: 1 nelsonluisgoncalvesdiasdesouza.pdf: 6400467 bytes, checksum: f13622d122292f1c2363e10cf9d7b85f (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-01-25T15:51:16Z (GMT) No. of bitstreams: 1 nelsonluisgoncalvesdiasdesouza.pdf: 6400467 bytes, checksum: f13622d122292f1c2363e10cf9d7b85f (MD5) / Made available in DSpace on 2016-01-25T15:51:16Z (GMT). No. of bitstreams: 1 nelsonluisgoncalvesdiasdesouza.pdf: 6400467 bytes, checksum: f13622d122292f1c2363e10cf9d7b85f (MD5) Previous issue date: 2015-05-18 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Os polímeros constituem um grupo particular de macromoléculas (moléculas de alto peso molecular constituídas por grandes cadeias de átomos) caracterizado pela repetição de um ou mais grupos atômicos (monômero), que são responsáveis pela formação da cadeia polimérica e, consequentemente, suas características físico-químicas. Suas propriedades derivam principalmente das interações que ocorrem entre os elementos da sua macroestrutura (interações intramoleculares) ou com outros compostos (interações intermoleculares). As blendas poliméricas são formadas a partir da mistura de dois ou mais polímeros com o intuito de obter um novo material com propriedades diferentes dos polímeros que os originaram. A produção de blendas é uma maneira simples e barata de se obter novos materiais poliméricos, pois não há a necessidade de realizar sínteses. No estudo de uma blenda polimérica dois fatores devem ser avaliados: a miscibilidade e a compatibilidade, sendo a preparação e o estudo das blendas uma parte importante da ciência dos polímeros. Apesar das blendas já serem amplamente usadas e estudadas, os efeitos da mistura de polímeros nos processos de estabilização e degradação não são compreendidos. Os polímeros podem ser divididos em diversas classes sendo uma delas relacionada com os polímeros biodegradáveis que fazem parte de um campo emergente de pesquisa. Um grande número de polímeros biodegradáveis tem sido sintetizado recentemente, e alguns microrganismos e enzimas são capazes de degradá-los. Assim nesse trabalho estudou-se num primeiro momento a compatibilidade de miscibilidade de blendas poliméricas envolvendo mistura de polímeros não biodegradáveis e biodegradáveis, através da utilização de técnicas espectroscópicas (infravermelho e Raman) e análises térmicas (TG e DSC). Em seguida a degradação desses polímeros foi realizada estudando sua estabilidade ao serem submetidos a ação de enzimas proteolíticas do rúmen (análise por Raman e infravermelho) e ao serem submetidos a degradação no solo, que nesse caso além das análises vibracionais estudou-se a perda da massa desses matérias ao decorrer do tempo. Por fim o estudo da toxicidade celular de algumas blendas foram realizados a fim de avaliar a possibilidade de sua aplicação em medicina veterinária. / The polymers are a particular group of macromolecules (high molecular weight molecules formed by long chains of atoms) characterized by the repetition of one or more atomic groups (monomer), which are responsible for the formation of the polymeric chain and consequently its physicochemical characteristics chemical. Its properties are principally derived from interactions among the elements of its macrostructure (intramolecular interactions) or other compounds (intermolecular interactions). The polymer blends are formed from a mixture of two or more polymers in order to obtain a new material with different properties of the polymers originated. The production of polymer blends is a simple and inexpensive way to obtain new polymeric materials, since there is no need to perform syntheses. In the study of a polymer blend two factors must be evaluated, the miscibility and compatibility the study of a polymer blend two factors must be evaluated, the miscibility and compatibility, and the preparation and study of the blends are an important part of polymer science. Although the blends are already widely used and studied the effects of polymer mixture in the degradation and stabilization processes are not understood. The polymers can be divided into several classes including biodegradable polymers that are part of an emerging field research; a great many biodegradable polymers have been synthesized recently and some microorganisms and enzymes are capable of degrading them. Thus this work we studied at first compatibility miscibility of polymer blends involving mixing of non-biodegradable and biodegradable polymers, using spectroscopic techniques (infrared and Raman) and thermal analysis (TG and DSC). Then the degradation of these polymers was carried out by studying their stability when subjected to the action of proteolytic enzymes in the rúmen (by Raman and infrared analysis) and undergoing degradation in the soil, in this case in addition to analysis by Raman and infrared spectroscopy it is study loss of mass of the material over time. In order to study the cellular toxicity of some blends were conducted to evaluate the possibility of its application in veterinary medicine.
344

Caracterização espectroscópica de blendas condutoras de poli(anilina) e a sua aplicação para a proteção ativa contra a corrosão de metais / Spectroscopic characterization of polyaniline conductive blends and their application for the active protection against corrosion of metals

Silva, José Eduardo Pereira da 04 June 2003 (has links)
Esta Tese apresenta a caracterização espectroscópica, eletroquímica e espectroeletroquímica de blendas condutoras de polianilina. Na primeira parte do trabalho foi realizada a caracterização dos materiais através das espectroscopias vibracionais Raman e infravermelho. Os resultados obtidos através da espectroscopia Raman ressonante indicaram que a conformação e a estrutura química do polímero condutor não sofrem mudanças dentro ou fora das matrizes isolantes. Além disso, demonstra-se que as diferenças de intensidade relativa entre as bandas em 574 e 607 cm-1 da polianilina dopada fornecem o grau da interação física entre os constituintes da blenda, sendo realizado também um estudo da relação entre a intensidade das bandas citadas e a condutividade das diferentes blendas obtidas. Na segunda parte do trabalho foi realizada a aplicação de blendas condutoras de polianilina para a proteção contra a corrosão do ferro e da liga de alumínio A2024. Os resultados obtidos mostraram a boa eficiência das blendas para esta finalidade, conforme comprovado pelas curvas de potencial de circuito aberto e a técnica de voltametria cíclica. Verificou-se que a proteção contra a corrosão depende diretamente da formação de um complexo passivante entre a blenda e o material metálico. Por outro lado, deve-se considerar a presença da barreira física causada pelas blendas, superior à existente quando se utiliza o polímero condutor puro, e que evita a penetração de ânions que promovem a degradação do material metálico. / This work shows the spectroscopic, electrochemistry and spectroelectrochemistry characterization of conducting polyaniline blends. In the first part it was done the characterization of the materials by Raman and infrared vibracional espectroscopies. Using resonance Raman spectroscopy it can be observed that conducting polymer conformation and chemical structure does not changed inside or outside insulating matrices. It was also possible to check that the relative intensities of 574 and 607 cm-1 bands indicate the degree of physical interaction of polymers in the blends, moreover the relationship between intensity of mentioned bands and the conductivity was investigated. In second part it was studied the application of conducting blends for corrosion protection on iron and aluminum alloys A2024. Results obtained showed the good eficiency of these materials, proved by open circuit potential and cyclic voltammetry. It was observed that the protection depends on the formation passive of a film between the coating and the metallic material. On the other hand, the physical barrier of blends are better than pure conducting polymer and decreases the penetration of anions that promote the degradation of metallic materials.
345

Rheology and morphology of polyolefin / functional oligomer blends : application to the formulation of polymer materials / Rhéologie et morphologie de mélanges polyoléfine / oligomère fonctionnel : application à la formulation de matériaux polymères

Robert, Michael 21 March 2019 (has links)
L’objectif de ces travaux était l’utilisation d’oligomères de polyéthylène fonctionnels comme agents d’interface pour la formulation de matériaux polymères. Une première partie s’est portée sur la compréhension de l’évolution de la morphologie de mélanges composés d’une résine polypropylène ou polyéthylène et d’un oligomère de polyéthylène de faible masse molaire au cours de leur mise en œuvre et de leur cristallisation. Il a été constaté qu’un tel oligomère pouvait être incorporé sans difficulté aux résines sélectionnées, et ce grâce à une diffusion rapide ainsi qu’à une bonne miscibilité à l’état fondu. Cependant, il est apparu que ces mélanges étaient sujets à une séparation de phase solide-liquide lors de leur cristallisation, entraînant la formation de matériaux biphasiques à l’état solide. Dans une deuxième partie, un système réactif composé de deux oligomères fonctionnels a été étudié comme une potentielle stratégie de compatibilisation de mélanges polyéthylène/polyamide. Malgré les morphologies et propriétés intéressantes observées, il a été conclu que l’utilisation d’un tel système réactif n’était pas efficace comparé aux agents compatibilisants usuels. Enfin, des oligomères de polyéthylène fonctionnels ont été étudiés en tant qu’agents d’interface dans du polyéthylène renforcé par des fibres de verre dans l’optique d’en améliorer la facilité de mise en œuvre et les propriétés mécaniques. Il a ainsi été démontré que des oligomères avec les fonctionnalités appropriées pouvaient être utilisés comme agents d’interface en réduisant les interactions interparticulaires au cours de la mise en œuvre et en améliorant l’adhésion interfacial matrice-fibre à l’état solide / The objective of this work was to use end-functionalized polyethylene oligomers as interface agents in glass fibre-reinforced thermoplastics as well as compatibilizer precursors in immiscible polymer blends. The first part of this work was focused on the understanding of the morphology developments occurring during the melt processing and crystallization of binary systems where a low molar mass polyethylene oligomer was blended with polypropylene and polyethylene resins. It was found that the polyethylene oligomer was easily incorporated into the selected polyolefins thanks to rapid molecular diffusion and good miscibility in the molten state. However, it appeared that the blends underwent solid-liquid phase separation upon crystallization, leading to biphasic materials in the solid state. In a second part, a reactive system consisting of two functional oligomers was studied as a new strategy for the compatibilization of immiscible polyethylene/polyamide blends. Despite the interesting morphologies and properties observed, it was concluded that the use of such a reactive system did not result in efficient compatibilization compared to commonly used compatibilizer precursors. Lastly, polyethylene oligomers with various functionalities were investigated as interface agents in glass fibre-reinforced polyethylene, with the aim of improving both processability and mechanical properties. It was demonstrated that polyethylene oligomers with adequate functional groups could be successfully used as dispersants by reducing interparticle interactions during melt processing as well as coupling agents improving matrix-filler interfacial adhesion in the solid state
346

Vlastnosti vláken na bázi polyhydroxybutyrátu / Properties of fibers based on polyhydroxybutyrate

Štulrajterová, Lujza January 2018 (has links)
Táto práca sa zaoberá zvlákňovaním biopolymérov z taveniny. V teoretickej časti sú zhrnuté doterajšie poznatky o zvlákňovaní poly(3-hydroxy butyrátu) (PHB) a poly(mliečnej kyseliny) (PLA). Následne boli zvláknené polymérne zmesi na báze PHB s rôznym zložením, čo umožnilo štúdium vplyvu PLA, zmäkčovadiel a ich množstva na vlastnosti pripravených vlákien. Boli použité tri komerčné zmäkčovadlá (ATBC, PEG, A6) a dva experimentálne syntetizované. Zvláknenie bolo prevedené na troch rôznych zvlákňovacích linkách. Konvenčné zvlákňovacie linky s odťahovými rýchlosťami nad 150 m/min sa preukázali ako nevhodné pre spracovanie našich zmesí. Kvôli nedostatočnej pevnosti taveniny sú potrebné nízke odťahové rýchlosti. Boli pripravené vlákna s dĺžiacim pomerom 6,4; ktoré boli následne analyzované pomocou GPC, MDSC a ťahovej skúšky. Na základe nameraných teplôt skelného prechodu zmäkčovadlá ATBC a PEG vykázali lepšiu schopnosť zmäkčiť skúmané PLA/PHB zmesi. Vlákna obsahujúce A6 vykazovali najvyššiu pevnosť v ťahu (250 MPa) a modul pružnosti (2,7 GPa). Nakoniec bol skúmaný vplyv starnutia, tepla a vriacej vody na mechanické vlastnosti týchto vlákien.
347

Propriétés barrières de films de polycarbonate modifiés par plasma froid, par dispersion de charges et par mélanges de polymères. / Barrier properties of polycarbonate films modified by cold plasma, by filler dispersion and by polymer blends

Diawara, Bassidi 21 October 2019 (has links)
L’objectif de ce travail de thèse a été d’améliorer les propriétés barrière du polycarbonate (PC), polymère rigide et transparent utilisé dans l’industrie automobile comme matériau pour phares de voiture. Le PC est le siège de transferts de molécules de gaz et vapeurs provenant de l’intérieur et/ou de l’extérieur des optiques et également de migration de petites espèces (monomères, additifs) au sein de la matière elle-même. Ces phénomènes amènent souvent une perte de transparence du PC et d’autant plus avec la technologie LED qui ne dissipe pas la condensation. Pour y remédier, nous avons utilisé trois approches différentes permettant d’accroître la résistance au transfert des matériaux, à commencer par le traitement de surface par plasma froid afin de déposer sur le substrat de PC une couche barrière organosiliciée. La polymérisation de cette couche est effectuée en mélangeant du dioxygène avec un précurseur organosilicié : l’hexaméthyldisiloxane (HMDSO), le 2,4,6,8-tétraméthylcyclotétrasiloxane (TMCTS) ou le triéthoxyfluorosilane (TEOFS). Les autres approches axées sur les mélanges et l’incorporation de charges ont consisté à élaborer d’une part des micr/nano composites de PC/mica et de l’autre des mélanges de polymères PC/poly(m-xylène adipamide) (MXD6) et enfin le mélange chargéPC/MXD6/mica. Ces films ont été préparés à l’aide d’une extrudeuse bis-vis équipée d’éléments mélangeurs ayant pour but d’améliorer la qualité de mélange de dispersion de la matière. L’ensemble des matériaux obtenus a été caractérisé afin d’établir des relations de structure/morphologie/propriétés. Le dépôt par plasma a permis non seulement d’augmenter la résistance thermique du PC, mais aussi d’accroître son effet barrière à l’eau mais surtout aux gaz (N₂, O₂ et CO₂). L’efficacité du traitement plasma vis-à-vis de l’eau est fortement dépendante du caractère hydrophile du dépôt et de sa densité. Si les composites PC/mica élaborés avec les mélangeurs sont plus barrière à l’eau qu’aux gaz, les mélanges PC/MXD6 sont au contraire bien plus efficaces vis-à-vis des gaz que de l’eau. Ainsi l’ajout du mica à faible taux dans le mélange PC/MXD6 a permis, par effet de piégeage, d’accroître davantage la résistance à l’eau du mélange tout en maintenant des bonnes propriétés barrière aux gaz. Outre les effets barrière obtenus, nous avons réussi, par l’utilisation des éléments mélangeurs, à augmenter la stabilité thermique du PC et à conserver la transparence des films de PC/mica, PC/MXD6 et PC/MXD6/mica. / The aim of the present thesis is to improve the barrier properties of polycarbonate (PC), a stiff and transparent polymer used in automotive industry as material for car headlights. PC represents a place of transfer of gas molecules and vapors coming from inside and/or outside the optics and also of migration of small species (monomers, additives) within the material itself. These phenomena often lead to a loss of the PC transparency, especially with the LED technology which does not allow the condensation dissipation. In order to overcome this limitation, three different approaches allowing the increase of materials transfer resistance were chosen. The first approach consists in the cold plasma surface treatment in order to obtain a barrier organosilicon layer on the PC substrate. This layer is obtained using a mixture of oxygen with an organosilicon precursor : hexamethyldisiloxane (HMDSO), 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS) or triethoxyfluorosilane (TEOFS). The other approaches focused on the incorporation of fillers and polymer blends permit the elaboration of micro/nano-composites of PC/mica, PC/poly(m-xylene adipamide) (MXD6) polymer blends and charged PC/MXD6/mica blends. These films were prepared using a double-screw extruder equipped with mix elements allowing the improvement of the quality and dispersion of the blend. The physico-chemical characterization of the obtained materials highlights the structure/morphology/properties relationship. The plasma deposition allows an increase of the PC thermal resistance as well as its barrier properties toward water and especially gas (N₂, O₂ and CO₂). The efficiency of the plasma treatment toward water molecules strongly depends on the layer hydrophilicity and density. PC/mica composites elaborated with mix elements are found to be more barrier toward water than toward gas, while PC/MXD6 blends are more efficient toward gas than water. Thus, the addition of low mica contents in the PC/MXD6 blend allowed to further increase the water resistance of the blend by trapping effect, while maintaining its high barrier properties toward gas. In addition, an increase of the PC thermal stability and a presevation of the transparency of PC/mica, PC/MXD6 and PC/MXD6/mica films were revealed using mix elements.
348

Potentials and limitations of welding incompatible polymers

Albrecht, Mirko, Hüllmann, André, Gehde, Michael 07 March 2018 (has links)
Due to the wide range of properties of plastics (e.g. low density, low electrical and thermal conductivity), conventional materials will be increasingly substituted by polymers. Multifarious requirements on technical parts intensify the demand for joining processes, which ensure the reliable joining of incompatible thermoplastics. In this case, material bonded joints are approaching their limits. The present study focusses on the welding of two incompatible thermoplastic polymers (polyamide and polyethylene) by using adapted blend materials, which are compatible to both joining components. The results prove the feasibility of this method and indicate the high potential regarding the reachable joint strength. Furthermore, the study demonstrates the challenges regarding the suitable application of blend materials and deals with open scientific questions concerning their industrial usage.
349

High Temperature Semiconducting Polymers and Polymer Blends

Aristide Gumyusenge (8086511) 05 December 2019
Organic semiconductors have witnessed a prolific boom for their potential in the manufacturing of lightweight, flexible, and even biocompatible electronics. One of the fields of research that has yet to benefit from organic semiconductors is high temperature electronics. The lightweight nature and robust processability is attractive for applications such as aerospace engineering, which require high temperature stability, but little has been reported on taking such a leap because charge transport is temperature dependent and commonly unstable at elevated temperatures in organics. Historically, mechanistic studies have been bound to low temperature regimes where structural disorders are minimal in most materials. Discussed here is a blending approach to render semiconducting polymer thin films thermally stable in unprecedented operation temperature ranges for organic materials. We found that by utilizing highly rigid host materials, semiconducting polymer domains could be confined, thus improving their molecular and microstructural ordering, and a thermally stable charge transport could be realized up to 220°C. With this blending approach, all-plastic high temperature electronics that are extremely stable could also be demonstrated. In efforts to establish a universal route towards forming thermally stable semiconducting blends, we found that the molecular weight of conjugated polymer plays a crucial role on the miscibility of the blends. Finally, we found that the choice of the host matrix ought to consider the charge trapping nature of the insulator.<br>
350

Silicone blends for aeronautic applications / Mélanges de silicones pour l'aéronautique

Spigolis, Camille 12 April 2018 (has links)
Ces travaux de thèse portent sur le développement d’un joint silicone pour la connectique dans l’aéronautique. Ce joint silicone doit être résistant aux solvants ainsi qu’aux huiles susceptibles de rentrer en contact avec celui-ci, et posséder de bonnes propriétés thermiques et mécaniques. Pour ce faire, les paramètres influençant ces propriétés ont été étudiés, comme la composition de la matrice, les conditions de sa réticulation et la formulation via différentes charges. Des matériaux silicones tels que le polydiméthylsiloxane (PDMS) et le polytrifluoropropylméthylsiloxane (PTFPMS) ont été sélectionnés pour composer la matrice. Leur flexibilité, leur large plage de température d’utilisation ainsi que leur excellente résistance aux attaques chimiques en font des matériaux de choix pour ce genre d’application. L’étude des mélanges de PDMS et de PTFPMS a démontré que les proportions idéales sont de 70/30 PDMS/PTFPMS. Le type de mélangeur sélectionné est une calandre bi-rouleaux, dont les rouleaux sont chauffés à 40°C. La réticulation de la matrice a été le sujet d’une étude approfondie. La cinétique de réticulation a été étudiée et l’influence des paramètres de réticulation tels que la température de réticulation, la nature et la quantité de peroxyde sur les propriétés finales ont été discutées. Finalement, l’influence de l’ajout de différentes charges sur le gonflement, la résistance thermique et les propriétés mécaniques de l’élastomère a été étudiée afin d’élaborer la formulation du joint silicone. / Polydimethylsiloxane (PDMS) and polytrifluoropropylmethylsiloxane (PTFPMS) elastomers are popular material in the aeronautic and connector fields. Their flexibility, wide service temperature range and chemical resistance make them first-choice materials for such applications. PTFPMS provides oil and apolar solvent resistance to the final material, while PDMS provides resistance to polar solvents, greater thermal resistance than PTFPMS, and cost reduction. Typically, connector seals comprising PDMS and PTFPMS can be composed of blends of homopolymers, of copolymers or of blends of homopolymers and copolymers. This present work deals only with blends of homopolymers. First, commercial PDMS and PTFPMS bases were selected and characterised, the blending process chosen and the PDMS/PTFPMS ratio tuned so as to minimise swelling in acetone and methylcyclohexane while maximising thermal properties. The optimal blend composition comprised 30 wt% PTFPMS. The second part of this work explored the influence of crosslinking conditions on final properties of the cured PDMS/FS blend. Crosslinking parameters, such as the temperature (160 and 180°C), the nature (DCP and DBPH) and the quantity (0.5 and 1 wt%) of peroxide, were varied. It appeared that co vulcanisation between PDMS and PTFPMS, occurs in certain conditions. Swelling as well is influenced by crosslinking conditions but not thermal properties. Finally, the formulation of the ideal elastomer was developed. Fillers, such as TiO2, CaCO3, quartz, CeO, a pigment, Fe2O3 and a platinum compound, were selected and their influence on thermal, mechanical and swelling properties studied. Regarding thermal and solvent properties, a high loading of fillers is a good strategy, however, an increase of permanent set was observed with the augmentation of filler fraction. Final formulations were selected for the compromise they offered between thermal and swelling properties and mechanical behaviour on the lab scale. Morphology observation revealed well dispersed domains, comparable to that of the non additivated blend.

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