L'objectif principal a été d'élaborer de nouveaux revêtements hybrides O/I de morphologie contrôlée afin de répondre des exigences de haute stabilité thermique (300°C) et résistance à la rayure et ayant des propriétés mécaniques spécifiques. Pour répondre à ces attentes, une phase inorganique est générée in-situ par des réactions d'hydrolyse/condensation d'un précurseur inorganique silicié (TEOS) au sein de matrices organiques de microstructures variées : polyesters hyperramifiés (Boltorn H20 and H40), oligoesters ramifiés (Synthoester et dérivés tanniques). Les nombreuses fonctions hydroxyles de la composante organique et leur forme spécifique permettent, dans les conditions de synthèse choisies, de contrôler les interactions entre les phases organiques et inorganiques et retarder les mécanismes de séparation de phases induite lors de la condensation du TEOS. Les matériaux hybrides ont été analysés par TEM, SAXS, ATG et DMA, microscratch testeur. L'influence de la masse molaire, de la teneur en composés inorganiques, de la teneur en fonctions hydroxyle de la composante organique sur la morphologie finale et les propriétés thermiques et mécaniques de surface.

This thesis aims at presenting the use and development of original catalytic systems based on lipases immobilized on clays which are efficient for the synthesis of biopolyesters and allowing the preparation of organic/inorganic nanohybrids based on clay nanoparticles (sepiolite and montmorillonite) grafted with such polyesters. These nanoclays were used as lipase supports and the clay-immobilized forms of Candida antarctica lipase B (CALB) were tested for ε-caprolactone and lactide isomers polymerization. Polymerization kinetics and characterization of resulting materials have shown that lipases immobilized on montmorillonite show better performances compared to the ones immobilized on sepiolite. Clay surface organo-modification has proved to greatly enhance the catalytic activity of the corresponding systems. CALB immobilized on montmorillonite allowed the elaboration of organic/inorganic nanohybrids as evidenced by the effective grafting of polyester chains from the clay surface. Finally, random PCL/PLA copolyesters were successfully obtained by lipase-catalyzed copolymerization of D-lactide with ε-caprolactone.

There is no abstract available for this thesis. / Department of Family and Consumer Sciences

Les poly(3-hydroxyalcanoate)s ou PHAs sont des biopolyesters linéaires biodégradables et biocompatibles synthétisés par des microorganismes bactériens en tant que réserve de carbone et d'énergie. Ils sont synthétisés par des bactéries à partir de ressources renouvelables et la diversité de leurs structures possibles se traduit par un large éventail de polymères ayant des propriétés mécaniques très différentes. Nous avons tout d'abord testé les capacités de production de PHAs de nouvelles souches bactériennes marines provenant de tapis microbiens de Polynésie française, en utilisant, entre autres, des substrats naturels comme l'huile de coprah, le glucose et l'acide oléique. Nous avons notamment montré que la souche Pseudomonas guezennei est capable de produire des PHAs avec des taux d'insaturation contrôlés et de masse molaire très élevée. Puis, des oligomères de PHAs fonctionnalisés de structures contrôlées portant des fonctions terminales alcynes ou alcènes ont été préparés par transestérification. Ces oligomères ont ensuite été utilisés pour l'élaboration par chimie click de copolymères amphiphiles greffés EPS-g-PHA avec des exopolysaccharides (EPS) bactériens. Enfin la dernière partie de ces travaux a consisté en la réalisation d'un support de croissance pour le développement de cellules souches pour l'ingénierie tissulaire combinant les propriétés mécaniques des PHAs et les propriétés hydrophiles et bioactives des EPS

Ce travail s'inscrit dans le développement de formulations performantes et processables pour les liners de réservoirs de stockage hyperbare. Une large gamme de formulations à base polyamide et polyépoxyde a ainsi été synthétisée en conditions contrôlées, représentatives du procédé de rotomoulage. Les systèmes polyamide ont été modifiés par copolymérisation statistique et les polyépoxydes par une phase dispersée micro- ou nano-structurée avec des thermoplastiques de haute Tg ou des copolymères blocs. Les propriétés morphologiques, thermiques, mécaniques et barrière de chaque formulation ont été caractérisées et confrontées au cahier des charges du matériau. En parallèle, l'influence des conditions opératoires et de la formulation sur les rhéocinétiques de polymérisation, de cristallisation, de gélification et/ou de séparation de phase a ainsi été établie. L'ensemble de ces résultats a été mis à profit afin d'identifier des relations structures - propriétés - processabilité en vue de l'application. Afin de valider le potentiel des formulations retenues, ces dernières ont été rotomoulées en conditions opératoires variables avec un suivi in situ de l'écoulement et ex situ de la viscosité. Ce travail a permis d'établir les fenêtres de processabilité de chaque formulation et de comprendre l'origine des défauts d'écoulement.

Made available in DSpace on 2014-12-17T14:07:17Z (GMT). No. of bitstreams: 1 ThercioHCC.pdf: 966680 bytes, checksum: d8523389bd9b4ff916fa03cde47c7153 (MD5) Previous issue date: 2006-06-14 / A polyester film has a vast application field, due some properties that are inherent of this kind of material such as, good mechanical resistance, chemical resistance to acids and bases and low production cost. However, this material has some limitations as low superficial tension, flat surface, low affinity to dyers, and poor adhesion which impede the use of the same ones for some finality as good wettability. Among the existent techniques to increase the superficial tension, plasma as energy source is the more promising technique, because of their versatility and for not polluting the environment. The plasma surface polymeric modification has been used for many researchers, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, polyester films were treated with oxygen plasma varying the treatment time from 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) varying the percentage of each gas the mixture from 0 to 100%, the treatment time remaining constant to all treatments (10 min). After plasma treatment the samples were characterized by contact angle, surface tension, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, with the aim to study the wettability increase of treated polyester films as its variables. In the (O2/N2) plasma treatment of polyester films can be observed an increase of superficial roughness superior to those treated by O2 plasma. By the other hand, the chemical modification through the implantation of polar groups at the surface is obtained more easily using O2 plasma treatment / Filmes de poli?ster possuem um vasto campo de aplica??o, devido algumas propriedades que s?o inerentes desse tipo de material, tais como boa resist?ncia mec?nica, resist?ncia qu?mica a ?cidos e bases e baixo custo de produ??o. Entretanto possuem limita??es, como baixa tens?o superficial, superf?cie n?o rugosa, pouca afinidade com corantes, e pouca ades?o, que impedem o uso dos mesmos para algumas finalidades principalmente quando esse uso requer que o material possua uma boa molhabilidade. Dentre as varias t?cnicas existentes para aumentar a tens?o superficial, as t?cnicas que utilizam o plasma, como fonte energ?tica, s?o as mais promissoras pela versatilidade e por n?o apresentar agentes nocivos ao meio. A modifica??o superficial de superf?cies polim?ricas por plasma tem sido bastante utilizada, pois a mesma n?o apresenta agentes nocivos ao ambiente, as altera??es promovidas no material s?o de escala nanom?tricas, e comprovadamente ? a t?cnica que tem apresentado resultados mais expressivos. Ent?o, tendo em vista a boa aceitabilidade do uso do plasma em materiais polim?ricos, tratou-se filmes de poli?ster usando plasma com atmosfera gasosa de oxig?nio variando-se o tempo de tratamento de 10 - 60 min com incremento de 10 min a cada tratamento subseq?ente, e tamb?m usou-se a atmosfera gasosa composta por uma mistura de nitrog?nio e oxig?nio, variando a concentra??o gasosa dos mesmos (de 0 100%), para um tempo de tratamento de 10 min. Ap?s o tratamento por plasma as amostras foram caracterizadas por medidas de ?ngulo de contato, tens?o superficial, espectroscopia Raman, Espectroscopia de infravermelho de reflex?o total atenuada (IR-ATR), e microscopia de for?a at?mica (AFM), onde foi caracterizado o aumento na molhabilidade dos filmes tratados por plasma bem como as vari?veis que contribu?ram para tal efeito. O Tratamento de filmes de poli?ster com a mistura de O2 e N2, apresenta uma rugosidade superficial das amostras superior a quando se utiliza somente O2 no tratamento com plasma. Por outro lado a modifica??o qu?mica, isto ?, a implementa??o de componentes qu?micos polares nas superf?cies das amostras ? obtido mais facilmente usando plasma com O2

There is a growing need for fibres with increasing population. One way to solve this is to recycle the fibres from textile waste. In mechanical recycling by shredding the textiles are shredded back to fibrous form. The biggest problem with shredding is that it is a harsh process that reduces the fibre length and damages the fibre.   To make the shredding process more gentle and preserve more of the fibre length, pre-treatment that lowers the friction between the fibres have been investigated. Polyethene glycol 4000 (PEG 4000) is an environmentally friendly chemical that could be used to lower the friction of cotton and polyester, the two most used textile fibres. Another treatment evaluated is glycerol. The treatment should not affect further processing of the fibres. For evaluating the treatment, a test of the interfibre friction was performed on carded webs and fabrics that were untreated and treated. Prior to shredding four samples were made of fabrics of cotton, polyester and polycotton. From each fabric, one was left untreated, and one was treated with a low concentration of PEG 4000. The concentration of PEG 4000 was chosen from the test on fibres. Also from each fabric, two treatments that were not prepared by the author; one with a high concentration of PEG 4000 and the other with glycerol. All 12 samples were shredded back to fibres. The shredded material was analysed, and the fibre length was measured. The reclaimed fibres from the shredded material were also tried to be processed into yarns.   The main result was that it was possible to rotor spin yarn of 100% reclaimed fibres from cotton and polyester treated with PEG 4000, which means that the treatment did not interfere with the spinnability of the reclaimed fibres. Untreated cotton was also spinnable, but untreated polyester was not possible to card. The cotton and polyester treated with glycerol were possible to carded and made into a sliver but not spinnable. The reclaimed fibres from the polycotton fabric were not possible to card or process further. This result correlates with the analyses of the shredded material and the fibre length measurement. The best results were for polyester treated with 0.71 w% PEG 4000 that had 121% longer mean fibre length than untreated polyester. The best result for cotton was treated with 0.29 w% PEG 4000.

Painéis sanduíche são largamente utilizadas em diversas aplicações de engenharia e o estudo de suas propriedades é fundamental para a ampliação de sua utilização. Neste trabalho, foram estudados painéis sanduíche com núcleo de poliuretano e faces de fibra de vidro fabricados pelo processo de laminação contínua. Na primeira configuração, as faces do painel foram fabricadas com manta de fibra de vidro e resina poliéster, com 39% de teor de vidro em massa e espessura de 1,9 mm. Na segunda configuração, as faces do painel foram fabricadas com tecido de fibra de vidro e resina poliéster, com 54% de teor de vidro em massa e espessura de 1,2 mm. Realizou-se o cálculo das propriedades mecânicas de cada compósito no programa MECH-Gcomp. As propriedades do núcleo foram retiradas, inicialmente, da literatura. Então, foi possível realizar a avaliação dos painéis pelo método dos elementos finitos utilizando elementos sólidos, comparando o comportamento dos dois tipos de painéis em relação aos carregamentos de compressão de núcleo, de compressão longitudinal e de flexão. Foram realizados ensaios nas faces isoladas e também nos painéis sanduíche completos. Para as faces, os ensaios foram de teor mássico de fibra de vidro, tração, compressão e cisalhamento Iosipescu, conforme as normas ASTM D5630, D3039/D3039M, D6641/D6641M e D7078/D7078M, respectivamente. Já para os painéis sanduíche, foram realizados os ensaios de compressão de núcleo, compressão longitudinal (edgewise) e cisalhamento do núcleo utilizando flexão, conforme as normas ASTM C365/C365M, C364/C364M e C393/C393M, respectivamente. Após os ensaios, foram calibrados os modelos do MEF, permitindo que os mesmos possam calcular outras configurações similares de painel sanduíche. Foi utilizado o programa Autodesk Simulation Composite Design para realizar a validação do ensaio de cisalhamento do núcleo. Concluiu-se que a análise de elementos finitos foi confiável em representar de forma realista o comportamento dos painéis sanduíche e a redução na espessura das faces do painel pode ser compensada com o aumento da sua resistência mecânica e rigidez por meio do aumento no teor mássico de reforço e trabalhando com a orientação do mesmo. / Sandwich panels are widely used in a variety of engineering applications and the study of their properties is fundamental for the expansion of their use. In this work, we studied sandwich panels with polyurethane core and fiberglass faces manufactured by the continuous lamination process. In the first configuration, the panel faces were made of fiberglass and polyester resin, with 39% glass content by mass and 1.9 mm thickness. In the second configuration, the panel faces were fabricated from fiberglass fabric and polyester resin, with 54% glass content by mass and 1.2 mm thickness. The mechanical properties of each composite were calculated in the MECH-Gcomp software. The properties of the core were initially taken from the literature. Then, it was possible to evaluate the panels by the finite element method using solid elements, comparing the behavior of the two types of panels in relation to the core compression loads, edgewise compression and bending. Tests were performed on the faces and also on the complete sandwich panels. For the faces, the tests were fiberglass mass content, tensile, compression and Iosipescu shear, according to ASTM D5630, D3039/D3039M, D6641/D6641M and D7078/D7078M, respectively. For sandwich panels, core compression, edgewise compression and core shear using bending tests were performed according to ASTM C365/C365M, C364/C364M and C393/C393M, respectively. After the tests, the FEM models were calibrated, allowing them to calculate other similar sandwich panel configurations. It was used Autodesk Simulation Composite Design software to validate the core shear test. It was concluded that the analysis of finite elements was reliable in realistically representing the behavior of the sandwich panels and the reduction in the thickness of the panel faces can be compensated with the increase of its mechanical resistance and stiffness by increasing the mass content of reinforcement and working with the orientation of the same.

Submitted by Daniel Magalhães de Oliveira (daniel.steiger@live.com) on 2018-09-18T00:49:16Z No. of bitstreams: 1 Dissertação - Daniel Magalhaes de Oliveira OK.pdf: 10110047 bytes, checksum: 86cc594889112132d78452c96ef59879 (MD5) / Approved for entry into archive by Pamella Benevides Gonçalves null (pamella@feg.unesp.br) on 2018-09-18T13:49:56Z (GMT) No. of bitstreams: 1 oliveira_dm_dm_guara.pdf: 10110047 bytes, checksum: 86cc594889112132d78452c96ef59879 (MD5) / Made available in DSpace on 2018-09-18T13:49:56Z (GMT). No. of bitstreams: 1 oliveira_dm_dm_guara.pdf: 10110047 bytes, checksum: 86cc594889112132d78452c96ef59879 (MD5) Previous issue date: 2018-07-30 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Maior conscientização em relação as questões ambientais, atrelada a escassez de recursos, problemas ambientais globais e a políticas ambientais cada vez mais fortes influenciaram indústrias e pesquisadores a apreciar, estudar e desenvolver novos materiais a partir de fontes renováveis e novas tecnologias de fabricação. Entretanto, na literatura é reportado que a adesão interfacial entre fibras naturais e matriz polimérica é um fator que afeta as propriedades mecânicas do biocompósito, podendo ser melhorada por diversos tipos de tratamentos superficiais. Assim sendo, mantas de fibra de coco foram tratadas superficialmente por jato de plasma atmosférico, considerado menos agressivo ao meio ambiente quando comparado a tratamentos químicos, com o intuito de melhorar a adesão interfacial do biocompósitos. As fibras de coco foram caracterizadas com o objetivo de verificar a influência do tratamento nas propriedades físicas, químicas e térmicas. Verificou-se que o tratamento modificou a superfície das fibras e, consequentemente, sua hidrofilicidade e energia superficial, diminuindo o valor da permeabilidade. Parâmetros de processamento e o ciclo de cura mais adequado foram determinados como 80 ºC por 210 min, 135 ºC por 180 min e 160 ºC por 120 min, sem a aplicação de vácuo durante o processo e com fração volumétrica de fibras de aproximadamente 40 %. Inspeção acústica por ultrassom permitiu avaliar o processamento das placas dos biocompósitos verificando possíveis imperfeições causadas pela impregnação da fibra pela resina e sua homogeneidade. As análises termogravimétricas indicaram que a temperatura inicial de degradação dos biocompósitos é de 175 ºC. A temperatura de transição vítrea, determinada por DMA, é de aproximadamente 80 ºC. Os ensaios mecânicos apresentaram maiores valores de resistência à tração e de resistência à flexão para os biocompósitos reforçados com fibras tratadas quando comparados aos biocompósitos reforçados com fibras in natura. Maiores valores do módulo em tração e módulo em flexão, bem como os módulos de perda e armazenamento calculados por DMA para os biocompósitos reforçados com fibras tratadas sustentaram melhores propriedades mecânicas como resultado do tratamento a plasma. A morfologia da fratura dos biocompósitos indicou uma melhor adesão reforço-matriz para os biocompósitos com fibras tratadas. / Greater awareness regarding environmental issues, coupled with scarcity of resources, global environmental problems, and increasingly strong environmental policies have influenced industries and researchers to appreciate, study and develop new materials from renewable resources and new manufacturing technologies. However, literature reports that interfacial adhesion between natural fibers and polymeric matrix is a factor that affects the biocomposite mechanical properties, able to be improved by several types of surface treatments. Thus, coconut fiber mats were surface treated by atmospheric plasma jet, considered less aggressive to the environment when compared to chemical treatments, in order to improve interfacial adhesion with the polymer matrix to obtain biocomposites. Data from coconut fiber characterization shown that the treatment modified the fibers surface and consequently their hydrophilicity and surface energy, decreasing their permeability value. Processing parameters and most appropriate curing cycle were determined and defined as 80 °C for 210 min, 135 °C for 180 min and 160 °C for 120 min, without application of vacuum during the process and approximately 40 % fiber volume fraction. Ultrasonic acoustic inspection allowed evaluating the biocomposite plates processing by verifying possible imperfections caused by impregnation of the coconut fiber by the resin and its homogeneity. Thermogravimetric analysis indicated that the initial biocomposite degradation temperature is 175 °C. Glass transition temperature, determined by DMA, is approximately 80 °C. Mechanical tests presented higher values of tensile strength and flexural strength for the biocomposites reinforced with treated fibers when compared to the biocomposites reinforced with untreated fibers. Higher values of tensile and flexural modulus, as well as DMA loss and storage modulus for biocomposites reinforced with treated fibers sustained better mechanical properties because of the plasma treatment. Fracture morphology indicated better reinforcement-matrix adhesion for biocomposite reinforced with treated fibers / 136348/2016-5

Cette thèse porte sur le développement de résines polyesterimides insaturés pour des applications de type vernis d'imprégnation pour isolation électrique. Il s’agit de matériaux polymères thermodurcissables, qui assurent la double fonction d'isolant et d'agent de cohésion du système isolé. Ils se différencient en classes thermiques, qui définissent leur température maximale d'utilisation. Dans le cadre de cette étude, nous cherchons à développer des produits de classe thermique supérieure ou égale à 180°C. Une première partie de cette étude a porté sur l'amélioration de deux produits commerciaux à base de polyesters insaturés à fonctions terminales imides. Notre attention s'est portée sur la modification de leur structure chimique, afin de voir comment les différents précurseurs utilisés influencent les propriétés des résines. Une seconde partie a consisté à développer de nouvelles résines à base de polyesterimides insaturés, à partir de trois types de précurseurs imides difonctionnels. / This thesis focuses on the development of unsaturated polyesterimide resins as impregnating varnishes for electrical insulation applications. These thermosetting polymer materials provide the dual function of insulating and cohesion agent of the isolated system. They differ in thermal classes, which define their maximum operating temperature. In this study, we tried to develop products with a thermal class above or equal to 180°C. The first part of this study focused on the improvement of two commercial products based on imide-endcapped unsaturated polyester. Our attention turned to the modification of their chemical structure, to see how the different precursors used affect the thermal and mechanical properties of resins. A second part was to develop new unsaturated polyesterimide resins, using three types of difunctional imide precursors.