Burkholderia sacchari é uma nova espécie bacteriana do solo brasileiro que tem a capacidade de crescer em sacarose e acumular grânulos intracelulares de poliésteres pertencentes à família dos polihidroxiaIcanoatos (PHA). Quando cultivado em sacarose, o homopolímero poli-3¬hidroxibutirato é acumulado por esta bactéria, que é usado como um plástico biodegradável e biocompatível. Quando sacarose e ácido propiônico são fornecidos como fontes de carbono, as células de B. sacchari acumulam o copolímero poli-3-hidroxibutirato-co-3-hidroxivalerato (P3HB-co-3HV). Entretanto, uma pequena porcentagem do ácido propiônico fornecido é convertido a unidades 3HV devido à eficientes vias catabólicas que convertem este substrato preferencialmente a biomassa, CO2 e água, reduzindo portanto a eficiência da produção do polímero. Ao menos duas vias do catabolismo de propionato foram previamente propostas em B. sacchari: a-oxidação e ciclo do 2-metilcitrato (2MCC), sendo somente a última confilmada no nível molecular. Mutantes UV, obtidos anteriormente, foram incapazes de crescer em propionato (prp) e também apresentaram fenótipo afetado no crescimento em intermediários da a-oxidação. No presente trabalho, após uma busca em bibliotecas genômicas de B. sacchari, uma delas construída também no presente trabalho, três diferentes fragmentos de DNA presentes nos clones AI, PI e P2 foram capazes de restaurar o fenótipo prp+ aos mutantes. Experimentos quantitativos revelaram que AI somente restaurou parcialmente a conversão de propionato a unidades 3HV aos mutantes. PI foi capaz de restaurar a capacidade de crescimento em propionato, e em outros intermediários da a-oxidação, a um dos mutantes. Um DNA de 1.2 Kb, subfragmento de PI, ainda capaz de complementar mutantes prp, foi subclonado e seqüenciado, demonstrando similaridade a seqüências de DNA codificadoras de reguladores transcricionais do tipo LysR de várias bactérias, incluindo espécies de Bllrkholderia. Regiões adjacentes a LysR em diferentes genomas de Burkholderia são anotados como codificadores de acil-CoA desidrogenases, ao lado de proposta acil-CoA transferases/carnitina desidrogenases e de uma permease do facilitador maior da superfamília MFS-l. Após confirmação das mesmas regiões adjacentes em B. sacchari e também a sua específica deleção, será possível provar a presença da via do catabolismo de propionato indicada neste trabalho. / Burkholderia sacchari is a new bacterial species from brazilian soil, able to grow in sucrose, accumulating intracellular granules of polyester belonging to the polyhydroxyalkanoate family (PHA). When cultivated on sucrose, the homopolymer poly-3-hydroxybutyrate is accumulated by this bacterium, which is used as biodegradable and biocompatible plastic. When sucrose and propionic acid are supplied as carbon sources, B. sacchari cells accumulate the copolymer poly-3-hydroxybutyrate-co-3-hydroxyvalerate (P3HB-co-3HV). However, a small percentage ofthe propionic acid supplied is converted to 3HV units, because efficient catabolic pathways convert this substrate preferentially to biomass, CO2 and water, thus reducing the efficiency of polymer production. At least two propionate catabolic pathways have been previously indicated in B. sacchari: a-oxidation and the 2-methylcitric acid (2MCC), the latter confirmed at molecular leveI. UV mutants previously obtained were unable to grow in propionate (prp) and also showed the phenotype affected concerning grow on intermediates of propionate a-oxidation. In the present work, after a screening in B. sacchari genomic libraries, one ofthem constructed also in the present work, the prp + phenotype was restored to the mutants by three different DNA fragments harbored by dones A), PI and P2. Quantitative experiments revealed that AI restored only partially the quantitative conversion of propionate to 3HV units to the mutants. PI restored the ability to grow in propionate and in other intermediates of a-oxidation to one prp mutant. A DNA 1.2 Kb subfragment of PI, still able to complement prp mutants, was subcloned and sequenced, showing similarity to DNA sequences encoding to LysR-type transcriptional regulators of various bacteria, including BlIrkholderia species. Adjacent regions to LysR in different genomes of BlIrkholderia are annotated as encoding to acyl-CoA dehydrogenases, neighboring a predicted acyl-CoA transferases/carnitine dehydratase and a permease ofthe major facilitator superfamily MFS-1. After confirmation ofthe same adjacent regions in B. sacchari and also their especific deletion, it will be possible to prove the presence of the pathway indicated here in the catabolism of propionate.

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.

The parcel shelf in a car is one of the things that are most exposed to ultraviolet light and heat. The sunlight causes ultraviolet radiation and excessive heat to this area. This can cause the material to degrade, fade or drift in colour. The parcel shelf production is today divided between three producers. This requires a good contact and cooperation between the different actors. As the automobile industry is a very complex industry, high demand is required of everyone involved. The goal of this study was to find improvements that could lead to a better ultraviolet and heat protection. Volvo Cars provided material and the experiments were held on their test facility. The tests were conducted based on the Volvo Cars requirements and methods. A Weather-Ometer is used to simulate the ultraviolet light and heat, the same way a parcel shelf is exposed to outdoors. Chemical analyses are used to determine whether there is any difference in the material when it is aged in a Weather-Ometer or not. The parcel shelf is made of needle punched, dispersed dyed polyester. The results showed that the present parcel shelf material does indeed show a colour shift after ageing. The authors present a number of suggestions to improve the material's characteristics. For example, Volvo could consider using an acrylic non-woven instead of polyester. Dyes that withstand ultraviolet radiation better can also be chosen and a variety of ultraviolet absorbers can be added. 2-(2-hydroxy-5-carboxy-phenyl)-2H-benzotriazole, Tinuvin P, 327 [2-(2-hydroxy-5-methyl-phenyl) 2H-benzotriazole, 2-(3,5-butyl-6-hydroxy)-2H-2-chloro-benzotriazole respectively] and 2,4-dihydroxy-benzophenone are example of absorbers that can be added to make the ultraviolet resistance better. / Program: Textilingenjörsutbildningen

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Os materiais poliméricos tem sido uma das causas dos problemas ambientais discutidos em todo mundo nos últimos tempos. Como uma das soluções para esse problema, estão os polímeros biodegradáveis que são materiais que se degradam pela ação de microorganismos. Uma Indústria sediada no Brasil lançou recentemente um poliéster biodegradável que surge boa alternativa para o crescimento no mercado dos polímeros biodegradáveis, principalmente por possuir em sua composição matéria prima de fonte renovável. Neste trabalho foram preparados compósitos com matriz de poliéster biodegradável e fibra de coco verde com e sem modificação química por acetilação em misturador interno Haake. Foi estudada a biodegradabilidade em solo simulado do polímero puro e de seus compósitos e foram avaliadas as propriedades térmicas, morfológicas e mecânicas do polímero puro e de alguns de seus compósitos. O teste de biodegradabilidade foi feito pelo enterro das amostras em solo simulado por períodos distintos, variando de duas a dezessete semanas, seguindo a Norma ASTM G 160 03. Após cada período de teste, as amostras foram retiradas do solo e analisadas por microscopia ótica (MO), microscopia eletrônica de varredura (MEV), análise termogravimétrica (TGA), calorimetria diferencial de varredura (DSC), espectroscopia na região do infravermelho (FTIR) e análise mecânica de tração. Os resultados obtidos indicaram que tanto o polímero puro quanto os seus compósitos sofreram biodegradação, a presença da fibra apenas atrasa o processo de biodegradação, as fibras de coco tiveram uma boa afinidade com a matriz polimérica, a incorporação de 5% fibra de coco na matriz torna o compósito mais rígido e a incorporação da fibra e o processo de biodegradação alteram as características da fase cristalina no material polimérico. / The final disposal of the polymer materials have been one of the causes of environmental problems discussed around the world in recent times. As one of the solutions to this problem comes the biodegradable polymers, which are materials that are degraded by microorganisms. An industry based in Brazil recently lauched a biodegradable polyester that comes good alternative for growth in the market for biodegradable polymer, mainly by having in its composition raw material from renewable resources. In this work, composites were prepared with biodegradable polyester matrix and green coconut fiber with and without chemical modification acetylation internal mixer Haake. The degradation of pure polymer and their composites in simulated soil were evaluated and also the morphology, thermal and mechanical properties of the polymer and some of its composites. The biodegradability test was carried out by burying the samples in simulated soil for different periods ranging from two to seventeen weeks, following the ASTM G 160-03. After each test, samples were removed from the soil and analyzed by optical microscopy (OM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR) and analysis of stress strength. The results indicated that both the polymer pure as their composites suffered biodegradation, the presence of the fiber only delays the process of biodegradation. The coconut fibers had affinity with the polymer matrix and the incorporation of 5% coconut fiber in the matrix polyester made it became stiffer. Besides, the incorporation of the fiber and the biodegradation process changes the characteristics of the polymer crystalline phase.

Textile processing methods such as conventional exhaustion dyeing, pre-treatments and printing consume high amounts of water and use partly toxic and hazardous chemicals which are non-degradable. These chemicals (e.g. excess amount of dye, additives and catalysts) remain partially in the waste-water which is drained out and ends up polluting the environment. The supercritical carbon dioxide dyeing technology presents an eco-friendly and water-free method with reduced use of chemicals and energy. The benefits of such technology are currently not overcoming the relative high investment costs which impede its full implementation into the textile industry. This study presents an approach to extent the application of the eco-friendly supercritical carbon dioxide technology. It combines the well-studied supercritical carbon dioxide dyeing process for polyester with the functionalisation process to obtain water repellent surface properties. As water repellent (substance) environmentally benign silicones are used. Results showed that the simultaneous dyeing and functionalisation process was feasible assessed by the compatibility of the dye and silicone in the system. Silicone and dye did not interfere in each other’s functionality (colour strength and water contact angle). Further the process temperature and silicone molecular weight showed no influence on the colour strength of the fabric whereas the water contact angle (water repellence) increased with increasing temperature. The resulting polyester fabric showed acceptable colour strength yet did not obtain sufficient water repellent properties despite the increase in water contact angle of the treated samples to the untreated reference sample. The poor water repellence is suggested to be caused by the hydrophobic functional groups of the silicones oriented towards each other rather than toward the outer fabric surface. Overall the thesis is promoting research which combines eco-friendly technologies including environmental benign chemicals for the textile industry. Silicones are widely used in textile processing not only as water repellents, but also as anti-foaming agents, lubricants and softeners. Therefore a water-free and eco-friendly application method can benefit a wide range of finishing processes.

Solvent-borne thermally cured coil-coating resins contain large amounts of volatile organic solvents in order to obtain suitable flow for film application. This work describes how the expensive and environmental hazardous volatile organic solvent content of a solvent-borne thermally cured polyester/melamine coil-coating system can be reduced by introduction of fatty acid methyl esters (FAMEs) as reactive diluents and modification of the polyester binder resin. The evaluated reactive diluents, two rape seed methyl esters (RMEs), two linseed oil methyl esters (LMEs), and a tall oil methyl ester (TOME) have been evaluated both in a fully formulated clear-coat system and via model studies. Viscosity measurements of wet paint mixtures showed that formulations with hyperbranched polyester binder hold lower viscosity than conventional polyester binder resins and that FAME works as a diluent. Fully formulated clear-coats were cured under simulated industrial coil-coating cure conditions and in a convection oven at lower temperatures respectively. FAME increases the mobility of the system enhancing the film formation process. Free-standing clear-coat films were analyzed with Raman, carbon-14 dating, extraction, dynamic mechanical analysis, and visual observation. Incorporation of FAME could not be confirmed by Raman analysis. However, carbon-14 dating indicated the presence of FAME that could not be extracted from the films. The mechanical properties of the films were also affected by the addition of FAMEs, oven temperature, choice of co-solvent, and flash-off period. Conventional film characterization tests on substrate supported coatings indicated that binder resin structure and cure conditions affect the final film properties. Model studies were performed to clarify how FAME can chemically react through transesterification with the hydroxyl-groups of the polyester. The transesterification reaction between different FAMEs and primary alcohols with and without tertiary hydrogen was monitored with 1H-NMR and real time IR. Evaporation and side reactions, e.g. alkene reactions, are competing factors to the transesterification reaction. The study showed that fatty acid structure, reaction time, and temperature affect the transesterification conversion, degree of side reactions, and choice of catalyst. A pigmented fully formulated polyester/melamine formulation with a reactive diluent was cured at full scale in an industrial coil-coating production facility. Evaluation of the final film properties showed that the coating fulfills the specification of conventional polyester/melamine coil-coating systems. / QC 20100817

In this study, the aim is to investigate the stiffness, longitudinal tensile strength and circumferential tensile strength of short fiber reinforced polyester composite pipes produced by centrifugal casting production method. To achieve this aim, theoretical calculation of modulus of elasticity of pipes was done and then test program was carried out on pipe samples produced with three different resin types which were orthophthalic, isophthalic and vinyl ester resin and three different fiber types which were E glass fiber, ECR glass fiber and basalt fiber. The tests were performed according to ISO (International Organization for Standardization) standards. When resin type and fiber type effect on the fiber reinforced polyester pipe samples were evaluated, calculated elastic modulus values were in accordance with the test results. According to the experimental test data, which were used to evaluate the effect of resin type on fiber reinforced polyester pipe properties, there is not a significant difference was observed in the stiffness, longitudinal and circumferential tensile strength test results of pipes having different resin types. In other words, there was not a significant effect of resin type on the stiffness, longitudinal tensile strength and circumferential tensile strength of short fiber reinforced pipes produced by centrifugal casting method. According to the experimental test data, which were used to evaluate the effect of fiber type on the properties of fiber reinforced polyester pipe, basalt fiber reinforced pipe samples showed higher mechanical performance over E glass fiber and ECR glass fiber reinforced pipes. However, the test results of basalt reinforced polyester pipe were not as good as the individual properties of basalt fiber. Finally, by comparing the basalt fiber reinforced pipe samples having almost the same stiffness and tensile test results as E glass fiber reinforced pipe samples, the gain in fiber and resin amount were investigated. Basalt fiber reinforced pipes were slightly lighter and thinner than E glass fiber reinforced pipes. However, the decrease in the amount of the fiber and resin in basalt reinforced pipe did not result in an overall cost reduction.

<p>A paper that shows motion when being exposed to heat has in this study been called a paper muscle. A paper muscle can be used for many different applications, e.g. smart advertisement or indicators in printed paper products. The muscles created in the present work were prepared by gluing or printing a polymer layer onto paper. The polymer layers consisted of MELINEX, MYLAR or toner, which are known to expand when exposed to heat. Furthermore, all three material systems showed bending when exposed to heat.</p><p>A mechanical bilayer model was implemented and used to quantitatively study the parameters that influence the bending of the muscles. The model indicated that the dimensional changes of the polymer layers relative to that of the copy paper was found to be approximately 0,1-0,5 % within the temperature range 23-60 °C. The experiments showed that the combined dimensional changes within the polymer and paper layers were not linear with respect to temperature, and that there was a significant difference in bending for muscles cut in the MD and in the CD. Also, when assuming that the polymer is the active component, the observed coefficient of thermal expansion was a factor ~10 greater compared to published literature data. These findings led to the conclusion that it was indeed the dimensional changes within the paper that were the dominant cause of the bending. This was confirmed by a muscle, comprising a bilayer of paper cut in the MD and the CD, which bended when exposed to heat. The results also indicate that a large part of the bending could be attributed to the hygrocontraction of paper.</p>

A paper that shows motion when being exposed to heat has in this study been called a paper muscle. A paper muscle can be used for many different applications, e.g. smart advertisement or indicators in printed paper products. The muscles created in the present work were prepared by gluing or printing a polymer layer onto paper. The polymer layers consisted of MELINEX, MYLAR or toner, which are known to expand when exposed to heat. Furthermore, all three material systems showed bending when exposed to heat. A mechanical bilayer model was implemented and used to quantitatively study the parameters that influence the bending of the muscles. The model indicated that the dimensional changes of the polymer layers relative to that of the copy paper was found to be approximately 0,1-0,5 % within the temperature range 23-60 °C. The experiments showed that the combined dimensional changes within the polymer and paper layers were not linear with respect to temperature, and that there was a significant difference in bending for muscles cut in the MD and in the CD. Also, when assuming that the polymer is the active component, the observed coefficient of thermal expansion was a factor ~10 greater compared to published literature data. These findings led to the conclusion that it was indeed the dimensional changes within the paper that were the dominant cause of the bending. This was confirmed by a muscle, comprising a bilayer of paper cut in the MD and the CD, which bended when exposed to heat. The results also indicate that a large part of the bending could be attributed to the hygrocontraction of paper.

On s'intéresse dans cette étude au potentiel de copolymères à blocs (BCP) de types PBA-b-P(MMA-co-DMA) et PBA-b-P(BA-co-DMA) en tant qu'additifs multifonctionnels nanostructurant la matrice thermodurcissable polyester insaturé de composites SMC et BMC. La nanostructuration de la résine polyester insaturé (UPR) est assurée par la ségrégation du bloc élastomère poly(acrylate de butyle), ainsi que par la miscibilité du deuxième bloc dans le réseau grâce à la bonne compatibilité des motifs diméthylacrylamide (auto-assemblage). Ces BCP sont tout d'abord étudiés en tant qu'agents renforçants et anti-retrait dans les composites SMC et BMC, en étant substitués et comparés aux additifs anti-retrait conventionnels PVAc et P(MMA-co-S) incorporés traditionnellement afin de compenser le retrait de la résine polyester. Ces additifs nanostructurants sont ensuite évalués en tant qu'agents de mûrissement des compounds SMC. La nanostructuration des BCP dans la résine UP réactive pouvant entrainer une importante augmentation de la viscosité (formation d'un gel), ces additifs pourraient peut-être constituer des agents de mûrissement plus efficaces que l'oxyde de magnésium couramment utilisé à cet effet. Une étude des matrices [UPR + BCP, UPR + PVAc et UPR + P(MMA-co-S)] est réalisée dans un premier temps, les composites BMC et SMC chargés par du carbonate de calcium et renforcés par des fibres de verre étant étudiés par la suite. En absence de charges et de fibres de verre (matrice seule), la nanostructuration est moins efficace que la macroséparation de phase des additifs conventionnels PVAc et P(MMA-co-S) pour compenser le retrait du réseau polyester. Dans un composite en revanche, la nanostructuration conduit à une compensation du retrait intermédiaire entre celles du P(MMA-co-S) et du PVAc. Au niveau de la matrice seule, la nanostructuration permet d'éviter une diminution conséquente de l'énergie de rupture du réseau polyester et permet même dans certains cas une amélioration significative de cette dernière, alors que les additifs conventionnels engendrent un effondrement de cette propriété. Cette différence est cependant beaucoup moins visible dans le cas des composites, les charges entrainant une fissuration prématurée de la matrice. Un composite nanostructuré peut tout de même présenter un renforcement significatif par rapport aux composites conventionnels lorsqu'il contient des nanovides compensateurs de retrait de tailles conséquentes qui améliorent la ténacité du matériau. En ce qui concerne le mûrissement d'un compound SMC par nanostructuration au cours du refroidissement (passage de la transition ordre-désordre), si l'augmentation de la viscosité d'un système réactif UPR + BCP semble suffisamment importante et abrupte, elle est cependant insuffisante en présence des charges ou alors intervient à une température trop faible en raison de l'influence de ces dernières sur la nanostructuration.