Made available in DSpace on 2017-06-01T18:20:28Z (GMT). No. of bitstreams: 1 dissertacao_alicia_jara.pdf: 8514825 bytes, checksum: e7811d2022af27360b50bd77f223f4ba (MD5) Previous issue date: 2007-12-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In recent years, the consumption of the poly ethylene terephtalate plastic - PET is used in the manufacture of bottles, comes increasing in Brazil. PET is a polar thermoplastic, with raised dimensional stability and temperature of fusion, high impermeability the acid gases and chemical resistance to solvents. The biodegradation has been described as a possible methodology to reduce the accumulation of plastics. In this work it was carried through the evaluation by Bacillus subtilis and Phanerochaete chrysosporium performance on the biodegradation of the polyethylene terephtalate. In this direction, particles of polymer were submitted to the treatments: exposition to ultra violet light (6 and 36 hours) and temperatures (35ºC and 50ºC), followed incubation with the microorganisms during 30 and 60 days. The polymer degradation process was accompanied by determination of pH, biofilm formation and the cells viability, enzymes detection (amylase, protease, esterase, and polyphenoloxidase), as well as the scanning electron microscopy of biofilm and toxicity tests. The results obtained observed the biofilm formation by Bacillus subtilis on polyethylene terephtalate surface particles. The treatment using the temperature of 50ºC demonstrated a higher alteration in the surface of the polymer, supported the colonization of the microorganisms followed of the hydrolytic enzymes production. It was observed that Bacillus subtilis does not produced polyphenoloxidase. The results indicated the temperature (50º.C), induces the esterase production and it is related to degradation process. The P. chrysosporium produced esterases and polyphenoloxidase, whose enzymes had demonstrated to be involved with the polyethylene terephtalate degradation process, and were formed products with higher toxicities to Artemia salina / O Tereftalato de Polietileno PET é um termoplástico polar,com elevada estabilidade dimensional e temperatura de fusão, alta impermeabilidade a gases e resistência química a ácidos e solventes, empregado na fabricação de garrafas no Brasil. A biodegradação tem sido descrita como uma possível metodologia para reduzir o acúmulo de plásticos. Neste trabalho foi avaliado o desempenho das linhagens de Bacillus subtilis e Phanerochaete chrysosporium isoladamente na biodegradação do tereftalato de polietileno. Neste sentido, foram preparadas partículas do polímero sendo submetidas aos tratamentos com luz ultra violeta (6 e 36 horas) e temperaturas (35ºC e 50ºC) em seguida, foram colocadas nos meios caldo nutriente (B.subtilis) e Sabouraud (P. chrysosporium), incubados por 30 e 60 dias, incubados a 35ºC e 28ºC, respectivamente. Com a degradação das partículas observou-se que o pH passou de 5 para >8, com formação de biofilmes e indução da produção de enzimas (amilase, protease, esterase e polifenoloxidases). A formação do biofilme foi evidenciada por microscopia eletrônica de varredura. Os produtos metabólicos formados no meio de cultura foram avaliados pelo teste de toxicidade utilizando Artemia salina. A microscopia eletrônica demonstrou que B. subtilis colonizou completamente a superfície das partículas do PET, tanto nas condições controle (sem tratamento), como tratados. Os melhores resultados foram observados com o tratamento à temperatura de 50ºC, onde ocorreu alteração na superfície do polímero, perda da massa polimérica, permitindo maior colonização de ambos os microrganismos. As enzimas hidrolíticas foram produzidas pelos microrganismos em todos os tratamentos, em especial, à temperatura de 50ºC. Contudo, observou-se que B. subtilis não produziu polifenoloxidases. Os subprodutos da degradação do PET nas condições estudadas apresentaram alta toxicidade para Artemia salina no caso do P. chrysosporium e baixa toxicidade para B. subtilis. Os resultados obtidos sugerem o tratamento o prévio com a temperatura de 50ºC como importante para o processo de biorremediação

Finite element simulation of thermoplastic components is gaining importance as the companies aim to avoid overdesign of the components. Cost of the component can be minimized by using an adequate amount of material for its application. Life of the component, in a particular application, can be predicted as early as during its design phase with the help of computer simulations. To achieve reliable simulation results, an accurate material model which can predict the material behaviour is vital. Most material models consist of a number of material parameters that needs to be fed into them. These material parameters can be identified with the inputs from physical tests. The accuracy of the data extracted from the physical tests, however, remains the base for the aforementioned process. The report deals with the implementation of optical measurement technique such as Digital Image Correlation (DIC) in contrast with the conventional extensometers. A tensile test is conducted on a glass fibre reinforced thermoplastic specimen, according to ISO 527-2/1A, to extract the experimental data with the help of DIC technique. The material behavior is reproduced within a finite element analysis software package LS-DYNA, with the combination of elastoplastic model called *MAT_024 and stress state dependent damage and failure model called GISSMO. The tensile test is performed under quasi-static condition to rule out the strain rate dependency of the thermoplastic material. The mesh sensitivity of the damage model is taken into account with the element size regularization. The thesis concerns setting up a routine for material parameter identification of thermoplastics by full-field calibration (FFC) approach. Also, comparison of the strain field in the specimen, obtained through the newly set up routine against the regular non-FFC i.e. extensometer measurement routine. The major objective being, through the comparisons, a qualitative assessment of the two routines in terms of calibration time vs. gain in simulation accuracy. Material models obtained through both the routines are implemented in three-point and four-point bending simulations. The predicted material behaviors are evaluated against experimental tests.

Cette thèse porte sur l’étude du comportement au moussage d’un élastomère silicone et de thermoplastiques vulcanisés (TPV) à base de silicone. Le moussage a été réalisé à l’aide des procédés batch et d’extrusion moussage en utilisant le CO2 comme agent moussant. Lamicrostructuration de fluorosilicone, ayant une grande affinité avec le CO2, dans la silicone favorise grandement le moussage par nucléation hétérogène. La morphologie du mélange et des mousses résultantes ainsi que la rhéologie en cisaillement et en écoulement biélongationnelont été améliorés en élaborant sous cisaillement des structures branchées de chaines silicones en présence d’un faible taux de peroxyde. En effet, la modification chimique sous écoulement permet de réduire la taille des nodules de fluorosilicone augmentant ainsi la densité volumique de sites de nucléation potentiels. Elle permet également de créer des structures hyperbranchées générant des propriétés de durcissementdes contraintes en écoulement bi-élongationnel ce qui a pour effet de réduire la croissance cellulaire et la coalescence lors de l’expansion de la mousse.La deuxième partie est dédiée à l’étude du moussage de TPV silicone pour lesquels la phase silicone est partiellement réticulée. Ces TPV ont étonnement le même comportement en rhéologie élongationnelle que la matrice polyéthylène basse densité (PEBD). Bien que les TPVs atteignent des bonnes propriétés en termes d’élongation à rupture à l’état fondu, leur comportement au moussage est très différent. En effet il est principalement lié à leur viscosité sous fort taux de cisaillement ainsi qu’aux conditions d’extrusion i.e. la pression avant filière et la détente en sortie de filière. Avec un taux de réticulation approprié de laphase élastomère, le TPV mousse de manière similaire que le PEBD / This work is devoted to the study of the foaming behavior of a silicone elastomer and thermoplastic vulcanizates (TPV) based silicone. The foaming step was carried out by batch and extrusion foaming processes with CO2 as blowing agent. The foamability of silicone elastomer was improved by a microstructuration of fluorosilicone which is a highly CO2-philic elastomer through heterogeneous nucleation. The foam and blend morphologies as well as the rheology in shear and bi-elongation modes were further fitted by branching silicone chains under shearing conditions in a roll mill with a small amount of peroxide. Indeed, this dynamic chemical modification reduces the size of fluorosilicone droplets which leads to increase the volume density of nucleating sites and consequently lowers the mean bubble size. Furthermore, it allows also the formation of multi-scale branched structures inducing a strain hardening behavior in bi-elongational flow which restrict the cell growth and coalescence during foam expansion.The second part deals with the foaming behavior of TPV silicone in which partially crosslinked silicone nodules are dispersed. Surprisingly, formulations exhibit close rheological behavior in elongation modes that the neat polyethylene (LDPE) matrix and reach prerequisites for foaming applications in terms of elongation at break. However, their foaming behavior are far different and are correlated to the extrusion foaming parameters which are known to control the nucleation i.e. the pressure before the die and the depressurization rate at the die exit. A proper choice of the gel content allows a TPV foamability close to that of LDPE

As applications for thermoplastic composites increase, the understanding of their properties become more important. Fabrication methods for thermoplastic composites continually improve to match designs specifications. These advanced thermoplastics have begun to show an improvement in mechanical properties over those found in thermoset composites commonly used in industry. Polyaryletherketones (PEK) have high service temperatures, good mechanical properties, and improved processing capabilities compared to thermoplastics used in the past making them important to the aerospace industry. The wide range of types of PEK make them suitable for a variety of applications, but selection of specific chemistries, processing parameters, and composite stack-ups determine the mechanical properties produced. Differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR) were used to determine crystallinity and chemical properties of several polyaryletherketones. Tensile, compressive, and Mode I interlaminar fracture toughness tests were conducted to analyze mechanical properties of these advanced thermoplastics. Several fabrication processes were also tested to determine optimal consolidation and aesthetic appearance of structural members. All testing was conducted at The Boeing Company in Seattle, Washington. Because all testing and conclusions are proprietary a general synopsis of the experience will be presented.

Some of the major obstacles the microfluidics industry has yet to overcome in order to facilitate large scale manufacturing of devices are costly back-end processes. Among these, bonding presents some of the most obvious difficulties and is often associated with structural deformation and surface modification. Off-stoichiometric thiol-ene (OSTE) is a relatively new material and hasn’t yet achieved the same level of adoption as Polydimethylsiloxane (PDMS) which has been the go-to material in the field of microfluidics for over two decades. OSTE offers an alternative to PDMS and promises bonding without surface treatment as well as a hydrophilic surface, removing a step in the manufacturing process. In this work, the property of OSTE to bond with a variety of commonly used thermoplastic materials were tested as well as its suitability for use in pharmaceutical devices such as Lab-on-a-chip. In addition to untreated OSTE, a surface modifier was used to examine the potential for surface modification when using OSTE as a microfluidics material. From the testing performed, we demonstrated OSTE’s capacity to form robust bonds with a range of thermoplastic materials as well as comparable biocompatibility to PDMS. / Bland de största hindren som industrin ännu ej löst när det kommer till storskalig produktion av mikrofluidiska produkter är kostsamma ”back-end” processer. Av dessa presenterar bindingsprocesser några av de mest uppenbara svårigheterna och medför ofta deformationer av finstrukturer samt ändringar i ytkemi. Off-stoichiometric thiolene (OSTE) är ett relativt nytt material och har ännu inte blivit lika utbrett i sin använding som Polydimethylsiloxane (PDMS) vilket har varit standardmaterialet i mikrofluidik i över två årtionden. OSTE erbjuder ett alternativ till PDMS, med bindingsprocesser som ej kräver ytterligare ytmodifikationer och en hydrofil yta, vilket eliminerar ett steg i tillverkningsprocessen. I detta arbete undersöktes egenskapen av OSTE att binda till en rad ofta använda thermoplaster samt dess lämplighet i medicinskt bruk, i system som ”Lab-on-a-chip”. Förutom obehandlad OSTE, så användes en ytmodifierare för att undersöka möjligheten för ytmodifiering vid användingen av OSTE i mikrofluidik. Resultaten av våra tester visade OSTE’s förmåga att forma robusta bindingar till en rad thermoplaster så väl som en jämförbar biokompatibilitet till PDMS.

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Nowadays, when environmental concerns are becoming increasingly important are there great interest in natural materials and recyclability. The possibility of reusing materials with maintained mechanical properties are essential for sustainability. Today produced approximately 90,000 tons of natural fiber reinforced composites in Europe of those are 40,000 tons compression molded of which the automotive industry uses 95%. Natural fiber reinforced composites is recyclable and therefore interesting in many applications. Also, natural fiber reinforced composites is inexpensive, light in weight and shows decent mechanical properties which makes them attractive to manufactures. However, the problem with natural fiber reinforced composites is the poor adhesion between fiber and matrix, the sensitivity of humidity and their low thermal stability. Those problems could be overcome by addition of compatibilizer and reactive filler. This study will examine the technical requirement in order to develop a sustainable and recyclable biocomposite. It investigates the composition of matrix (polypropylene), fiber (flax), compatibilizer (maleic anhydride grafted polypropylene) and reactive filler (CaO) in order to obtain various combinations of stiffness, strength and processability. The two main methods used for preparing samples were compounding and injection molding. Results shows that 20 wt% flax was the optimal fiber content and that maleic anhydride grafted polypropylene is a very good compatibilizer by enhancing the strength significant. Surprisingly was the strength impaired due to the addition of CaO. The composition of 20 wt% flax, 1 wt% maleic anhydride grafted polypropylene and 79 wt% polypropylene is the technically most favorable composition.

Punktförmige Verbindungen, wie das Clinchen, bieten vorteilhafte Eigenschaften und werden in zunehmendem Maße in der Dünnblech verarbeitenden Industrie für metallische Verbindungen eingesetzt. Sie spielen gegenwärtig für Metall-Kunststoff-Verbindungen eine untergeordnete beziehungsweise gar keine Rolle. Dies ist wahrscheinlich der Tatsache geschuldet, dass Kunststoffe aufgrund ihrer mechanischen Eigenschaften ungeeignet für das Clinchen scheinen. In der vorliegenden Dissertation werden die Grundlagen für das Clinchen von Metall-Kunststoff-Verbindungen erarbeitet und qualifiziert, so dass es möglich ist, damit eine Verbindung dieser Werkstoffe reproduzierbar herzustellen. Im Speziellen werden Prozessmerkmale und mechanische Verbindungseigenschaften des Clinchens von Metall-Kunststoff-Verbindungen sowie der Feuchtigkeitseinfluss des Kunststofffügepartners und der Einfluss von Wärme vor und/oder nach dem Fügen untersucht. / Because of its advantageous properties there is an extended utilization of point-shaped joints, like the clinching, in the sheet processing industry for metal-metal joints. These joining technologies are not relevant for metal-thermoplastic joints currently. The main reason for this could be the fact that the clinching process seems not to be eligible for thermoplastic materials. In the present thesis the fundamentals for clinching metal to thermoplastics were worked out and qualified. The results allow creating reproducible joints out of these materials. Process features and mechanical properties of clinched metal-thermoplastic joints were investigated. Also the influence of moisture and heat input during and after the clinching process was in focus.

Au cours de cette étude, il a été question de développer une méthodologie d’élaboration et d’évaluation de la qualité de l’interface fibre-matrice au sein d’un composite à matrice polyamide 12 renforcé par du verre. Un modèle macroscopique a été élaboré dans un premier temps sous forme d’un assemblage lame de verre/film polyamide 12, et plusieurs promoteurs d’adhésion, principalement des organosilanes, de fonctionnalités différentes et compatibles avec la matrice polyamide ont été testés. La qualité du greffage a pu être caractérisée grâce à des techniques d’analyses physico-chimiques adaptées (AFM, PM-IRRAS, mouillabilité,…), et la performance adhésive des assemblages a pu être évaluée par des tests mécaniques spécifiques (pelage, clivage). Dans une seconde étape, le protocole de dépôt décrit à l’échelle macroscopique a été adapté à l’échelle des fibres de verre, plus particulièrement à l’échelle mésoscopique des fibres optiques. Des essais mécaniques spécifiques à l’échelle microscopique (fragmentation) ont été réalisés afin d’évaluer la performance adhésive de l’interface dans les assemblages concernés. Une étude focalisée sur la compréhension des mécanismes interfaciaux a également été réalisée afin de clarifier la nature des interactions établies à l’interface fibre-matrice. Grâce aux différentes techniques de caractérisation physico-chimiques il a été possible de mettre en évidence l’influence de différents paramètres expérimentaux, tels que la durée du greffage, la densité de greffage et la chimie des surfaces traitées, sur la cristallisation de la matrice à l’interface. La dernière partie de ce travail de thèse concerne le passage à l’échelle du semi-produit sous forme de rubans. Des analyses des propriétés de l’interface ainsi que des caractéristiques mécaniques ont été réalisées. / During this study, the aim was to develop a methodology to elaborate and evaluate the quality of the fiber-matrix interface in a glass fiber reinforced polyamide 12 composite.At first, a macroscopic model was developed using a glass slide/polyamide 12 film assembly. Several organosilane adhesion promoters with different features and compatible with the polyamide matrix were tested. The grafting quality was characterized through appropriate physico-chemical analytical techniques (AFM, PM-IRRAS, Wetting…), and the adhesive performance of the assemblies was evaluated by specific mechanical tests (Peel test, Wedge test). In a second step, the deposition procedure described in macroscopic scale has been adapted to the glass fibers’ scale, more particularly to optical fibers. Specific mechanical tests were performed (fragmentation test) to assess the adhesive performance at the interface of the concerned assemblies.A study focused on the understanding of the interfacial mechanisms was also conducted to clarify the nature of the interactions established at the fiber-matrix interface. Thanks to the different physico-chemical characterization techniques, it has been possible to demonstrate the influence of various experimental parameters such as the surface treatment time, the grafting density and the chemistry on the treated surfaces on the crystallization of the matrix at the interface. The last part of this work concerns the transition to the semi-scale form of ribbons. The analysis of the interface’s properties and the mechanical characteristics has been investigated.

L’allégement des véhicules est une préoccupation majeure de l’industrie automobile, puisque cela permet de réduire les émissions des gaz à effet de serre, ce qui entraînerait une réduction des impacts de ceux-ci sur l’environnement à l’échelle mondiale. Cette volonté d’allégement des véhicules tout en restant accessible en termes de coûts, a conduit au remplacement des matériaux métalliques par des composites à matrices thermoplastiques pour de nombreuses applications. Le compromis entre la tenue thermomécanique et le coût massique du matériau amène à sélectionner des matrices polyamides renforcées par des fibres de verre courtes, et mises en forme par injection. Cependant, les outils prédictifs du comportement et les critères robustes pour la caractérisation des propriétés en fatigue, manquent encore. Ils sont pourtant indispensables pour la conception de pièces structurelles dans l’industrie automobile. La caractérisation en fatigue des polyamides renforcés de fibres de verre courtes présente de nombreuses difficultés, liées au comportement fortement non linéaire de la matrice dans les conditions de service visées (température et humidité), à la nature composite de ces matériaux, à l’influence du procédé de fabrication (orientation des fibres) et au caractère fortement dissipatif de la matrice thermoplastique (augmentations de température non négligeables lors des chargements cycliques). Un enjeu majeur est de comprendre les liens entre la microstructure, le chargement thermo-(hygro)-mécanique et les propriétés de fatigue (sites d’initiation, scénarios d’évolution, critère de rupture). Le premier objectif de cette thèse est de proposer des protocoles d’analyse permettant de caractériser l’influence de chaque paramètre sur le comportement en fatigue. Par ailleurs, la complexité des pièces industrielles en termes de géométrie et d’orientation des fibres soulève la question de la pertinence des éprouvettes classiques. Le second objectif principal de cette thèse est donc de concevoir des éprouvettes représentatives en terme d’orientation des fibres et d’accidents géométriques des pièces industrielles (appelées éprouvettes de structure) et de valider pour ces cas complexes, les démarches et critères proposés. Pour répondre à ces objectifs, nous souhaitons proposer un protocole basé sur des mesures d’auto-échauffement, qui donnerait accès d’une part aux champs d’énergie dissipée pour les cas hétérogènes investigués et qui offrirait, d’autre part, une opportunité de caractérisation rapide des propriétés en fatigue au travers de critères énergétiques / Vehicle weight reduction is a major issue in the automotive industry, because this contributes to reducing global warming emissions, resulting in a reduction of negative environmental impacts at the worldwide scale. To replace heavy metallic materials conventionally used, short fiber reinforced thermoplastics (SFRT) provide today a major opportunity to obtain lightweight automotive parts at a reasonable cost for several applications. The cost and the thermomechanical properties motivate the choice of polyamide matrix reinforced with glass fibers manufactured by injection molding. However, predictive modeling behavior tools and robust fatigue criteria must be identified. Both are needed for the design of structural pieces in the automotive industry. The fatigue design of SFRT components for structural applications in the automotive industry requires an accurate knowledge of several factors because the material features are complex, these features are related to the strong nonlinear behavior of the matrix under the service conditions (temperature and humidity), the composite nature of the material, the influence of the injection molding (fiber orientation) and the dissipative characteristics of the thermoplastic matrix (significant temperature rise during the cyclic loadings). A major issue is to understand the relations between the microstructure, the thermo-hydro-mechanical loading and the fatigue properties (fatigue initiation sites, evolution scenarios, and failure criterion). The first objective of this thesis is to suggest methods that allow for the characterization of the influence of each parameter on the fatigue behavior. Furthermore, the complexity of the industrial pieces in terms of geometry and fiber orientation challenges the relevancy of the classical samples. The second objective of this thesis is consequently to design more complex samples that intend to be representative in terms of fiber orientation and geometric details found in the industrial pieces (called structural samples) and to validate the methods and the fatigue criteria suggested for these complex cases. To achieve these objectives, a method based on thermal measurements giving access to the dissipation fields for the heterogeneous cases considered is proposed, this method also offers a very high reduction of the characterization duration of the fatigue properties through energetic criteria