L'objectif de cette thèse est de mener une caractérisation expérimentale complète du comportement mécanique et thermomécanique d'un polyuréthane thermoplastique compact et sous forme moussée, utilisé dans la fabrication de pièces antivibratoires dans l'industrie automobile. Cette caractérisation est effectuée en s'appuyant sur des techniques d'imagerie quantitative, la thermographie infrarouge en particulier. D'un point de vue mécanique, la dépendance des différents phénomènes - effet Mullins, hystérésis mécanique, déformation résiduelle et variation de volume - à la densité initiale et à la vitesse de chargement a été établie. Sur le plan thermique et calorimétrique, la signature de ces différents phénomènes a été caractérisée et les bilans énergétiques menés ont permis d'estimer la dissipation mécanique en fonction des conditions d'essais et de la densité initiale du matériau. Les résultats de ces travaux constituent une base de données expérimentale pour l'identification de paramètres constitutifs et l'enrichissement de lois de comportement. / This PhD thesis deals with the full mechanical and thermomechanical characterization of thermoplastic polyurethane, in its compact and foam states, dedicated to antivibratory systems for automotive. This characterization has been carried out by using quantitative imaging techniques, especially infrared thermography. From a mechanical point of view, the dependency of the different phenomena involved in the material deformation - Mullins effect, mechanical hysteresis, residual deformation and volume change - on the initial density and loading rate has been established. The thermal and calorimetric signature of these phenomena has been characterized and the mechanical dissipation was estimated from energy balances. The results obtained provide an experimental database for the identification of constitutive parameters and the enrichment of behavior laws.

Les stents urétéraux et les sondes de néphrostomie sont constitués de silicone ou de polyuréthane thermoplastique (TPU). Afin de limiter les risques infectieux lors de leur implantation, une modification topographique par création de pores permettrait de limiter l’adhésion des bactéries et de former des réservoirs pour une libération in situ de substances antiinfectieuses. Ce travail vise à préparer des surfaces en polymère ayant un motif poreux tubulaire ordonné. Une réplication en deux temps à partir de surfaces ordonnées poreuses d’oxyde d’aluminium (PAAO) préparées par 2 méthodes (double anodisation douce et double anodisation dure/douce) a été mise en œuvre pour reproduire le motif initial sur des surfaces en silicone et TPU. Pour le moule intermédiaire trois matériaux ont été testés (acrylonitrile butadiène styrène, polystyrène et résine polyacrylate). Les surfaces ont toutes été caractérisées par des techniques microscopiques et spectroscopiques. Les surfaces en PAAO préparées par double anodisation douce possédaient des pores d’environ 50 nm de diamètre et 100 nm de profondeur, alors que celles obtenues après mise au point de la méthode dure/douce étaient de taille supérieure, d’environ 125 nm de diamètre et ayant des profondeurs de quelques centaines de nanomètres. La surface du moule intermédiaire est constituée de picots. Une adhésion latérale de ceux-ci a été observée pour certaines conditions. La meilleure réplication du motif a été obtenue pour le TPU. Les surfaces ainsi obtenues pourront être utilisées et optimisées lors de l'étude ultérieure de l'adhésion du biofilm. / Ureteral stents and nephrostomy catheters are made of silicone or thermoplastic polyurethane (TPU). A topographical modification creating an ordered porous surface could limit the infectious risks during their implantation, by reducing bacterial adhesion and creating a loading platform from which anti-infectious compounds could be released.In this work, a two-steps replication method was used to create ordered porous polymer surfaces (silicone or TPU) using porous anodic aluminium oxide (PAAO) as master template. The PAAO surfaces were prepared by double mild or double hard/mild anodization. Three intermediate mould materials were tested (acrylonitrile butadiene styrene, polystyrene, polyacrylate resin). The polymer material (silicone or TPU) was then moulded onto the intermediate mould surfaces that possessed freestanding pillar arrays, to imprint pores. The obtained surfaces were characterized by microscopic and spectroscopic methods. The initial PAAO surfaces prepared by double mild anodization possessed pores of about 50 nm diameter and 100 nm depth, whereas those prepared after development of the double hard/mild anodization method were bigger, of about 125 nm diameter and several hundred nanometers deep. The intermediate mould structure possessed freestanding arrays, but instabilities (lateral adhesion) were noted for certain conditions. The best pattern replication was observed for TPU. In conclusion, these novel porous polymeric surfaces could be optimized and tested for an anti-biofilm effect.

No description available.

[pt] As mangueiras termoplásticas, um dos componentes funcionais mais importantes dos umbilicais, são compostas de tubo interno, reforço de fibra sintética e capa externa fabricada em material termoplástico com proteção contra ozônio e radiação ultravioleta (UV). A poliamida 11 (PA11) e o poliuretano termoplástico (TPU) são geralmente especificados para as capas externas, mas outros materiais que atendam a função podem ser utilizados, como o polietileno de alta densidade (PEAD). Independentemente do polímero selecionado para a fabricação das capas, elas precisam garantir a integridade das camadas inferiores da mangueira em um ambiente offshore severo devido à exposição constante ao sol e ao ambiente marítimo. Não é grande a quantidade de trabalhos que estudaram e correlacionaram os efeitos da sobreposição da radiação UV e ambiente salino nos materiais PA11, TPU e PEAD. Assim, o objetivo deste trabalho foi comparar as propriedades mecânicas e térmicas de PA11, TPU e PEAD, por meio de análises térmicas, espectroscópicas e de tração antes e após o envelhecimento por UV e névoa salina, a fim de simular um mecanismo de degradação semelhante ao da vida real das mangueiras termoplásticas e correlacionar o comportamento termomecânico dos três materiais após o envelhecimento. Os materiais utilizados para a fabricação das amostras deste estudo foram obtidos a partir de mangueiras não utilizadas, extrudadas com PA11, TPU e PEAD comerciais. As capas virgens foram submetidas as análises por infravermelho (FTIR), termogravimetria (TGA), termogravimetria derivativa (DTGA), calorimetria exploratória diferencial (DSC) e ensaio de tração, para obtenção das propriedades iniciais dos materiais. Em seguida, foram realizados os testes de envelhecimento, que foram desenvolvidos em quatro ciclos. O primeiro ciclo foi o envelhecimento por UV por 720h das amostras inicialmente na condição virgem (1° ciclo: UV), o segundo ciclo foi o envelhecimento por névoa salina por 720h das amostras envelhecidas do primeiro ciclo (2° ciclo: UV+NS), o terceiro ciclo foi o envelhecimento por névoa salina por 720h das amostras inicialmente na condição virgem (3° ciclo: NS) e o quarto ciclo foi o envelhecimento UV por 720h das amostras envelhecidas do terceiro ciclo (4° ciclo: NS+UV). Após o término de cada ciclo de envelhecimento, as amostras de PA11, TPU e PEAD foram submetidas à mesma análise das amostras virgens para fins comparativos. No FTIR todos os materiais apresentaram redução na intensidade dos picos característicos do material, associado a quebra de ligações das cadeias. No PEAD ocorreu o aumento do índice de carbonila e no TPU o surgimento de novo grupo funcional (estiramento C=C em alcenos), associados à oxidação da cadeia polimérica, cisão da cadeia e possível reticulação. Os testes térmicos mostraram um aumento na temperatura de degradação e pequena alteração na temperatura de fusão do PA11 associado à extração de plastificante; no PEAD e TPU ocorreu a diminuição da estabilidade térmica dos materiais após os envelhecimentos e não foram identificadas alterações na temperatura de fusão. Nos ensaios de tração foi verificado no PA11 e PEAD uma diminuição do módulo de elasticidade após os envelhecimentos, atribuída ao processo de cisão das cadeias poliméricas e consequente diminuição da massa molar e no TPU foi observado uma tendência ao aumento da tensão na deformação de 300% nas amostras envelhecidas por UV+NS, NS e NS+UV e uma tendência ao aumento da tensão de ruptura nas amostras envelhecidas por NS+UV, associado a uma concorrência entre a cisão de cadeias e reticulação. A partir dos resultados encontrados nesse estudo, pode-se concluir que o material menos afetado com os ciclos de envelhecimento em sua estrutura química e termicamente foi o PA11. Em relação ao comportamento mecânico, o TPU sofreu menos influência em suas propriedades comparado aos demais materiais. / [en] Thermoplastic hoses, one of the most important functional components of umbilicals, are composed of inner liner, synthetic fibre reinforcement and outer sheath manufactured from thermoplastic material with protection against ozone and ultraviolet (UV) radiation. Polyamide 11 (PA11) and thermoplastic polyurethane (TPU) are generally specified for the sheaths, but other materials that meet the function can be used, as high density polyethylene (HDPE). Regardless of the polymer selected for the sheath manufacturing, they need to guarantee the hose lower layers integrity in an offshore environment due to constant sun exposure and to the maritime environment. The amount of works that studied and correlated the effects of the overlap of UV radiation and saline environment on PA11, TPU and HDPE materials is not large. So, the objective of this work was to compare the mechanical and thermal properties of PA11, TPU and HDPE, by thermal, spectroscopic, and tensile analysis before and after UV and salt spray aging, in order to reproduce a degradation mechanism similar to real life of the thermoplastic hoses and relate the thermomechanical behavior of the three materials after aging to evaluate the material which best suits the use of the sheath. The materials used to manufacture the samples in this study were obtained from unused hoses, extruded with commercial PA11, TPU and HDPE. The virgin sheaths were submitted to infrared (FTIR), thermogravimetric (TGA), derivative thermogravimetric (DTGA), differential scanning calorimetry (DSC) analysis and tensile test, to obtain the initial properties of the materials. Then the aging tests were carried out, which were developed in four cycles. The first cycle was UV aging for 720h of samples initially in the virgin condition (1st cycle: UV), the second cycle was salt spray aging for 720h of aged samples from the first cycle (2nd cycle: UV+NS), the third cycle was salt spray aging for 720h of samples initially in the virgin condition (3rd cycle: NS) and the fourth cycle was UV aging for 720h of aged samples from the third cycle (4th cycle: NS+UV). After the end of each aging cycle, the PA11, TPU and HDPE samples were submitted to the same analysis as the virgin samples for comparative purposes. In FTIR, all materials had a reduction in the intensity of the material characteristic peaks, associated with breaking chain bonds. In HDPE, there was an increase in the carbonyl index and in TPU, the formation of a new functional group (C=C stretching in alkenes), associated with oxidation of the polymeric chain, chain scission and possible crosslinking. Thermal tests showed an increase in the degradation temperature and a small change in the melting temperature of PA11 associated with plasticizer extraction; in HDPE and TPU, there was a decrease in the thermal stability of the materials after aging and no changes in the melting temperature were identified. In the tensile tests, a decrease in the modulus of elasticity was observed in PA11 and HDPE after aging, attributed to the process of scission of the polymeric chains and consequent decrease in molar mass, and in TPU, a tendency to increase tension in deformation of 300% was observed in the samples aged by UV+NS, NS and NS+UV and a tendency to increase tensile strength in samples aged by NS+UV, associated with competition between chain scission and crosslinking. From the results found in this study, it can be concluded that the material least affected by aging cycles in its chemical structure and thermally was PA11. Regarding the mechanical behavior, TPU suffered less influence in its properties compared to other materials.

No description available.

A novel laser light-sensitive yarn based on a thermoplastic polyester–urethane (TPU) has been prepared and analyzed. Since the thermosensitive shape memory polymer yarn (SMP yarn) has been functionalized using nanoscale heat sources exhibiting light-induced heat generation, the yarn is capable of an optically triggered shape memory effect (SME). For this purpose gold nanorods (GNR) have been employed. In addition to the incorporation of GNR into the yarn, a coating of GNR on the yarn is also proposed, applied by a semi-continuous layer-by-layer (LBL) technique. The SME of the functionalized yarns can be triggered either thermally or optically and has a strain recovery of almost 100%. The light-induced SME is triggered by a low-powered laser (808 nm, 2 W for a GNR-incorporated and 1W for a GNRcoated TPU yarn). A reference yarn without GNR showed no significant effect. An adaptive structure featuring a SMPyarn backed shape memory effect has been proposed and demonstrated.

<p>Multifunctional additive manufacturing has the immense potential of addressing present needs within structural health monitoring by enabling a new additive manufacturing paradigm that redefines what a sensor is, or what sensors should resemble. To achieve this, the properties of printed components must be precisely tailored to meet structure specific and application specific requirements. However due to the limited number of commercially available multifunctional filaments, this research investigates the in-house creation of adaptable piezoresistive multifunctional filaments and their potential within structural health monitoring applications based upon their characterized piezoresistive responses. To do so, a rigid polylactic acid based-filament and a flexible thermoplastic polyurethane based-filament were modified to impart piezoresistive properties using carbon nanofibers. The filaments were produced using different mixing techniques, nanoparticle concentrations, and optimally selected manufacturing parameters from a design of experiments approach. The resulting filaments exhibited consistent resistivity values which were found to be less variable under specific mixing techniques than commercially available multifunctional filaments. This improved consistency was found to be a key factor which held back currently available piezoresistive filaments from fulfilling needs within structural health monitoring. To demonstrate the ability to meet these needs, the piezoresistive responses of three dog-bone shaped sensor sizes were measured under monotonic and cyclic loading conditions for the optimally manufactured filaments. The characterized piezoresistive responses demonstrated high strain sensitivities under both tensile and compressive loads. These piezoresistive sensors demonstrated the greatest sensitivity in tension, where all three sensor sizes exhibited gauge factors over 30. Cyclic loading supported these results and further demonstrated the accuracy and reliability of the printed sensors within SHM applications.</p>