Les procédés de fabrication additive permettent, à partir d'un fichier de CAO, la fabrication de pièces complexes sans outillage, dans des délais de développement très courts et avec une grande flexibilité. Parmi les procédés de fabrication additive employés avec les polymères, le frittage laser de poudre est le plus utilisé. Ces travaux de thèse sont consacrés à l'étude et la compréhension des mécanismes fondamentaux impliqués lors du procédé de frittage laser de poudres de polyamide 12. Au cours du procédé de frittage laser de nombreux paramètres interviennent. Ainsi l'énergie fournie à la poudre par l'intermédiaire du rayon laser dépend de la puissance de celui-ci, de la vitesse de balayage et de l'espacement entre deux balayages successifs. De plus, le matériau subit un cycle thermique sévère : avant d'être frittée, la poudre est préchauffée. Puis, dans le bac de fabrication, la poudre non frittée ainsi que les pièces séjournent pendant toute la durée de la fabrication à des températures élevées. Cette histoire thermique entraîne un vieillissement et donc une modification des propriétés de la poudre ce qui complique sa réutilisation. L'influence de ces différents paramètres sur la microstructure et les propriétés mécaniques des pièces finales a été mise en évidence. De plus l'utilisation de différentes poudres de polyamide 12 a permis l'identification des paramètres-clés de la matière.Le frittage laser des polymères semi-cristallins est régi par plusieurs mécanismes fondamentaux : la fusion des particules de poudre, l'interdiffusion des chaînes macromoléculaires aux interfaces, la coalescence des particules fondues, la densification et enfin la cristallisation. L'étude et la modélisation de la cristallisation ont été effectuées pour l'un des polyamides 12 employés au cours de cette thèse. De ce traitement théorique ont pu être déduits les temps de maintien du polymère à l'état fondu au cours du procédé. Dans une seconde phase, des analyses rhéologiques menées dans le cadre de la viscoélasticité linéaires des polymères à l'état fondu ont permis de déduire les temps d'interdiffusion des chaînes macromoléculaires. Par ailleurs, le processus de coalescence des particules de poudres à l'état fondu a été suivi expérimentalement et modélisé pour différentes températures. Ces temps ont été confrontés à la durée de maintien du polymère à l'état fondu, confirmant ainsi la bonne consolidation obtenue lors du frittage du polyamide 12. En conclusion, ce travail contribue à la compréhension des différents mécanismes physico-chimiques intervenant au cours du frittage laser : il permet d'expliciter de façon assez approfondie les relations entre les propriétés des poudres, les paramètres du procédé et les propriétés finales des pièces. De nombreuses préconisations relatives à l'optimisation des propriétés des poudres pourront être déduites de ce travail et aideront au développement de nouveaux matériaux adaptés à ce procédé.

Members of the elderly population is disproportionately prone to experiencing mobility impairment due to their aging bodies and as a result have frail bodies that are at a higher risk of grave injury due to falling. In order to combat this assistive mobility devices such as exoskeletons have been developed to help patients enhance their range of motion. With additive manufacturing techniques, such as fused deposition modeling (FDM), becoming a more mainstream form of design, the inclusion of lightweight polymers such as nylon 12 as primary construction materials for these devices has increased. In this thesis computer aided design (CAD) software was used to design a prototype lower body exoskeleton and simulation software was used to give the device the characteristics of Stratasys' nylon 12 carbon fiber FDM material to verify it if could be used as the primary construction material for this device when extruded from a FDM printer on either the XZ or ZX printing plane. From the simulations it was found that the material printed along the XZ plane could create a device that could withstand the weight of an average elderly male patient (200 lbs.) as well as the 35 lbs. of force applied to the device by a linear actuation motor that would be used to extend and contract the exoskeleton leg.

No description available.

Objectives. Polyamide-12 (PA) is a flexible material suited for denture bases and clasping. This study investigated its potential aging effects with a focus on surface roughness, color stability, and elasticity. Methods. PA specimens (Valplast) of 40 × 10 × 2mm and equally measuring PMMA specimens (Palapress) as control were fabricated. Color changes after storage in air, water, coffee, and red wine (n = 10) were measured using the CIE L*a*b color specification. Elasticity after thermocycling (1000, 3000, and 7000 cycles, n = 15) was measured by three-point bending testing. Mean surface roughness (Ra) was determined after storage in the liquids mentioned above and thermocycling (n = 10). Results. Tukey’s HSD test (P < 0.05) revealed statistically significant color changes of PA in red wine (ΔE = 4.27 after 12 days, EΔE = 6.90 after 12 days) and coffee (ΔE = 3.93 after 36 days) but no color changes in PMMA. Elastic modulus of PA was 845MPa and not affected by thermocycling (Tukey’s HSD test, P > 0.81). Dry specimens showed significantly decreased elasticity (P < 0.001). Mean surface roughness (PA 0.20 μm, PMMA 0.28 μm) did not change significantly after thermocycling or storage (Mann-Whitney U-test, 0.16 < P < 0.65). Significance. PA exhibited a higher susceptibility to discoloration than PMMA. Neither surface roughness nor elasticity of PA was altered by artificial aging.

La miniaturisation des pièces est une étape importante pour la progression de la microtechnologie dans plusieurs domaines (connectique, médical, optique, microsystèmes mécaniques). Pour cela, le moulage par microinjection, semble être la solution clé pour la production à grande échelle de micro-composants de polymères. Pour les polymères semi-cristallins, la cristallisation, sous fort taux de cisaillement et sous des vitesses de refroidissement élevées (about 100 K/s), induit des morphologies et des propriétés spécifiques. Elle prend donc une importance considérable dans le processus de microinjection par rapport au moulage par injection classique où les épaisseurs injectées sont généralement supérieures à 1 mm. Ces microstructures ont une grande influence sur les propriétés mécaniques du produit final. La prédiction de ces propriétés à partir de la description de la microstructure est un défi technique et scientifique. Durant cette thèse, deux polymères semi-cristallins ont été microinjectés, le polyéthylène haute densité et le polyamide 12. Les analyses obtenues par la microscopie otiques montrent que les morphologies cristallines varient entre les micro- et les macro-pièces. Tandis que la morphologie de 'peau-cœur' est présente dans les macropièces, les micropièces présentent une morphologie plutôt particulière. Les analyses combinées de diffusion et de diffraction des rayons X (SAXS et WAXS) avec un microfaisceau synchrotron, nous ont permis de déterminer la microstructure induite par le processus de microinjection dans toute l'épaisseur des pièces. Nous avons constaté que la morphologie et les orientations cristallines induites sont très dépendantes des conditions d'injection ou de microinjection. Une diminution de l'épaisseur, de la vitesse et de la température du moule, augmente l'orientation cristalline en limitant la relaxation des chaînes de polymères.

Additive manufacturing has increased in popularity in recent years partly due to the possibilities of producing complex geometries in a rapid manner. Selective laser sintering (SLS) is a type of additive manufacturing technique that utilizes polymer powder and a layer-by-layer technique to build up the desired geometry. The main drawbacks with this technique are related to the reproducibility, mechanical performance and the poor surface finish of printed parts. Surface roughness increase the risk of bacterial adhesion and biofilm formation, which is unbeneficial for parts to be used in the healthcare industry. This thesis investigated the possibility in reducing the surface roughness of SLS printed polyamide 12 with the fully automated post-processing technology PostPro3D. The postprocessing relies on chemical post-processing for smoothening of the parts’ surface. PostPro3D utilizes vaporized solvent which condenses on the printed parts causing the surface to reflow. By this roughness, in terms of unmolten particles, is dissolved and surface pores are sealed. The influence of alternating post-processing parameters; pressure, temperature, time and solvent volume was evaluated with a Design of Experiments (DoE). The roughness reduction was quantified with monitoring the arithmetic mean average roughness (Ra), the ten-point height roughness (Rz) and the average waviness (Wa) using a stylus profilometer and confocal laser scanning microscope (CLSM). The effect of post-processing on mechanical properties was evaluated with tensile testing and the effect on microstructure by scanning electron microscopy (SEM). A comparison was made between post-processed samples and a non-postprocessed reference, as well as between samples post-processed with different degree of aggressivity, with regards to the roughness values, mechanical properties and the microstructure. Results indicated that solvent volume and time had the largest effect in reducing the roughness parameters Ra and Rz, while time had the largest influence in increasing the elongation at break, tensile strength at break and toughness. The post-processing’s effect on waviness and Young’s modulus was less evident. SEM established that complete dissolution of powder particles was not achieved for the tested parameter ranges, but a clear improvement of the surface was observed for all different post-processing conditions, as compared to a non-post-processed specimen. The reduction in roughness by increased solvent volume and time was thought to be due to increased condensation of solvent droplets on the SLS-parts. The increase in mechanical properties was likely related to elimination of crack initiation points at the surface. In general, the mechanical properties experienced a wide spread in the results, this was concluded to be related to differences in intrinsic properties of the printed parts, and highlighted the problems with reproducibility related to the SLS. An optimal roughness of Ra less than 1 µm was not obtained for the tested post-processing conditions, and further parameter optimization is required. / Möjligheten att tillverka komplexa geometrier på ett snabbt sätt, har fått additiv tillverkning att öka i popularitet. Selective laser sintering (SLS) är en typ av additiv tillverkning där polymer pulver sintras samman succesivt lager för lager. Dessa lager bygger tillsammans upp den önskade geometrin. De största nackdelarna med SLS är att de tillverkade delarna har bristande mekaniska egenskaper, har brister i reproducerbarheten samt att ytan har en dålig kvalitet, den är ojämn. Ytojämnheten ökar risken för att bakterier fastnar och ett en biofilm bildas. Då produkten ska användas inom sjukvården, är det viktigt att biofilm bildning undviks. Den här uppsatsen har undersökt möjligheterna att reducera ytojämnheten av SLS-printad polyamid 12 med hjälp av kemisk efterbehandling i PostPro3D. Denna maskin är helt automatisk och åstadkommer ytbehandling genom att förånga lösningsmedel som sedan kondenserar på det SLS-printade materialet. Ytan på materialet löses upp vilket minskar ytojämnheter i form av pulver partiklar samt sluter porer på ytan. Genom att ändra på parametrarna för efterbehandlingen kan graden av aggressivitet påverkas, detta gäller tryck, temperatur, tid och lösningsmedels volym. De optimala parametrarna för att åstadkomma en jämn yta utvärderades med en Design of Experiments (DoE). Reducering av ytojämnhet mättes med hjälp av aritmetisk genomsnittlig ojämnhet (Ra), tio-punkts höjd ojämnhet (Rz) och medel-vågighet (Wa), med nålprofilometer och konfokal mikroskop. Efterbehandlingens påverkan på de mekaniska egenskaperna utvärderades i ett dragprov, medan mikrostrukturen undersöktes med svepelektronmikroskop (SEM). Ytjämnheten, de mekaniska egenskaperna och mikrostrukturen jämfördes mellan icke behandlade prover och ytbehandlade prover, med varierad grad av aggressivitet. Resultaten indikerade att tid och volym hade störst effekt på Ra och Rz, medan tid hade störst positiv inverkan på töjning, styrka och seghet. Effekten på styvheten (E-modulen) och vågigheten (Wa) var mindre uppenbar, och någon tydlig påverkan kunde inte observeras. SEM-analys visade att fullständig upplösning av partiklar på ytan inte sker för de testade behandlingarna, men en tydlig förbättring kunde ses vid jämförelse av ett obehandlat prov och ett behandlat prov. Den ökade ytjämnheten för längre tid och högre volym tros bero på en ökad kondensering av lösningsmedel på ytan under efterbehandlingen. Ökningen i mekaniska egenskaperna är troligtvis relaterade till eliminering av kritiska defekter på ytan. Generellt visade de mekaniska egenskaper en stor spridning i resultaten, detta tros bero på inneboende egenskaper i provstavarna. Denna slutsats understryker den bristande reproducerbarheten för SLS-printning. En optimal ytjämnhet antas vara ett Ra värde under 1 µm, denna ytjämnhet har inte uppnåtts med de testade efterbehandlingsparameter värdena, därför krävs ytterligare parameter optimering för att nå optimal efterbehandling.

[pt] Nos últimos anos surgiram algumas alternativas para as tubulações de aço carbono que são a grande maioria no transporte de petróleo e gás, com grande destaque para os materiais poliméricos, principalmente por apresentarem baixa densidade em relação aos metais, boa resistência à corrosão e boa processabilidade. Além disso, os polímeros apresentam maior facilidade de manutenção e instalação, tornando-os economicamente viáveis. No entanto, esses materiais podem sofrer degradação quando expostos a produtos químicos e ao calor. O objetivo desse trabalho e avaliar a variação das propriedades mecânicas das poliamidas 12 e dos polietilenos de alta densidade quando envelhecidos em água durante 6 meses a temperatura ambiente e a 70 graus Celsius, tendo em vista que a temperatura de serviço desses materiais varia entre 70 a 80 graus Celsius. Para a caracterização do material foram realizados, ensaio mecânicos de tração, impacto de excitação por impulso sonoro, como a caracterização por microscopia eletrônica. Os resultados das caracterizações das amostras após envelhecimento foram comparados com os resultados obtidos dos materiais originais, de forma a percebermos que todas as amostras sofreram variações em suas propriedades mecânicas. A temperatura ambiente as amostras de PEAD sofreram um aumento em sua rigidez, aumentando sua resiliência, reduzindo sua resistência ao impacto, reduzindo também a tensão de escoamento e reduzindo seu amortecimento. Já para as amostras de PEAD envelhecidas a 70 graus Celsius houve uma redução na sua rigidez e tensão de escoamento, no entanto houve um aumento em sua resistência ao impacto e na resiliência do material. Para as poliamidas 12 envelhecidas a temperatura ambiente houve uma significativa redução na sua rigidez, na sua tensão de escoamento e tensão máxima, houve um aumento na resiliência do material coerente com um aumento da resistência ao impacto e um aumento no amolecimento. A 70 graus Celsius a poliamida 12 mostrou uma redução na sua rigidez, tensão de escoamento e tensão máxima, houve um aumento na resiliência e na resistência ao impacto, seguido de uma redução no amolecimento. Em todas as situações de envelhecimento as PEAD sofreram uma degradação na cor do material, o que não ficou tão visível para as poliamidas 12 principalmente para o envelhecimento a temperatura ambiente. Sendo assim o comportamento mecânico dos polímeros foi influenciado pela temperatura, sempre acarretando variações em suas propriedades mecânicas e dependendo da situação podendo ser mais ou menos relevante. / [en] In recent years, some alternatives have emerged for carbon steel pipelines, which are the majority in the transport of oil and gas, with a great prominence for polymeric materials, mainly due to their low metal density, good corrosion resistance and good processability. In addition, the polymers present greater ease of maintenance and installation, making them economically viable. However, such materials may be degraded when exposed to chemicals and heat. The objective of this work is to evaluate the variation of the mechanical properties of polyamides 12 and high density polyethylenes when aged in water for 6 months at ambient temperature and at 70 degrees Celsius, considering that the service temperature of these materials ranges from 70 to 80 degrees Celsius. For the characterization of the material, mechanical tests of traction, impact and excitation by sonorous impulse were carried out, such as the characterization by electron microscopy. The results of the characterization of the samples after aging were compared with the results obtained from the original materials, in order to realize that all the samples suffered variations in their mechanical properties. At ambient temperature samples of HDPE increased their stiffness, increasing their resilience, reducing their impact resistance, also reducing the yield stress and reducing their damping. However, for HDPE samples aged 70 degrees Celsius, there was a reduction in their stiffness and yield stress, however, there was an increase in their impact strength and material resilience. For polyamides 12 aged at ambient temperature there was a significant reduction in stiffness, flow stress and maximum stress, there was an increase in the resilience of the material consistent with an increase in impact strength and an increase in softening. At 70 degrees Celsius polyamide 12 showed a reduction in stiffness, yield stress and maximum stress, there was an increase in resilience and impact strength, followed by a reduction in softening. In all aging situations the HDPE suffered a degradation in the color of the material, which was not so visible for the polyamides 12 mainly for aging at ambient temperature. Thus, the mechanical behavior of the polymers was influenced by temperature, always leading to variations in their mechanical properties and depending on the situation, being more or less relevant.

This work studied the rheological and mechanical properties of polyamide 12 modified montmorillonite clays and bentonita (the organo-modified commercial montmorillonite and a bentonite modified by various routes. Two polyamides 12 were used for the polyamide matrix, a virgin and another reprocessed. The polyamide 12 reprocessed was derived from tailings lines of fluid transport in automotive vehicles. Ten different compositions were prepared in single-screw extruder, and subsequently molded test specimens by injection. For formulations reprocessed polyamide 12, were added 5 to 7 wt.% of a commercial organo-modified montmorillonite ( I44P ) and the virgin polyamide 12 , 3 and 5 wt.%. For virgin polyamide matrix, also formulations were studied with 3 and 5% by weight of bentonite treated with Agent Titanate. The nanocomposite structure formation was evaluated by X-ray diffraction. For all developed formulations, mechanical and rheological tests, and their results were correlated performed: polyamide matrices, the content and the treatments of the clays. Clay dispersion and morphology of the fracture surface were analyzed by SEM. The analysis results showed distinct mechanical and rheological behaviors depending on the type of matrix, the degree of dispersion of clay, content and type of treatment of clays. There was formation of nanocomposites for polyamide 12 modified with I44P clay and composites for polyamide 12 modified bentonite. The rheological properties confirm the increase of the elastic properties of the nanocomposites due to the restriction to macromolecular mobility. The addition of organophilic commercial montmorillonite (I44P) promoted the increased stiffness of the nanocomposites without significant loss of toughness. / Este trabalho estudou as propriedades reológicas e mecânicas de poliamida 12 modificadas com montmorilonitas, sendo uma montmorilonita organofilica comercial (I44P) e montmorilonita sódica (bentonita) modificada por diversas rotas. Para a matriz de poliamida, foram utilizadas duas poliamidas 12, sendo uma virgem e a outra reprocessada oriunda de rejeito de linhas de transporte de fluídos em veículos automotores. Foram preparadas dez composições diferentes em extrusora monorrosca e, posteriormente, moldados corpos de prova por injeção. Para as formulações de poliamida 12 reprocessada, foram adicionados 5 e 7% em massa de montmorilonita organofílica comercial e para a poliamida 12 virgem, 3 e 5%. Para esta mesma matriz de poliamida virgem, também foram estudadas formulações com 3 e 5% em massa das bentonitas tratadas com agente titanato. A formação de estrutura de nanocompósitos foi avaliada por difração de raios-X. Para todas as formulações desenvolvidas, foram realizados ensaios mecânicos e reológicos, e seus resultados correlacionados com: as matrizes de poliamida, o teor e os tratamentos das argilas. A dispersão da argila e a morfologia da superfície de fratura foram avaliadas por MEV. Os resultados das análises mostraram comportamentos mecânicos e reológicos distintos em função do tipo de matriz, grau de dispersão das argilas, o teor e o tipo de tratamento das argilas. Houve formação de nanocompósitos para poliamida 12 modificada com a argila I44P e de compósitos para poliamida 12 modificada com bentonitas. As propriedades reológicas confirmam o aumento das propriedades elásticas dos nanocompósitos devido à restrição a mobilidade macromolecular. A adição da montmorilonita organofilica comercial (I44P) promoveu o aumento da rigidez dos nanocompósitos sem perdas significativas da tenacidade.

Objectives. Polyamide-12 (PA) is a flexible material suited for denture bases and clasping. This study investigated its potential aging effects with a focus on surface roughness, color stability, and elasticity. Methods. PA specimens (Valplast) of 40 × 10 × 2mm and equally measuring PMMA specimens (Palapress) as control were fabricated. Color changes after storage in air, water, coffee, and red wine (n = 10) were measured using the CIE L*a*b color specification. Elasticity after thermocycling (1000, 3000, and 7000 cycles, n = 15) was measured by three-point bending testing. Mean surface roughness (Ra) was determined after storage in the liquids mentioned above and thermocycling (n = 10). Results. Tukey’s HSD test (P < 0.05) revealed statistically significant color changes of PA in red wine (ΔE = 4.27 after 12 days, EΔE = 6.90 after 12 days) and coffee (ΔE = 3.93 after 36 days) but no color changes in PMMA. Elastic modulus of PA was 845MPa and not affected by thermocycling (Tukey’s HSD test, P > 0.81). Dry specimens showed significantly decreased elasticity (P < 0.001). Mean surface roughness (PA 0.20 μm, PMMA 0.28 μm) did not change significantly after thermocycling or storage (Mann-Whitney U-test, 0.16 < P < 0.65). Significance. PA exhibited a higher susceptibility to discoloration than PMMA. Neither surface roughness nor elasticity of PA was altered by artificial aging.

The work deals with structrural and morphological characterization of polyamide buckles used to fasten webbins. The buckles were produced in five different years, a few of those produced in 2000 and 2004 were broken. The aime is to determine the type of polyamide and the cause of fracture of the buckles during using. The buckles were characterized in terms of structure and composition by Fourier-transform infrared spectroscopy in a mode of attenuated total reflaction, differential scanning calorimetry, thermogravimetry and X-ray diffraction. The buckles were made of polyamide 12. The broken buckles showed higher melting point, lower thermal stability and, in addition to modification it also contains modification, which is more fragile and probably represents the cause of fracture.