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Les assiettes de fibrage utilisées pour la production de fibres de verre subissent d’importantes contraintes mécaniques, chimiques et thermiques. Par conséquent, cette pièce se dégrade et doit être périodiquement remplacée. Le but de ces travaux est d’augmenter la durée de vie des assiettes de fibrage en améliorant les propriétés mécaniques et chimiques des superalliages qui les constituent. Plus précisément, l’objectif de cette thèse est, dans un premier temps, d’améliorer les alliages utilisés pour le fibrage à 1000°C, puis dans un second temps, de trouver un superalliage pouvant fibrer à 1125°C. Ces travaux ont été menés sur deux familles de superalliages : base nickel et base cobalt. Les propriétés chimiques ont été caractérisées par des essais thermogravimétriques et les propriétés mécaniques par des essais de fluage flexion 3 points. Pour l’alliage base Ni, l’influence des éléments minoritaires subis, Mn et Si, a été étudiée. Les propriétés mécaniques de cet alliage ont fait, ensuite, l’objet d’essais d’amélioration par l’addition de titane, zirconium, tantale, hafnium et de niobium. L’addition d’aluminium a été aussi expérimentée mais ayant pour but d’améliorer les propriétés chimiques de l’alliage. Enfin, des études ont été aussi menées sur l’addition de métaux nobles (Pd et Ru) et de terres rares (Y, La et Ce). Concernant les superalliages base cobalt, l’étude s’est portée sur un alliage base Co qui a antérieurement montré de bonnes propriétés générales pour une utilisation à 1125°C et non à 1000°C. Des variantes avec une teneur abaissée en tantale, sans hafnium et sans tungstène ont été étudiées. Pour clore ces travaux, l’augmentation de la teneur en nickel et un traitement thermique ont été étudiés afin d’améliorer la résistance à l’oxydation de ce second alliage / The fiberizing spinners used to produce the glass fibers undergo sizable mechanical, chemical and thermal solicitations. Therefore, this piece is degraded and must be periodically replaced. The purpose of these works is to increase the lifetime of the fiberizing spinners by improving the mechanical and chemical properties of the superalloys that constitute them. More precisely, the objective of this thesis is, in the first time, to improve the alloys used to fiberize at 1000°C, and in a second time, to find a superalloy that can fiberize at 1125°C. These works are focused on two families of superalloys: nickel-based and cobalt-based. The chemical properties are characterized by the thermogravimetry tests and the mechanical properties by 3 points flexural creep tests. For the Ni-based alloy, the influences of unwanted minority elements, Mn and Si, were studied. The mechanical properties of this alloy are subject to improvement tests by the addition titanium, zirconium, tantalum, hafnium and niobium. The aluminium addition was also experimented but with the aim of improving the chemical properties of the alloy. Finally, the studies were also driven on the addition of noble metals (Pd and Ru) and of rare earths (Y, La and Ce). Concerning the cobalt-based superalloys, the study focused on an alloy which has previously shown good general properties to be used at 1125°C and no at 1000°C. The versius with a lowered content in tantalum, without tungsten and without hafnium were studied. To close this work, the increase of nickel and a heat treatment were studied in order to improve the oxidation resistance of this second alloy

Made available in DSpace on 2014-06-11T19:28:20Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-03-05Bitstream added on 2014-06-13T19:57:38Z : No. of bitstreams: 1 araujojunior_ib_me_bauru.pdf: 1185170 bytes, checksum: e49c1ae91dff4591b5bc770366352cc9 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A indústria busca uma melhor otimização e performance de seus equipamentos, há muito notou-se a importância da contenção do desgaste para o aumento de vida útil dos componentes de máquinas. Em condições operacionais onde há o desgaste por abrasão, comumente faz-se o endurecimento da camada superficial ou a aplicação de uma liga mais nobre e de dureza mais elevada, visando conter este desgaste. A técnica também é chamada de revestimento. Entender melhor os parâmetros que influenciam nos resultados da aplicação destes revestimentos torna-se importante possibilitando menores perdas e uma maior economia, pois busca-se como alvo trabalhar com a melhor performance do revestimento. Objetivou-se neste trabalho o estudo das ligas a base de Cobalto que são aplicadas cada vez mais rotineiramente nas indústrias petroquímicas, onde os componentes e órgãos de máquinas estão expostos a condições severas de desgaste por abrasão e corrosão além da severidade dos trabalhos a altas temperaturas e pressão. Relacionando o desgaste, as ligas a base de Cobalto possuem uma posição destacada e a liga é conhecida comercialmente como “Stellite 6”. Em alguns trabalhos é chamada também de liga coringa por sua versatilidade e destaque em especial. Neste trabalho procurou-se variar as velocidades de resfriamento em cinco patamares, analisou-se a influência da diluição na micro-dureza e os efeitos da variação da velocidade de resfriamento no mecanismo de endurecimento. A aplicação do revestimento ocorreu em três camadas através do processo TIG. Verificamos ainda a interferência da diluição na dureza em cada camada de revestimento. A terceira e última camada foi a que apresentou maior dureza devido à menor diluição com o metal base principalmente no corpo de prova que possuía à menor velocidade de resfriamento devido ao tempo para a formação de precipitados e carbonetos na liga metálica. / The industry searchs a better optimization and performance of their equipment, long noted the importance of containment to increase the wear life of components of machines. In operating conditions where there is wear by abrasion, usually it is the hardening of the surface layer or the application of a more noble alloy and high hardness, wear it to contain. The technique also called hardfacing. Better understand the parameters that influence the results of applying these coatings becomes important because it enables lower losses and greater economy as it seeks to target work with the best performance of the coating. The objective of this research is complements the study of cobalt-based alloys that are applied more routinely in petrochemical industries, where the component units and machines are exposed to severe conditions of wear by abrasion and corrosion than the severity of the work at high temperatures and pressure. Relating the wear, the cobalt-based alloys have a prominent position and the league is known commercially as “Stellite 6”. Some work is also called the league wildcard for its versatility and highlight in particular. In this work we have tried to vary the speed of cooling in five steps, looked up the influence of dilution on micro hardness and the effects of variation in the rate of cooling in the hardening mechanism. The application of the coating occurred in three layers using the TIG process. We note also the interference of dilution in hardness in each layer of coating. The third and final layer was the one with higher hardness due to less dilution with the base metal mainly in the body of evidence that had the lowest rate of cooling due to the time for the formation of precipitates and carbides in the metal.

The diploma thesis deals with the topic of machinability of materials. The theoretical part describes the aspects according to which machinability can be evaluated. The material side of the thesis is focused on various types of difficult-to-machine materials. The cobalt alloy UmCo50 belongs to the group of difficult-to-machine materials and it is the subject of the experimental part. UmCo50 is an alloy for high temperature use. The primary aim of the thesis was to monitor the wear of the selected cutting tool when turning this alloy. Other aspects of the selected machining process were also monitored, such as force effects or the quality of the machined surface. Despite the fact that machinability of tested materials cannot be expressed in terms of the absolute value of a quantity, it is necessary to compare the various aspects of the machining processes by reference materials. However, certain conditions of this comparison must be met. Based on this, a comparison of tested and reference material was performed.

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Lack of crystalline order and microstructural features such as grain/grain-boundary in metallic glasses results in a suite of remarkable attributes including very high strength, close to theoretical elasticity, high corrosion and wear resistance, and soft magnetic properties. In particular, low coercivity and high permeability of iron and cobalt based metallic glass compositions could potentially lead to extensive commercial use as magnetic heads, transformer cores, circuits and magnetic shields. In the current study, few metallic glass compositions were synthesized by systematically varying the iron and cobalt content. Thermal analysis was done and included the measurement of glass transition temperature, crystallization temperature, and the enthalpies of relaxation and crystallization. Magnetic properties of the alloys were determined including saturation magnetization, coercivity, and Curie temperature. The coercivity was found to decrease and the saturation magnetization was found to increase with the increase in iron content. The trend in thermal stability, thermodynamic properties, and magnetic properties was explained by atomic interactions between the ferromagnetic metals and the metalloids atoms in the amorphous alloys. Mechanical behavior of iron based metallic glasses was evaluated in bulk form as well as in the form of coatings. Iron based amorphous powder was subjected to high power mechanical milling and the structural changes were evaluated as a function of time. Using iron-based amorphous powder precursor, a uniform composite coating was achieved through microwave processing. The hardness, modulus, and wear behavior of the alloys were evaluated using nano-indentation.

Os objetivos deste trabalho foram processar e caracterizar microestrutural e mecanicamente superligas à base de cobalto do sistema Co-Al-W-Ni-Cr-(Nb,Ta)- C-B com microestrutura ?/?\'. Visando possível aplicação em ferramenta para Soldagem por Atrito com Pino Não Consumível (SAPNC), em inglês Friction Stir Welding (FSW) nas composições: (Co-10Al-7,5W-30Ni-10Cr-3,0Nb-0,6C-0,06B %at. ) - 30Ni-3Nb, (Co-10Al-7,5W-40Ni-10Cr-3,0Nb-0,6C-0,06B %at.) - 40Ni-3Nb, (Co-10Al-7,5W-50Ni-10Cr-3,0Nb-0,6C-0,06B %at.) - 50Ni-3Nb além da liga patenteada (Co-10Al-7,5W-40Ni-10Cr-3,0Ta-0,6C-0,06B %at.) - 40Ni-3Ta considerada padrão para este projeto. A caraterização microestrutural foi feita por microscopia eletrônica de varredura (MEV), microscopia eletrônica de varredura por emissão de campo (MEV-FEG), medidas de microanálise semi-quantitativa e mapeamento químico por EDS, caracterização por difração de raios X, além do ensaio mecânico de dureza Vickers em todas as amostras. Os resultados da caracterização microestrutural e mecânica para a liga 40Ni-3Ta mostraram-se semelhantes aos encontrados na literatura enquanto que a composição 40Ni-3Nb foi a que apresentou resultados mais próximos em relação à liga padrão. / The objectives of this study were to process and characterize microstructural and mechanical cobalt-based superalloys from Co-Al-W-Ni-Cr-(Nb,Ta)-C-B system with ?/? \' microstructure. Aiming possible application for Friction Stir Welding (FSW) tool in the compositions: (Co-10Al-7.5W-30Ni-10Cr-3.0Nb-0.6C-0.06B %at.) - 30Ni-3Nb, (Co-10Al-7.5W-40Ni-10Cr-3.0Nb-0.6C-0.06B %at. ) - 40Ni-3Nb, (Co-10Al-7.5W-50Ni-10Cr-3.0Nb-0.6C-0.06B %at.) - 50Ni-3Nb, including the patented alloy (Co-10Al-7.5W -40Ni-10Cr-3.0Ta-0.6C-0.06B %at.) - 40Ni-3Ta considered the standard alloy for this project. The microstructural characterization was made by Scanning Electron Microscopy (SEM), Scanning Electron Microscopy with Field Emission Gun (SEM-FEG), semi-quantitative microanalysis measures and chemical mapping by EDS, characterization by X - ray diffraction and mechanical test of hardness Vickers in all the samples. The results of the microstructural and mechanical characterization for 40Ni-3Ta alloy were similar to those found in the literature. The 40Ni-3Nb alloy showed the closest results, among the other alloys studied in comparison with the standard alloy.

Os objetivos deste trabalho foram processar e caracterizar microestrutural e mecanicamente superligas à base de cobalto do sistema Co-Al-W-Ni-Cr-(Nb,Ta)- C-B com microestrutura ?/?\'. Visando possível aplicação em ferramenta para Soldagem por Atrito com Pino Não Consumível (SAPNC), em inglês Friction Stir Welding (FSW) nas composições: (Co-10Al-7,5W-30Ni-10Cr-3,0Nb-0,6C-0,06B %at. ) - 30Ni-3Nb, (Co-10Al-7,5W-40Ni-10Cr-3,0Nb-0,6C-0,06B %at.) - 40Ni-3Nb, (Co-10Al-7,5W-50Ni-10Cr-3,0Nb-0,6C-0,06B %at.) - 50Ni-3Nb além da liga patenteada (Co-10Al-7,5W-40Ni-10Cr-3,0Ta-0,6C-0,06B %at.) - 40Ni-3Ta considerada padrão para este projeto. A caraterização microestrutural foi feita por microscopia eletrônica de varredura (MEV), microscopia eletrônica de varredura por emissão de campo (MEV-FEG), medidas de microanálise semi-quantitativa e mapeamento químico por EDS, caracterização por difração de raios X, além do ensaio mecânico de dureza Vickers em todas as amostras. Os resultados da caracterização microestrutural e mecânica para a liga 40Ni-3Ta mostraram-se semelhantes aos encontrados na literatura enquanto que a composição 40Ni-3Nb foi a que apresentou resultados mais próximos em relação à liga padrão. / The objectives of this study were to process and characterize microstructural and mechanical cobalt-based superalloys from Co-Al-W-Ni-Cr-(Nb,Ta)-C-B system with ?/? \' microstructure. Aiming possible application for Friction Stir Welding (FSW) tool in the compositions: (Co-10Al-7.5W-30Ni-10Cr-3.0Nb-0.6C-0.06B %at.) - 30Ni-3Nb, (Co-10Al-7.5W-40Ni-10Cr-3.0Nb-0.6C-0.06B %at. ) - 40Ni-3Nb, (Co-10Al-7.5W-50Ni-10Cr-3.0Nb-0.6C-0.06B %at.) - 50Ni-3Nb, including the patented alloy (Co-10Al-7.5W -40Ni-10Cr-3.0Ta-0.6C-0.06B %at.) - 40Ni-3Ta considered the standard alloy for this project. The microstructural characterization was made by Scanning Electron Microscopy (SEM), Scanning Electron Microscopy with Field Emission Gun (SEM-FEG), semi-quantitative microanalysis measures and chemical mapping by EDS, characterization by X - ray diffraction and mechanical test of hardness Vickers in all the samples. The results of the microstructural and mechanical characterization for 40Ni-3Ta alloy were similar to those found in the literature. The 40Ni-3Nb alloy showed the closest results, among the other alloys studied in comparison with the standard alloy.

Les travaux de cette thèse sont centrés sur le développement de systèmes moléculaires en solution homogène pour la production photocatalytique de dihydrogène dans l'eau utilisant des catalyseurs de cobalt à ligands pentadentate tétrapyridinique ou tétra- et pentaaza macrocycliques. Associés au photosensibilisateur et à l’ascorbate comme donneur d’électron sacrificiel, les complexes à ligands macrocycliques présentent d’excellentes performances pour la production d’H2, bien supérieures à celles des complexes à ligands polypyridiniques en termes d’efficacité et de stabilité, en raison de la grande stabilité de leur état réduit «Co(I)». Enfin, [Ru(bpy)3]2+ a pu être substitué par un colorant organique très robuste du type triazatriangulénium conduisant à un système photocatalytique encore plus performant. Ces résultats démontrent que les colorants organiques sont une alternative viable aux photosensibilisateurs à base de métaux nobles, même en milieu aqueux acide. / The work of this manuscript is focused on the design of molecular systems in homogeneous solution for photocatalytic production of molecular hydrogen in water using cobalt catalysts with pentadentate tetrapyridinic and tetra- and pentaza macrocyclic ligands. In association with [Ru(bpy)3]2+ as photosensitizer and sodium ascorbate as sacrificial electron donor, the macrocycle based catalysts display high performances for H2 production, far exceeding those of the polypyridine based catalysts, both in terms of activity and stability, because of the stability of their reduced state «Co(I)». Finally, [Ru(bpy)3]2+ was successfully substituted with a robust organic dye belonging to the triazatriangulenium family, leading to an even more efficient photocatalytic system. These results demonstrate well that organic dyes are a truly efficient alternative to noble metal based photosensitizers, even in acidic aqueous medium.

Dans le domaine du forgeage à chaud de pièces aéronautiques, les matrices en acier sont couramment rechargées, sur quelques millimètres d’épaisseur, par un alliage base cobalt (Stellite 21) déposé par procédé de soudage à l’arc (MIG). Dans le cadre de ce travail de thèse, ce rechargement « classique» est comparé à des rechargements Stellite 21 et Stellite 6 déposés par deux procédés émergents dans ce domaine, le PTA et le LASER. L’objectif est d’apporter des éléments de compréhension aux mécanismes d’endommagement de surface, notamment par écoulement plastique, de ces différents rechargements afin de dégager des voies d’amélioration pour augmenter la durée de vie des matrices. Pour cela, des essais tribologiques (semi-industriels et laboratoire) ont été mis en œuvre pour créer des endommagements de surface comparables à ceux observés sur matrices industrielles. Associées à ces essais, des investigations microstructurales, structurales et mécaniques multi-échelles ont été réalisées (traction, flexion, microdureté, MO, MEB, MEB-STEM, DRX, EBSD). Selon les couples « nuance/procédé » de rechargement, des mécanismes de déformation plastique par glissement des dislocations parfaites et par transformation de phase CFC en HC ont été identifiés. L’activation de ce dernier a pu être reliée à la température de transformation allotropique CFC/HC du cobalt. Cette température dépend à la fois (i) des éléments d’addition, variant en fonction de la nuance déposée (Cr, C,...), (ii) de la dilution (variation de la teneur en Fe) liée aux paramètres de soudage et (iii) du nombre de couches déposées. De plus, une influence significative de la transformation de phase sur l’évolution du coefficient de frottement a été mise en évidence. En effet, dans le cas où la transformation de phase n’est pas observée, le coefficient de frottement est stable durant l'essai alors qu'une chute de la courbe de coefficient de frottement a été reliée avec la transformation de phase CFC en HC. Parallèlement, l'écoulement plastique des dendrites est observé en extrême surface sur quelques dizaines de micromètre d'épaisseur dans la direction de glissement. Cet écoulement est associé à une forte texturation morphologique et cristallographique de la phase identifiée (CFC ou HC), avec une orientation des plans de plus grande densité atomique parallèlement à la surface de glissement. Les résultats montrent également que sous sollicitations tribologiques, un important durcissement est observé en surface (jusqu'à 90%) et une corrélation a pu être établie entre l'augmentation de la microdureté et le taux de déformation plastique. / In the field of hot forging of aeronautical parts, the steel dies are commonly hardfaced, on few millimeters thick, by a cobalt-based alloy (Stellite 21) deposited by arc welding (MIG). As part of this thesis, this "classic" hardfacing is compared to Stellite 21 and Stellite 6 hardfacings deposited by two emerging processes in this area, the PTA and the LASER one. The objective is to assess surface damage mechanisms, especially induced by plastic strain, of these various hardfacings. Tribological tests (laboratory and semi-industrial) were used to create surface damage comparable to those observed in industrial dies. Associated with these tests, multiscale microstructural, structural and mechanical investigations have been performed (tensile, bending, microhardness, OM, SEM, STEM, XRD, EBSD). According to the « material/process » couple, plastic strain mechanisms by perfect dislocation glide and by FCC to HCP phase transformation have been identified. The activation of the latter has been connected to the temperature of the allotropic phase transformation (FCC/HCP) in cobalt. This temperature depends on (i) the alloying elements, varying according to the deposited grade (Cr, C, ...), (ii) the dilution (Fe content evolution) connected to the welding parameters and (iii) the number of deposited layer. Moreover, a significant influence of the phase transformation on the evolution of the friction coefficient has been evidenced. Indeed, if the phase transformation is not observed, the friction coefficient is stable during the test, while a drop of the friction coefficient curve is connected with the FCC to HCP phase transformation. Moreover, the plastic flow of dendrites is observed at the extreme surface, on a few tens of micrometres in thickness, in the direction of sliding. It is associated with a high morphologic and crystallographic texturing of the identified phase (FCC or HCP), with the highest atomic density planes mostly oriented parallel to the sliding surface. The results also show that, under tribological laodings, a significant hardening is observed on the surface (up to 90%) and a correlation has been established between the increase in the microhardness and the plastic deformation ratio.