Orientador: Marcos Valério Ribeiro / Resumo: Apesar de ser amplamente utilizado em componentes aeroespaciais, o Inconel 718 apresenta algumas características que dificultam a sua usinagem: dureza elevada, resistência em altas temperaturas, forte afinidade para reagir com materiais de ferramentas e baixa condutividade térmica. Além do mais, esta liga possui tendência para a formação da aresta postiça de corte, endurecimento por deformação, assim como efeito abrasivo de carbonetos e fases intermetálicas, que resultam em tensões mecânicas e térmicas elevadas na aresta de corte. A qualidade de acabamento exigido pela indústria, para este material, é de 1,6 µm de rugosidade média (Ra) e 6 µm de rugosidade total (Rt). Sabendo da importância do Inconel 718, assim como da necessidade de conciliar os desafios de usinagem com a qualidade exigida, o objetivo deste trabalho foi encontrar a condição experimental que resulte em melhores resultados de usinagem. Para encontrar a condição ótima, a liga foi usinada utilizando duas ferramentas: experimental de cerâmica – Al2O3 + MgO (perfil S) e comercial de metal duro revestido (perfil C). Com a metodologia de Taguchi foram planejadas duas matrizes experimentais. Para a ferramenta cerâmica, a usinagem ocorreu a seco e nas seguintes condições: avanços de 0,10–0,20–0,30 mm/rev; velocidades de corte de 300–400–500 m/min; profundidades de usinagem de 0,20–0,35–0,50 mm. A ferramenta de metal duro revestido foi utilizada em profundidade fixa de 0,5 mm, nas seguintes condições experimentais: av... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Despite being widely used in aerospace components, the Inconel 718 presents some characteristics that make difficult its machining: high hardness, resistance at high temperatures, strong affinity to react with tools materials and low thermal conductivity. Moreover, this alloy has a tendency to form the built up edge, hardening by deformation, as well as the abrasive effect of carbides and intermetallic phases, which result in high mechanical and thermal tensions in the cutting edge. The surface finishing quality required by the industry, for this material, is 1.6 μm of average roughness (Ra) and 6 μm of total roughness (Rt). Knowing the importance of Inconel 718, as well as the need to combine the machining challenges with the required quality, the objective of this work was to find the experimental condition that results in better machining results. To find the optimal condition, the alloy was machined using two tools: experimental ceramic – Al2O3 + MgO (profile S) and commercial coated tungsten carbide (profile C). With Taguchi methodology, two experimental matrices were planned. For the ceramic tool, the machining occurred in the dry and under the following conditions: feed rates of 0.10–0.20–0.30 mm/rev; cutting speeds of 300–400–500 m/min; machining depths of 0.20–0.35–0.50 mm. The coated carbide tool was employed at a fixed machining depth of 0.5 mm, under the following experimental conditions: feed rates of 0.10–0.15–0.20–0.25 mm/rev; cutting speeds of 55–70–85–100 m/m... (Complete abstract click electronic access below) / Doutor

In this Master Thesis work, the effect of pressure on sintering of cemented carbides is investigated. Special focus hasbeen given to the residual porosity after sintering. It is well known that sintering shrinkage depends on binder phasecontent, grain size, temperature and pressure. Thus 4 different cemented carbides grades were selected. The gradeswere pressed into standard products and TRS (Tensile Rupture Strength) rods with two different shrinkage factors.These were then sintered at different pressures and temperatures. Thereafter the impact of pressure on propertiessuch as Density, Coercivity, Porosity and TRS were analyzed. The observations were further supported with Weibullprobability analysis and fracture surface analysis in SEM.It has been shown that there exists a distinct threshold pressure at which significant reduction in porosity occurs forgiven compacted densities. For 3 out of 4 cemented carbide grades it has been observed that P2 sintering pressure issufficient to meet desired product characteristics. The fourth grade required a minimum sintering pressure of P4 toachieve desired quality criteria. Moreover it has been concluded that an increased sintering pressure increasesmaterial strength, as compared to vacuum sintering, thereby reducing the amount of early failures caused by poresduring TRS test.                                    Keywords: Cemented Carbides, Pressurized Sintering, Tungsten carbide, Porosity, Vacuum sintering, TensileRupture Strength, Weibull analysis, Fracture surface analysis.

Inhalative Partikel können gesundheitsschädigende Wirkungen im Respirationstrakt ausüben. Für Hartmetallstäube aus Wolframcarbidcobaltpartikeln wurden in epidemiologischen Studien Zusammenhänge mit dem Auftreten einer chronisch fibrotischen Lungenerkrankung aufgezeigt, der Hard Metal Lung Disease (HMLD). Zur Aufklärung ihrer Pathogenese wurden die biologischen Effekte mikroskaliger Wolframcarbidpartikel erforscht. Seit einigen Jahren werden zunehmend Pulver zur Herstellung von Hartmetall verwendet, deren Partikel Durchmesser im Nanometerbereich aufweisen. In der vorliegenden Arbeit wurden daher in vitro die Effekte nanoskaliger Wolframcarbidpartikel an humanen Zellen untersucht. Dabei wurden Partikelsuspensionen mit unterschiedlichen Partikelgrößen und –zusammensetzungen verglichen. Beurteilt wurden die Aufnahme der Partikel in die Zellen, ihre toxikologische Wirkung und inflammatorische Mediatoren, die die exponierten Zellen als Reaktion auf die Partikel sezernierten. In Bezug zur Exposition durch Inhalation wurden eine Lungenepithelzelllinie, eine Monozytenzelllinie und primäre mononukleäre Zellen aus dem Blut untersucht. Es zeigte sich, dass die beobachteten Effekte sowohl partikelspezifisch als auch zelltypspezifisch variierten. Dabei wurden die Partikel in alle Zelltypen aufgenommen mit den stärksten Internalisierungsraten in humanen primären Monozyten. Die Wolframcarbidcobalt-Partikel wirkten im Allgemeinen am stärksten vitalitätsmindernd. Alle Partikelarten bewirkten in primären Monozyten eine stark erhöhte Produktion von Zytokinen und Chemokinen. Untersuchungen zum Mechanismus der Partikeleffekte wiesen auf die Beteiligung reaktiver Sauerstoffspezies hin. Es konnten in der vorliegenden Arbeit bestehende Erkenntnisse zur Toxizität von Wolframcarbidcobaltpartikeln bestätigt werden und Hinweise auf die Beeinflussung biologischer Effekte durch verschiedene Partikelgrößen und Oberflächeneigenschaften von Nanopartikeln gefunden werden.

We performed atomistic modeling to study magnetic, mechanical, and thermal properties of materials. We executed molecular statics and dynamics simulations for this study, using density functional theory (DFT) and semi-empirical methods, such as embedded atom method (EAM) and modified embedded atom method (MEAM) potentials. In our first study, we showed that when Al atoms are substituted in barium hexaferrite, the total magnetization monotonically decreases due to the fact that Al atoms preferentially occupy the majorly contributing magnetic sites. The second study was to explore the diffusion mechanism of Ba atoms in hematite in order to study new techniques to build spherical nano-magnetic-particles. In the third study, we showed tungsten carbide growth is inhibited in the presence of vanadium carbide. In the fourth study, we showed how the mechanical and thermal properties of iron changes with vanadium doping with a newly developed MEAM interatomic potential. The physical properties of calcium were calculated in the next study, by the development of a MEAM potential which can be used for multiscale modeling. In the sixth study, the melting temperature of nanoparticles was analyzed and shown to decrease with a decrease of its size, confirming that the bulk properties of the material significantly change in its nano counterpart. Finally a portion of this research was dedicated for the simulation of sintering mechanisms of tungsten nanoparticles at different temperatures and pressures. While the first three studies were based on DFT, the last four studies focused on understanding physical phenomena using EAM/MEAMpotentials.

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Ces travaux de thèse s'inscrivent dans le contexte des efforts de recherches menés pour proposer des matériaux susceptibles de lever les verrous technologiques au développement des piles à combustible à membrane. L'un de ces enjeux est l'augmentation de la température de fonctionnement (150 - 250 °C) afin d'améliorer les cinétiques réactionnelles permettant une diminution de la quantité de catalyseur ainsi qu'une simplification de la gestion de l'eau, une réduction du système de refroidissement et une meilleure résistance à l'empoisonnement au monoxyde de carbone du platine. La motivation de cette étude a été de substituer au carbone un matériau support de catalyseur avec une plus grande résistance électrochimique.Notre choix s'est porté sur le carbure de tungstène qui, en plus d'une conductivité électronique élevée, présente une activité catalytique pour l'oxydation de l'hydrogène et la réduction de l'oxygène en milieu acide. La mise au point d'une méthode de synthèse innovante par voie hydrothermale a permis l'élaboration de microsphères de carbure de tungstène (MCT) de surface spécifique élevée (68 m2.g-1 avec 4 % de carbone résiduel) et d'architecture inusuelle. Des nanoparticules de platine de taille contrôlée ont été préparées par méthode polyol afin d'être déposées en surface des MCT. Après caractérisations électrochimiques ex-situ couplées à des analyses de surface (XPS) de ces catalyseurs Pt/WC, la mise en forme d'électrodes par enduction et transfert sur la membrane a permis la réalisation d'assemblages membrane - électrode et leurs caractérisations en pile à combustible. Des membranes polybenzimidazole dopé acide phosphorique (PBI-H3PO4) ont été utilisées pour remplacer les membranes Nafion afin d'augmenter la température de fonctionnement. / The objective of this work was to develop alternative suitable materials to increase operating temperature of a Proton Exchange Membrane Fuel Cell. The increase of the operating temperature (150 - 250 °C) is attractive for cost reduction and reliability in terms of reaction kinetics, catalyst tolerance, heat rejection and water management. Our work was focused on tungsten carbide which has an high electrical conductivity and exhibits a significant catalytic activity for hydrogen oxidation and oxygen reduction in acidic environment. We have reported a novel approach to produce tungsten carbide microspheres (TCM) with an high surface area (68 m2.g-1 including only 4 % of residual carbon) and an unusual architecture. Platinum nanoparticles were prepared by polyol method and were then deposited on TCM. Physical, chemical as well as electrochemical characterisations of WC supported platinum nanoparticles Pt/WC are described and discussed in comparison with a platinum electrocatalyst on a commercial carbon support (Vulcan XC-72R). Membrane Electrode Assembly was then prepared by coating - decal process, and characterised by single cell test and compared to conventional Pt/C assembly. Phosphoric acid doped polybenzimidazole PBI(H3PO4) was used as electrolyte to replace Nafion membrane in order to carry out fuel cell testing at higher temperature.

L’objectif de ce travail est de concevoir un outil d’atomisation adapté à la production de poudres de carburede tungstène dans l’entreprise Technogenia, située à Saint-Jorioz (74). Plus généralement, nous avons étudiéune nouvelle conception d’atomiseur rotatif pour lequel les surfaces d’atomisation sont orientées selon un angled’incidence non nul. Une telle orientation permet alors d’exploiter de façon plus efficace la fréquence de rotationde l’atomiseur ainsi que les forces de centrifugation et de Coriolis. A partir de cette base de réflexion, troisgéométries de surface d’atomisation ont été étudiées : des surfaces lisses, des surfaces pourvues de structurationsde long de leur bord de fuite et des surfaces matricées de perforations.Les différents modes de déstabilisation des écoulements liquides ont été observés grâce à l’acquisition de vidéosultra-rapides des différentes étapes de l’impact d’une goutte unique sur les différentes géométries de surfacesd’atomisation étudiées. Les processus d’atomisation peuvent ainsi varier entre la rupture de jets liquides régulierscausée par des instabilités de type Rayleigh-Plateau et la rupture de nappes liquides causée par des instabilitésde type Rayleigh-Taylor et/ou l’initiation de perforations au coeur des nappes et films liquides. Les vidéos dessprays aqueux ainsi que l’observation au microscope des poudres métalliques nous permettent de caractériser lessprays produits. Sur l’ensemble de nos expériences nous observons que la finesse de l’atomisation s’améliore àmesure que la fréquence de rotation augmente ; ce qui constitue l’objectif prioritaire du procédé développé dans lathèse. Cependant, les surfaces texturées, certes compatibles avec les liquides classiques (aqueux ou organiques),ne le sont plus avec les contraintes induites par du métal à haute température de fusion, tel le carbure detungstène fondu objet de la thèse. En conséquence, seules les surfaces lisses sont aujourd’hui retenues et fontl’objet de développements dans le cadre de la production de poudres métalliques au sein de Technogenia. / The aim of this work is to design a spray tool for the production of tungsten carbide powder for the companyTechnogenia, located in Saint-Jorioz (74). Thus, we have studied a new design of rotary atomizer based onatomization surface oriented at a non-zero incidence angle. Such an orientation can then allow to use moreeffectively the rotation frequency of the atomizer and the centrifugal and Coriolis forces. From this base reflection,three geometries of atomization surface were studied : smooth surfaces, surfaces with serrated structurationsalong their trailing edge and multi-perforated surfaces.The different destabilization modes of liquid flows were observed through high-speed videos of the different stagesof the single drop impact on each atomization surfaces. The atomization process can thus vary between liquid jetbreakup caused by Rayleigh-Plateau instabilities and liquid sheet breakup caused by Rayleigh-Taylor instabilitiesand/or initiating of holes in liquid films or sheets. Videos of aqueous sprays and microscopic observation of metalpowders allow us to characterize sprays. On all of our experiments, we observe that the atomisation gets better(producing finer spray), as the frequency of rotation increases. Although the textured surfaces are compatiblewith usual liquids (aqueous or organical), they can’t stand the constraints imposed by metal with a high meltingtemperature such as tungsten carbide, the object of this thesis. Therefore, only the smooth surfaces are nowthe subject of an industrial development to produce metallic powder with Technogenia company.

Este trabalho apresenta o estudo da usinabilidade do carbeto de tungstênio utilizando ferramenta de ponta única de diamante em máquina-ferramenta de ultraprecisão, em função de suas características de dureza e potencial uso para a fabricação de micromoldes. O carbeto de tungstênio foi submetido a testes de usinagem para a determinação dos parâmetros e condições de corte para a obtenção do regime dúctil. Com base nos resultados experimentais, concluiu-se que, para os avanços da ordem de 1 micrômetro/revolução, a profundidade de corte (AP) não influencia significativamente no resultado de rugosidade, e para avanços da ordem de 3 micrômetros, observou-se a formação de trincas na superfície usinada. Além disso, para profundidades de corte maiores que 2 micrômetros as ferramentas começaram a apresentar lascamento. Para avanços da ordem de 3 micrômetro/revolução a profundidade de corte influencia com grande significância no resultado de rugosidade. O torneamento do carbeto de tungstênio usando ferramenta de diamante mostrou-se uma opção viável à produção de superfícies em termos de qualidade óptica, porém, devido à alta dureza deste material (aproximadamente 4000HV) o torneamento mostrou ser um processo com condições limitadas para a produção em série de componentes em função da baixa taxa de remoção de material permitida. É possível que a retificação possa apresentar taxas de remoção maiores, mesmo assim garantindo a qualidade superficial atingida pelo torneamento, ou ainda, a retificação possa ser usada como um processo no desbaste do carbeto de tungstênio seguido do torneamento de ultraprecisão como a opção viável a produção em série de peças. Portanto, para obtenção de uma superfície de carbeto de tungstênio sem danos e com acabamentos da ordem de 10 nm, a profundidade e avanço não devem ser superiores a 2,00 \'mü\'micrômetros e 1,00 \'mü\'micrômetro/revolução, respectivamente, usando uma ferramenta de diamante nova com ângulo de saída 0 ou - 25 graus e uma máquina-ferramenta de alta precisão. / The single point diamond turning of the Tungsten Carbide is presented. The motivation for this study is the material´s high hardness and potential application for micromolds. A Tungsten Carbide sample was subjected to tests for determination of cutting parameters to achieve the ductile regime of material removal. Based on experimental results it was concluded that for the feedrate of the order of 1 \'mü\'m/revolution, the depth of cut did not affect significantly the surface roughness and for federates of the order of 3 \'mü\'m/revolution, the dept of cut influenced results of roughness greatly. Moreover chipping of the cutting edge occurs for depths of cut of 2 \'mü\'m. The diamond machining of tungsten carbide tool using diamond proved to be a viable option for the production of surfaces in terms of optical quality, but due to the high hardness of this material (approximately 4000HV) showed to be limited for the production of components due to the low material removal rate. It is possible that the precision griding may provide higher material removal rates along with the acceptable surface quality. Therefore, to obtain a damage free surface in tungsten carbide with surface finishe in the order of 10 nm, cutting depth and feedrate should be smaller than 2,00 \'mü\'m and 1,00 \'mü\'m/revolution, respectively, using a new diamond tool with rake angle of 0 or - 25 degrees and precision high stiffness machine tool.

Este trabalho apresenta o estudo da usinabilidade do carbeto de tungstênio utilizando ferramenta de ponta única de diamante em máquina-ferramenta de ultraprecisão, em função de suas características de dureza e potencial uso para a fabricação de micromoldes. O carbeto de tungstênio foi submetido a testes de usinagem para a determinação dos parâmetros e condições de corte para a obtenção do regime dúctil. Com base nos resultados experimentais, concluiu-se que, para os avanços da ordem de 1 micrômetro/revolução, a profundidade de corte (AP) não influencia significativamente no resultado de rugosidade, e para avanços da ordem de 3 micrômetros, observou-se a formação de trincas na superfície usinada. Além disso, para profundidades de corte maiores que 2 micrômetros as ferramentas começaram a apresentar lascamento. Para avanços da ordem de 3 micrômetro/revolução a profundidade de corte influencia com grande significância no resultado de rugosidade. O torneamento do carbeto de tungstênio usando ferramenta de diamante mostrou-se uma opção viável à produção de superfícies em termos de qualidade óptica, porém, devido à alta dureza deste material (aproximadamente 4000HV) o torneamento mostrou ser um processo com condições limitadas para a produção em série de componentes em função da baixa taxa de remoção de material permitida. É possível que a retificação possa apresentar taxas de remoção maiores, mesmo assim garantindo a qualidade superficial atingida pelo torneamento, ou ainda, a retificação possa ser usada como um processo no desbaste do carbeto de tungstênio seguido do torneamento de ultraprecisão como a opção viável a produção em série de peças. Portanto, para obtenção de uma superfície de carbeto de tungstênio sem danos e com acabamentos da ordem de 10 nm, a profundidade e avanço não devem ser superiores a 2,00 \'mü\'micrômetros e 1,00 \'mü\'micrômetro/revolução, respectivamente, usando uma ferramenta de diamante nova com ângulo de saída 0 ou - 25 graus e uma máquina-ferramenta de alta precisão. / The single point diamond turning of the Tungsten Carbide is presented. The motivation for this study is the material´s high hardness and potential application for micromolds. A Tungsten Carbide sample was subjected to tests for determination of cutting parameters to achieve the ductile regime of material removal. Based on experimental results it was concluded that for the feedrate of the order of 1 \'mü\'m/revolution, the depth of cut did not affect significantly the surface roughness and for federates of the order of 3 \'mü\'m/revolution, the dept of cut influenced results of roughness greatly. Moreover chipping of the cutting edge occurs for depths of cut of 2 \'mü\'m. The diamond machining of tungsten carbide tool using diamond proved to be a viable option for the production of surfaces in terms of optical quality, but due to the high hardness of this material (approximately 4000HV) showed to be limited for the production of components due to the low material removal rate. It is possible that the precision griding may provide higher material removal rates along with the acceptable surface quality. Therefore, to obtain a damage free surface in tungsten carbide with surface finishe in the order of 10 nm, cutting depth and feedrate should be smaller than 2,00 \'mü\'m and 1,00 \'mü\'m/revolution, respectively, using a new diamond tool with rake angle of 0 or - 25 degrees and precision high stiffness machine tool.

The purpose of this study was to evaluate four different measuring methods as potentialquality control tests for Tungsten Carbide (WC) raw material used in the hard metalmanufacturing at Seco Tools Fagersta. This was warranted as the current quality testcalled the HcK test, is very time consuming and the results provided that are used formilling time calculations cannot be relied on. The four measuring methods chosen wasLaser diffraction, X-Ray diffraction, Brunauer Emmett Teller analysis and Fisher Sub-Sieve Sizer measurement. These measuring techniques were chosen by Seco ToolsThe project followed the general structure of the project cycle modified to fit the projectand involving the steps project planning, present state analysis, goals and requirementdetermination, evaluation elimination of options and final of choice of option. Thealternative methods were evaluated using an evaluation matrix containing therequirements determined to be the most relevant for the quality control process. Therequirements were measurement precision, operator influence, ease of use, time requiredand operator time required. The ability of the measurement method to distinguishbetween all of the different WC powders used a Seco Tools was put as a must requirementas the new method is meant to serve as a verification test as well as a quality test.The analysis methods were evaluated practically through experiments and therefore atesting strategy was established. Initial test on two powder types was performed so thatan early evaluation could be done. During this stage both the Laser diffraction and the XRaydiffraction were eliminated due to poor results. The BET analysis and the Fisher Sub-Sieve Sizer performed better and was therefore tested further. Randomized testing wasthe method chosen when testing with all powders to minimize the environmental impacton the testing as this could affect the results of the study.The testing showed that only the Fisher SSS was able to distinguish between all thedifferent powders making it the only viable option as a new quality test. This was onlypossible when measuring on agglomerated material and the values extracted couldtherefore not be used further in the production. The Fisher SSS also performed the bestwhen ranked against the rest of the requirements, showing a high precision whenmeasuring on deagglomerated material and a combination of the two tests was thereforeconsidered.When compared to the HcK test the Fisher SSS showed a significant reduction in lead timebut also a reduction in information gathered and eventual defects controlled. The FisherSSS provides only an average particle size measurement and since no correlation has yetbeen established between the measured particle size and the required milling times it wasrecommended that the HcK test remains.It was recommended that a study is started aimed at establishing a correlation betweenthe measured particle size and the required milling time is started to investigate if this ispossible.