Grâce à leurs excellentes propriétés de dureté et de résistance à l’usure, les carbures cémentés sont les meilleurs candidats pour la réalisation d’outillage de coupe. Elaborés par la métallurgie des poudres, ils sont majoritairement composés de carbure de tungstène, choisis pour ses propriétés de dureté et d’un liant métallique à haute ductilité, le plus souvent le cobalt. Néanmoins, l’utilisation du cobalt comme liant est remis en question depuis quelques années par la commission européenne REACH à cause de sa toxicité. En conséquence, des liants alternatifs tels que les alliages de Fe et Ni sont étudiés. Malgré les différents travaux menés, il subsiste un manque de compréhension fondamental sur l’effet spécifique du liant sur le frittage et le grossissement de grains des carbures cémentés. Le but de cette étude est la compréhension de l’effet de la composition du liant sur le frittage et le grossissement de grains. Dans cet objectif, différent liants WC-20vol%M (M=Fe, Ni or Co) et différent taux de carbone sont considérés. Le frittage et le grossissement de grains seront étudiés à l’aide de caractérisations macroscopiques et microstructurales, puis les résultats discutés en comparaison avec la littérature. Comme il a été déjà observé dans le cas d’alliages WC-Co, le retrait au cours du frittage survient plus tôt dans le cas d’alliages riches en W qu’en C, quelque soit le liant considéré. Concernant l’effet de la nature du liant, le frittage en phase solide est décalé vers les hautes températures pour WC-Fe en comparaison avec WC-Co et WC-Ni. Dans cette étude le retrait est directement corrélé avec la capacité d’étalement du liant dans la porosité, comme le confirme l’analyse de la microstructure. Quant au grossissement de grain, il est inhibé pour un faible ratio C/W, quelque soit la nature du liant. Néanmoins, pour un ratio C/W élevé, celui-ci augmente, ainsi que la tendance au grossissement anormal, en particulier dans le cas du liant nickel. Les mécanismes de grossissement de grains sont discutés en lien avec les observations structurales des interfaces. / Thanks to their exceptional hardness and wear resistance, cemented carbides are the best candidates to make efficient cutting and drilling tools by the powder metallurgy route. Known as a very hard ceramic material, tungsten carbide is used as the major component of cemented carbides. A ductile metal binder is added as the matrix, which in most cases is cobalt. Nevertheless the use of cobalt as a binder is questioned by the new European regulation on chemicals (REACH). Therefore, new alternative binders are considered, especially Fe and Ni-alloys. Although a few studies exist for Fe-based and Ni-based WC cemented carbides, there is still a lack of fundamental understanding of the specific effect of the binder on sintering and grain growth. This work discusses the effect of binder composition on sintering and grain growth of cemented carbides. For this purpose, different binder compositions WC-20vol%M (M= Fe, Ni or Co) and different C/W ratio are considered. Sintering and grain growth behaviors are investigated using several macroscopic and microstructural characterizations, and results are discussed and compared to the literature. As already observed in previous works on WC-Co, shrinkage occurs earlier for W-rich than for C-rich alloys for the three binders. Regarding the influence of the binder nature, solid state sintering is delayed to higher temperature for WC-Fe in comparison to WC-Co and WC-Ni alloys. Shrinkage is directly related to the spreading efficiency of the binder into the porosity, as confirm by the microstructure analysis. Grain growth is inhibited for low C/W ratio whatever the binder nature. Nevertheless, for a high C/W ratio, grain growth is enhanced and the abnormal character of grain growth increases, especially in the case of a Ni binder. Grain growth mechanisms are discussed in relation with the observed structure of phase boundaries.

O metal duro é um material compósito utilizado em diversas áreas de usinagem, mineração e construção civil, podendo ser aplicado diretamente em componentes de equipamentos de perfuração de petróleo e gás. O presente trabalho teve como objetivo principal a aplicação da técnica de moagem de alta energia visando produzir o compósito WC-Ni e estudar os efeitos do tempo de moagem nas propriedades do material. A moagem do metal duro WC-20Ni, partindo dos pós de WC e Ni, foi realizada para tempos de moagem de 1, 2, 4, 8, 16, 32 e 64 horas. Os pós de partida foram caracterizados por granulometria à laser, MEV e EDS. Nas amostras sinterizadas foi realizada análise microestrutural por microscopia ótica, medição de microdureza e medida de densidade pelo método de Arquimedes. Os melhores resultados para o compósito WC-20%Ni, foram conseguidos para o tempo de 8 horas de moagem, onde a densificação e dureza alcançaram após a sinterização 97,09% e 1058 ± 54 HV respectivamente. Tempos de moagem maiores que 8 horas foram prejudiciais nas propriedades do material. / The hard metal is a composite material used in several areas of machining, mining and construction, it can be applied directly in components of the drilling equipment for oil and gas. This work had as main objective the application of high energy milling technique to produce the composite WC-Ni and studying the effects of time milling in the material properties. The milling of hard metal WC-20Ni, from the WC and Ni powders, was performed for milling times of 1, 2, 4, 8, 16, 32 and 64 hours. The starting powders were characterized by laser granulometry, SEM and EDS. Microstrutural analysis of the sintered samples was performed by optical microscopy, microhardness and density by Archimedes. The best results for the composite WC-20%Ni, was achieved for 8 hours milling, where the density and hardness reached after sintering 97.09% and 1058 ± 54 HV respectively. Longer times of milling, after 8 hours milling, provided a detrimental effect on the properties of the material.

O metal duro é um material compósito utilizado em diversas áreas de usinagem, mineração e construção civil, podendo ser aplicado diretamente em componentes de equipamentos de perfuração de petróleo e gás. O presente trabalho teve como objetivo principal a aplicação da técnica de moagem de alta energia visando produzir o compósito WC-Ni e estudar os efeitos do tempo de moagem nas propriedades do material. A moagem do metal duro WC-20Ni, partindo dos pós de WC e Ni, foi realizada para tempos de moagem de 1, 2, 4, 8, 16, 32 e 64 horas. Os pós de partida foram caracterizados por granulometria à laser, MEV e EDS. Nas amostras sinterizadas foi realizada análise microestrutural por microscopia ótica, medição de microdureza e medida de densidade pelo método de Arquimedes. Os melhores resultados para o compósito WC-20%Ni, foram conseguidos para o tempo de 8 horas de moagem, onde a densificação e dureza alcançaram após a sinterização 97,09% e 1058 ± 54 HV respectivamente. Tempos de moagem maiores que 8 horas foram prejudiciais nas propriedades do material. / The hard metal is a composite material used in several areas of machining, mining and construction, it can be applied directly in components of the drilling equipment for oil and gas. This work had as main objective the application of high energy milling technique to produce the composite WC-Ni and studying the effects of time milling in the material properties. The milling of hard metal WC-20Ni, from the WC and Ni powders, was performed for milling times of 1, 2, 4, 8, 16, 32 and 64 hours. The starting powders were characterized by laser granulometry, SEM and EDS. Microstrutural analysis of the sintered samples was performed by optical microscopy, microhardness and density by Archimedes. The best results for the composite WC-20%Ni, was achieved for 8 hours milling, where the density and hardness reached after sintering 97.09% and 1058 ± 54 HV respectively. Longer times of milling, after 8 hours milling, provided a detrimental effect on the properties of the material.

O metal duro é um material compósito utilizado em diversas áreas de usinagem, mineração e construção civil, podendo ser aplicado diretamente em componentes de equipamentos de perfuração de petróleo e gás. O presente trabalho teve como objetivo principal a aplicação da técnica de moagem de alta energia visando produzir o compósito WC-Ni e estudar os efeitos do tempo de moagem nas propriedades do material. A moagem do metal duro WC-20Ni, partindo dos pós de WC e Ni, foi realizada para tempos de moagem de 1, 2, 4, 8, 16, 32 e 64 horas. Os pós de partida foram caracterizados por granulometria à laser, MEV e EDS. Nas amostras sinterizadas foi realizada análise microestrutural por microscopia ótica, medição de microdureza e medida de densidade pelo método de Arquimedes. Os melhores resultados para o compósito WC-20%Ni, foram conseguidos para o tempo de 8 horas de moagem, onde a densificação e dureza alcançaram após a sinterização 97,09% e 1058 ± 54 HV respectivamente. Tempos de moagem maiores que 8 horas foram prejudiciais nas propriedades do material. / The hard metal is a composite material used in several areas of machining, mining and construction, it can be applied directly in components of the drilling equipment for oil and gas. This work had as main objective the application of high energy milling technique to produce the composite WC-Ni and studying the effects of time milling in the material properties. The milling of hard metal WC-20Ni, from the WC and Ni powders, was performed for milling times of 1, 2, 4, 8, 16, 32 and 64 hours. The starting powders were characterized by laser granulometry, SEM and EDS. Microstrutural analysis of the sintered samples was performed by optical microscopy, microhardness and density by Archimedes. The best results for the composite WC-20%Ni, was achieved for 8 hours milling, where the density and hardness reached after sintering 97.09% and 1058 ± 54 HV respectively. Longer times of milling, after 8 hours milling, provided a detrimental effect on the properties of the material.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-03-14T20:59:53Z No. of bitstreams: 1 GerlaneaSilvaDeOliveira_DISSERT.pdf: 3478391 bytes, checksum: 594895a6c6a847cb2a39bb6ce51e2b62 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-03-15T20:06:06Z (GMT) No. of bitstreams: 1 GerlaneaSilvaDeOliveira_DISSERT.pdf: 3478391 bytes, checksum: 594895a6c6a847cb2a39bb6ce51e2b62 (MD5) / Made available in DSpace on 2017-03-15T20:06:06Z (GMT). No. of bitstreams: 1 GerlaneaSilvaDeOliveira_DISSERT.pdf: 3478391 bytes, checksum: 594895a6c6a847cb2a39bb6ce51e2b62 (MD5) Previous issue date: 2016-07-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / O n?quel tem sido bastante utilizado, em estudos, como substituto do cobalto no metal duro - WC-Co, devido apresentar maior resist?ncia ? corros?o e ? oxida??o, al?m das propriedades mec?nicas e de aspectos econ?micos. Atualmente, carbetos e metais s?o adicionados ao metal duro, para aumentar a sinterabilidade do material, e, consequentemente, as suas propriedades de dureza e tenacidade. Neste trabalho, foram estudados os efeitos da varia??o percentual de Ni e dos par?metros de sinteriza??o (temperaturas de sinteriza??o e isotermas) nas propriedades do sinterizado WC-Ni. Os produtos sinterizados foram obtidos atrav?s das etapas de processamento da metalurgia do p?, no qual p?s de carbeto de tungst?nio ? WC com adi??o de 5 e 15%p. de N?quel ? Ni foram mo?dos em um moinho planet?rio de alta energia durante 8 horas. Em seguida, os p?s particulados foram compactados em uma prensa uniaxial sob carga de 300 Mpa numa matriz cil?ndrica de 5 mm de di?metro. A sinteriza??o dos compactados a verde foi realizada nas temperaturas de 1350 ?C e 1450?C, com isotermas de 30 e 90 minutos, no dilat?metro; e, na temperatura de 1350? C, com isotermas de 30 e 90 minutos, em forno ? v?cuo. Os p?s de partida (WC e Ni) e os mo?dos foram caracterizados por difra??o de raios ? X (DRX), microscopia eletr?nica de varredura (MEV) e espectroscopia de energia dispersiva (EDS); e as amostras sinterizadas foram caracterizadas por MEV, EDS e medidas de microdureza. Os valores de microdureza Vickers foram maiores para as amostras de WC-5%p.Ni sinterizadas a 1450?C, com isotermas de 30 e 90 minutos no dilat?metro (1078,6 HV e 1246,1 HV, respectivemente). No forno a v?cuo, o melhor resultado de microdureza, tamb?m, foi para as amostras WC-5%p.Ni sinterizadas a 1350?C com isoterma de 30 e 90 minutos (849,6 HV e 914,7 HV, respectivemente). As amostras de WC-5%p.Ni sinterizadas no forno a v?cuo a 1350?C com isotermas de 30 e 90 minutos mostraram maiores valores de microdureza comparados aos das amostras WC-5%pNi sinterizadas no dilat?metro a 1350?C com isoterma de 30 e 90 minutos. / Nickel has been widely used as a substitute for cobalt in WC-Co hardmetal studies due to greater corrosion and oxidation resistance as well as mechanical properties and economic aspect. Currently, carbides and metals are added to hard metal in order to increase the sinterability of the material, and consequently their hardness and toughness. In this study, the effects of different amount of Ni and sintering parameters (sintering temperatures and holding time) on properties of sintered WC-Ni were studied. The sintered products were obtained via powder metallurgy processing steps, in which powders of tungsten carbide (WC) with 5 and 15 wt% Nickel (Ni) were milled in a planetary high energy ball milling for 8 hours. Then, the particulate powders were compacted into a cylindrical die with 5 mm in diameter under a uniaxial load of 300 MPa. Sintering of the green samples was carried out at 1350 and 1450?C with holding time of 30 and 90 minutes, in resistance furnace and at 1350? C, with 30 and 90 minutes holding time in vacuum furnace. Starting (WC and Ni) and milled powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). Sintered samples were also characterized by SEM, EDS and microhardness measurements. Hardness results were higher for WC-5 wt% Ni sintered in the resistance furnace at 1450 ? C with 30 and 90 minutes holding time (1078.6 and 1246.1 Hv respectively). WC-5wt% Ni Samples sintered in vacuum furnace at 1350 ?C with 30 to 90 minutes holding time obtained a higher microhardness compared to ones sintered in the resistance furnace at 1350 ?C with holding time of 30 and 90 minutes.

The aim of this work was to systematically study how the microstructure evolution is affected by the carbon activity in WC-Ni cemented carbides. Seven WC-9.59at%Ni alloys with different carbon activity were sintered at 1500 °C. From investigating these alloys, the carbon window has been experimentally evaluated using light optical microscopy and compared to theoretical carbon window calculated using Thermo-Calc. The overall microstructure of cross sections and raw surfaces have been investigated using scanning electron microscopy. Finally, the WC grain size and distribution have been evaluated using electron backscatter diffraction. It was found that the experimental carbon window was slightly wider than the theoretical carbon window. The WC grain size increased and the grain size distribution got wider with increasing carbon activity. In addition, the largest WC grains showed the largest grain growth by increasing carbon activity. By comparing the present results of grain size and distribution of WC-Ni to previous results of WC-Co, it was found that the WC grain growth was more pronounced and more influenced by the carbon activity.