No description available.

Fatigue and ductility properties in various tool steels, produced by powder metallurgy, spray forming or conventionally ingot casting, have been analysed experimentally and successfully compared to developed models. The models are able to predict the fatigue limit and cause for fatigue fracture, and strain- and stress-development until fracture during the ductile fracture process respectively. Total fracture in a tool steel component, both in fatigue and ductility testing, is caused by a propagating crack initiated by particles, i.e. carbides or non-metallic inclusions. The models are based on experimentally observed size distributions. The axial fatigue strength at two million cycles was determined for various tool steels. The fracture surface of each test bar broken was examined in SEM to determine the cause for fatigue failure, i.e. a single carbide or inclusion particle or a cluster of carbides, and the size of the particle. The particles act as stress concentrators where a crack is easily initiated when the material is subjected to alternating stresses. The developed models calculate the probability that at least one particle will be present in the material which is larger than the threshold level for crack initiation at a certain stress range. The ductility testing was performed on various tool steels by four-point bending under static load. The load and displacement until total fracture were recorded and the maximum strain and stress acting in the material were calculated. The fracture surface of each broken test bar was examined in SEM, though the crack initiating area appears different compared to a fatigue failure. Ductile fracture is caused by a crack emanating from voids nucleated around many particles in a joint process and then linked together. By finite element modelling of void initiation and propagation in 2D of an experimentally observed carbide microstructure for each tool steel, successful comparisons with experiments were performed. Carbides were modelled as cracked when larger than a certain size, based on fracture surface observations, and the matrix cracked above a pre-defined plastic deformation level. The stresses and strains at total failure were in good agreement between model and experiments when evaluated. The use of these developed models could be a powerful tool for optimisation of fatigue and ductility properties for tool steels. With good fatigue and ductility properties normal failures appearing during operation of a tool steel product could be minimised. By theoretical tests in the developed models of various carbide microstructures the optimum mechanical properties could be achieved with a minimum of experiments performed. / QC 20101119

No description available.

No description available.

L’acier Ferrium® M54® présente une composition chimique optimisée, basée sur 40 ans d’évolution et de développement des aciers à durcissement secondaire à précipitation de carbures M2C. Le compromis de propriétés Rm/KIC/KISCC obtenu par la nuance M54® permet d’envisager son utilisation dans les trains d’atterrissage d’avions gros porteurs. Cependant, les premiers essais mécaniques, réalisés par l’utilisateur pour la montée en maturité de la nuance, ont montré une variabilité des propriétés mécaniques suivant le traitement thermique appliqué. Ce travail de thèse s’applique donc à décrire les évolutions microstructurales au cours du traitement thermique de la nuance M54® et les impacts sur les propriétés mécaniques en se concentrant notamment sur le traitement par le froid. Les différentes conditions de mise en solution et de revenu testées ont montré une certaine stabilité de la précipitation au revenu et des propriétés mécaniques qui en découlent. La précipitation a été caractérisée à différentes échelles afin de la comparer avec celle issue des nuances de la même famille. En revanche, selon les conditions de traitement par le froid réalisées, la limite d’élasticité varie de manière significative sans qu’aucun des paramètres liés à la précipitation ne soient modifiés. Le taux d’austénite est en revanche un paramètre déterminant pour la limite d’élasticité et est très sensible aux conditions de traitement par le froid : temps et température entre la trempe à l’huile et le traitement cryogénique et température de traitement cryogénique. Un traitement thermique amélioré a ainsi été proposé pour obtenir un taux d’austénite réduit et constant et limiter ainsi les variations de limite d’élasticité. / Ferrium® M54® steel presents an optimized composition, based on 40 years of research and development on secondary hardening steels. This alloy exhibits an excellent Rm/KIC/KISCC balance that allows considering its use in landing gears applications of wide-body aircrafts in the future. However, initial mechanical tests performed by the end-user have shown variability in mechanical properties depending on the applied heat treatment. The main goal of this work is to describe the microstructural evolutions of the alloy M54® during heat treatment and their impact on the resulting mechanical properties with a specific focus on the effect of the cryogenic treatment.The different austenitizing and tempering conditions investigated have shown a stability of the tempering precipitation and mechanical properties. This precipitation has been characterized at different scales and compared with other grades of the same family. On the other hand, depending on cryogenic treatment conditions, a significant variation of the mechanical properties and in particular of the yield strength is observed without any modification in the precipitation distribution and volume fraction or size. Austenite content is critical for the yield strength and is very sensitive to the cryogenic treatment conditions: time and temperature before cryogenic treatment and temperature of cryogenic treatment. An improved heat treatment to obtain reduced and constant austenite content is proposed.

Este trabalho teve como objetivo investigar eletrocatalisadores de baixo custo à base de carbeto de tungstênio, carbono e ferro submetidos a diferentes processos de nitretação quanto à atividade catalítica para reação de redução do oxigênio (RRO) nos eletrólitos ácido e alcalino. Os catalisadores foram divididos em três séries distintas, a primeira compreendendo aqueles onde houve variação da carga de carbeto de tungstênio em relação ao suporte de carbono, que foram impregnados com o complexo Fe2+(2,4,6-Tris(2-piridil)-1,3,5-Triazina)2, [Fe(TPTZ)2]2+ e tratados em duas temperaturas diferentes, 700 e 800 oC em atmosfera de nitrogênio. Na segunda série foi mantida constante a carga de carbeto de tungstênio (30% de W/C, m/m) sendo que esta mescla foi preparada usando carbonos dopados previamente com três fontes distintas de nitrogênio (HNO3, NH3 e HNO3/NH3); isto foi seguido pela incorporação do complexo Fe[TPTZ]2+ e pelos mesmos tratamentos térmicos acima mencionados. Na terceira série, os eletrocatalisadores foram preparados com três tipos de carbonos (Vulcan, Ketjenblack e Monarch), aos quais foi incorporado o complexo Fe[TPTZ]2+, seguido pelo tratamento térmico a 800 °C em atmosfera de nitrogênio e então por dopagem com amônia a 950 °C. As três séries de eletrocatalisadores sintetizados neste trabalho foram cuidadosamente caracterizadas por espectroscopia infra-vermelho e UV-Visível, difratometria de raio-x, microscopia eletrônica de transmissão, energia dispersiva de raios-x, espectroscipia Raman, espectroscopia fotoeletrônica de raios-x. As investigações eletroquímicas foram realizadas por voltametria cíclica (VC) e pelo levantamento de curvas de polarização de estado estacionário para a RRO, usando a técnica de eletrodo de disco/anel rotatório, com materiais catalíticos formando filmes finos depositados no eletrodo de disco. Nas três séries de catalisadores foram desenvolvidos materiais com bom desempenho para a RRO. Nos estudos da primeira série de catalisadores, notou-se que o material mais ativo foi aquele formado por WC-FeNx/C com 30 % de W/C e 5% de Fe pirolisado a 800 °C. Na segunda série foi observado que os desempenhos dos catalisadores variaram de acordo com o tipo de protocolo de nitretação, presença de ferro e temperatura de tratamento térmico. Em eletrólito alcalino, os eletrocatalisadores apresentaram maiores desempenhos, que resultaram bastante próximos em relação ao do catalisador de Pt dispersa em carbono usado como referência. Na terceira série de eletrocatalisadores investigados, verificou-se que o melhor desempenho obtido foi com o catalisador com carbono Monarch com amônia, cuja atividade catalítica resultou superior à dos demais, devido ao maior número de estruturas ativas FeNx e N/C formadas pelo tratamento com amônia. Os resultados nos meios ácido e alcalino para a primeira e segunda séries de eletrocatalisadores sugerem a ocorrência de um mecanismo indireto (2e- + 2e-), ou seja, em meio ácido (alcalino) primeiro o O2 reduz para H2O2 (HO2 ) e depois de H2O2 (HO2 ) para H2O. Os sítios predominantemente envolvidos na catálise da reação são WC e FeNx em meio ácido e WC e N/C em meio alcalino. Finalmente, para a terceira série de eletrocatalisadores o mecanismo reacional em meio ácido envolve um mecanismo direto de 4e-, com participação importante dos sítios ativos de Fe-N2. / This work aims to investigate low cost electrocatalysts based on tungsten carbide, carbon and iron submitted to different nitriding processes for the catalytic activity for the oxygen reduction reaction (ORR) in acid and alkaline electrolytes. The catalysts were divided into three distinct series, the first one comprising those with different tungsten carbide loads with respect to the carbon support, which were impregnated with the Fe2+ (2,4,6-Tris (2-pyridyl) - 1,3,5-triazine)2, [Fe (TPTZ)]2+, complex and treated at two different temperatures, 700 and 800 oC in nitrogen atmosphere. In the second series, the tungsten carbide load (30% W/C, m/m) was kept constant but this mixture was prepared using previously doped carbons using three different sources of nitrogen (HNO3, NH3 and HNO3/NH3); this was followed by the incorporation of the Fe[TPTZ]2+ complex and by the same heat treatments as mentioned above. In the third series, the electrocatalysts were prepared with three carbon types (Vulcan, Ketjenblack and Monarch), to which the Fe[TPTZ]2+ complex was added, followed by heat treatment at 800 °C under nitrogen and then by nitriding using a flow of ammonia at 950 °C. The three series of electrocatalysts synthesized in this work were carefully characterized by infra-red and UV-Visible spectroscopy, x-ray diffraction, transmission electron microscopy, x-ray energy dispersive, Raman spectroscopy, x-ray photoelectron spectroscopy. The electrochemical investigations were performed by cyclic voltammetry (CV) and by measurements of steady-state polarization curves for ORR using rotating ring-disc electrode technique, with catalytic materials forming thin films deposited on the disc. In the three catalyst series, materials with good performance for the ORR were developed. In the studies of the first series of catalysts, it was seen that the most active material was that formed by WC-FeNx/C with 30%W/C and 5% Fe pyrolyzed at 800 ° C. In the second series it was observed that the performances of the catalysts varied according to the type of nitriding protocol, presence of iron and temperature of heat treatment. The electrocatalysts showed higher performances in alkaline electrolyte, which were very close to that of a reference Pt/C catalyst. In the third series of electrocatalysts, the best performance was obtained with the Monarch carbon catalyst heat-treated with ammonia, whose catalytic activity was higher than all others, due to the greater number of FeNx and N/C active structures formed by the treatment with ammonia. The results in acidic and alkaline conditions for the first and second series of electrocatalysts suggest the occurrence of an indirect ORR mechanism (2e- + 2e-), that is, in acid (alkaline) media first O2 is reduced to H2O2 (HO2) followed by the reduction of H2O2 (HO2). The active sites predominantly involved in the reaction electrocatalysis are WC and FeNx in acid media and WC e N/C in alcaline media. Finally, for the third series of electrocatalysts, the acidic reaction involves a direct 4e- mechanism, having important participation of the Fe-N2 active sites.

Orientador: Juno Gallego / Resumo: As superfícies desgastadas são normalmente revestidas com ligas metálicas resistentes ao desgaste abrasivo, nos quais durante a soldagem o metal de solda com matriz ferrosa é reforçado pela formação de carbonetos grosseiros durante a solidificação da poça de fusão. O propósito deste trabalho é investigar a aplicação de micro-ondas para o preparo de cavacos das ligas de titânio ASTM F67 e ASTM F136, visando a sua fragilização pela formação de uma fina camada de carbonetos que facilitam a moagem e a obtenção de pós finos. O pó obtido da reciclagem do titânio foi misturado com grafite, tornando possível a formação de carbonetos de titânio (TiC) durante a fusão da mistura sobre peças de aço-carbono ABNT 1020 com uma tocha a arco elétrico com proteção gasosa (GTAW). A aplicação de micro-ondas foi bem sucedida, permitindo a obtenção da mistura carbonetante com granulometria inferior a 45m. O metal de solda mostrou uma microestrutura ferrítica reforçada por partículas grosseiras TiC, que incrementaram significativamente a dureza do material. Os resultados obtidos indicam que a reciclagem de cavacos de titânio seja potencialmente interessante para o desenvolvimento de um consumível de soldagem para revestimentos resistentes ao desgaste abrasivo, mais econômico e ambientalmente sustentável. / Abstract: The worn surfaces are usually coated with abrasive resistant metal alloys, where the weld metal is reinforced by the formation of coarse hard carbides during the melt pool solidification. The aim of this work is investigate the irradiation of microwaves on scrap (chips) of ASTM F67 and ASTM F136 titanium alloys, becoming easier grinding of the residues for obtaining fine powder due to chips embrittlement by thin TiC coating. The titanium-rich recycled powder was mixed with graphite, making possible the formation of titanium carbides (TiC) during the melting of the mixture by Gas-Tungsten Arc Welding (GTAW) carried out on ABNT 1020 carbon steel pieces. The microwave application was very successful, allowing to obtain a fine carbide-former mixture with granulometry less than 45m. The weld metal have showed a microstructure composed by ferrite (BCC iron) reinforced by coarse dendritic TiC particles, which promoted significantly hardness increasing. The experimental results have indicate that microwave irradiation for titanium alloys chips recycling is potentially interesting for the development of a economical and environmentally sustainable consumables for abrasive wear resistant hardfacing. / Mestre

The aim of the project was to establish rate and mechanisms of solid state reduction of manganese ores. The project studied carbothermal reduction of manganese oxide MnO, two Groote Eylandt (Australian) and Wessels (South African) manganese ores in hydrogen, helium and argon atmospheres at temperatures up to 1400C for MnO and 1200C for manganese ores. Experiments were conducted in the fixed bed reactor with on-line off-gas analysis. The major findings are as follows. ?? Rate and degree of reduction of MnO and ores increased with increasing temperature. ?? Reduction of MnO and manganese ores at temperatures up to 1200C was faster in helium than in argon, and much faster in hydrogen than in helium. The difference in MnO reduction in hydrogen and helium decreased with increasing temperature to 1400C. ?? Addition of up to 7 vol% of carbon monoxide to hydrogen had no effect on MnO reduction at 1200C. ?? In the process of carbothermal reduction of ores in hydrogen at 1200C, silica was reduced. ?? Reduction of both GE ores was slower than of Wessels ore. This was attributed to high content of iron oxide in the Wessels ore. ?? Carbon content in the graphite-ore mixture had a strong effect on phases formed in the process of reduction; thus, in the reduction of Wessels ore with 12-16 wt% C, a-Mn and Mn23C6 were formed; when carbon content was above 20 wt%, oxides were reduced to carbide (Mn,Fe)7C3. ?? Kinetic analysis showed that mass transfer of intermediate CO2 from oxide to graphite in carbothermal reduction in inert atmosphere was a contributing factor in the rate control. ?? High rate of reduction of manganese oxide in hydrogen was attributed to formation of methane which facilitated mass transfer of carbon from graphite to oxide. Hydrogen was also directly involved in reduction of manganese ore reducing iron oxides to metallic iron and higher manganese oxides to MnO. Reduction of Wessels and Groote Eyland Premium Fines ores in the solid state is feasible at temperatures up to 1200C; while temperature for solid state reduction of Groote Eyland Premium Sands is limited by 1100C.

Experiments on the production of porous metallic materials were performed on Fe-base and Al-base alloys. The method involves dissolution of gases in the liquid state and solidification at various cooling rates. The alloy compositions were selected to induce solidification of primary particles intended to control the pore distribution. For the Fe-base alloys, nitrogen was introduced into the melt by dissolution of chromium nitride powder. Fe-Cr-Mn-Si-C alloys featuring M7C3 carbide particles were selected. For the Al-base alloys, hydrogen gas was dissolved into the melt by decomposition of water vapor. Al-Ti and Al-Fe alloys featuring primary Al3Ti and Al3Fe intermetallic particles, respectively, were considered. In the Fe-base alloys, a homogeneous distribution of gas pores through the specimens’ volume was obtained at high cooling rate (water quenching) and after introduction of external nucleating agents. In the case of the Al-base alloys, a good pore distribution was observed at all cooling rates and without addition of nucleating agents. Calculations of the variation of nitrogen (respectively hydrogen) solubility based on Wagner interaction parameters suggest that pore nucleation and growth occur during precipitation of the primary particles (M7C3 carbides, Al3Ti or Al3Fe intermetallics), due to composition changes in the melt and resultant supersaturation with gas atoms. Microscopic analyses revealed that the primary particles control the pore growth in the melt and act as barriers between adjacent pores, thereby preventing pore coalescence and promoting a fine pore distribution. Uniaxial compression testing of the porous Al-Ti and Al-Fe materials showed the typical compressive behavior of cellular metals. Further work is needed to improve the quality and reproducibility of the porous structures which can possibly be used in energy absorption or load-bearing applications. As a corollary result of the quenching of hypereutectic Fe-Cr-Mn-Si-C alloys in the experiments of synthesis of porous metals, a homogeneous featureless structure was observed in some parts of the samples, instead of the equilibrium structure of M7C3 and eutectic phases. Subsequent investigations on rapid solidification of Fe-base alloys at various alloy compositions and cooling rates led to the formation of a single-phase structure for the composition Fe-8Cr-6Mn-5Mo-5Si-3.2C (wt.%), at relatively low cooling rates (≈103 K/s) and for large sample dimensions (2.85 mm). The single phase, which is likely to be the hcp ɛ-phase, was found to decompose into a finely distributed structure of bainite and carbides at ≈600 °C. The annealed structure showed very high hardness values (850 to 1200 HV), which could be exploited in the development of high-strength Fe-base materials. / QC 20100809

The present work was initiated to investigate the stability, structural and thermodynamic properties of transition metal carbides, nitrides and carbo-nitrides by atomistic simulations and experimentations. The interatomic pair potentials of Cr-Cr, Mn-Mn, Fe-Fe, C-C, Cr-C, Mn-C, Fe-C, Cr-Fe, Cr-N and Mn-N were inverted by the lattice inversion method and ab initio cohesive energies, and then employed to investigate the properties of Cr-, Mn- and Fe-carbides by atomistic simulations in this work. For the binary M7C3 carbide, the structural properties of M7C3 (M = Cr, Mn, Fe) were investigated by atomistic simulations. The results show that the stable structure for these compounds is hexagonal structure with P63mc space group. The cohesive energy of M7C3 calculated in this work indicates that the stability of carbides decreases with the increasing in metal atomic number. Further, the vibrational entropy of Cr7C3 was calculated at different temperatures and compared with the entropy obtained by experimentations. The comparison demonstrates that the main contribution to the entropy is made by the vibrational entropy. For the binary τ-carbides, the structural properties of Cr23C6 and Mn23C6, as well as the vibrational entropy of Cr23C6 were computed. Further, the site preference of ternary element Fe among 4a, 8c, 32f and 48h symmetry sites in Cr23-xFexC6 was studied. It has been seen that Fe atoms would firstly occupy 4a sites and then 8c sites. The lattice constant and stability of Cr23-xFexC6 were also computed with different Fe content. In order to understand the relative stability of the transition metal carbides and nitrides, the standard formation Gibbs energies of carbides and nitrides for Cr, Mn and Fe were compared. The order of carbon and nitrogen affinities for Cr, Mn and Fe was further clarified by the comparison of the interatomic pair potentials among Cr-C, Mn-C, Fe-C, Cr-N and Mn-N. It was found that Cr-N interaction was very strong in comparison with other binary interactions above and consequently, nitrogen addition would lead to a strong decrease in the thermodynamic activity of chromium in Cr-containing alloys. This was confirmed by the investigations of thermodynamic activities of Cr in the Fe-Cr-N and Fe-Cr-C-N alloys. The activities were measured in the temperature range 973-1173 K by solid-state galvanic cell method involving CaF2 solid electrolyte under the purified N2 gas. In addition, the analysis of nitrogen content and phase relationships in the Fe-Cr-N and Fe-Cr-C-N alloys equilibrated at 1173 K were carried out by inert-gas fusion thermal conductivity method, X-ray diffraction and scanning electron microscopy technique. The experimental results show that the solubility of nitrogen in the alloys decreases with the decreasing chromium content, as well as the increasing temperature. The addition of nitrogen to the alloys was found to have a strong negative impact on the Cr activity in Fe-Cr-N and Fe-Cr-C-N systems. / QC 20100929