Made available in DSpace on 2016-03-15T19:36:39Z (GMT). No. of bitstreams: 1 Eduardo Nocera.pdf: 12755331 bytes, checksum: 08a19b90827b2e4f2954b2f799e3d18d (MD5) Previous issue date: 2013-09-19 / MAHLE / Piston rings are metal parts which, when installed on the pistons in the cylinders of the engine, become circular with variable pressure and self-expansive, providing a movable seal between the combustion chamber and the crankcase. These components are subjected to intense functional demand, being asked to submit a low wear rate and maintain their structural and functional integrity under high temperatures and pressures. Due to these requirements, the technique is known of providing up-to-face contact with coatings or surface treatments to improve wear. Currently the majority of applications in the compression rings are martensitic stainless steels. These rings have their tribological properties improved by gas nitriding treatment which gives the steel surface intermediate properties between metallic and ceramic materials with high resistance to adhesive wear, as well as to wear by abrasion. This technology has been applied since the 90s with great success and high market penetration. With demand growing for reducing emissions was introduced in the market the Otto cycle engines with bifuel, better known as Flex engines. The principle of operation of these engines is the use of gasoline and ethanol at any mixing. The compression ratio of the piston is optimized for gasoline and not optimized for ethanol, since the latter does not have limitations to the phenomenon of detonation and this fact makes it occurs more Ethanol injection into the combustion chamber providing an improper fuel does not wash burnt in the cylinder wall. The result was the creation of a different tribological system in the area of operation of the rings where the nitrided layer began to suffer a detachment. This study aimed to find a solution for this detachment, where the nitride layer was changed. The modification consisted in decreasing the precipitation of carbides in the grain boundaries through migration carbon more to the core of the ring making it more robust to cracks and less susceptible to hydrogen embrittlement. Was created two nitriding stages, one richer in nitrogen which provides the wear resistance required for applying and the second stage causes the carbon to become more concentrated in the core hindering the generation of cracks and, consequently, the detachment. There was a decrease in the hardness of the nitrided layer without deteriorating the wear resistance, creating a unique solution and extending the life of this technology. / Os Anéis de Pistão são peças de metal que, quando instaladas nos pistões dentro dos cilindros dos motores, tornam-se circulares com pressão variável e auto-expansivas, proporcionando uma vedação móvel entre a câmara de combustão e o carter do motor. Estes componentes são submetidos à intensa demanda funcional, sendo solicitados a apresentarem uma baixa taxa de desgaste e a manterem sua integridade estrutural e funcional sob temperaturas e pressões elevadas. Em função destas exigências, é conhecida a técnica de prover-se a face de contato com o cilindro destes componentes revestimentos ou tratamentos de superfície para melhorar a resistência ao desgaste. Atualmente grande parte das aplicações nos anéis de compressão são em aços inoxidáveis martensíticos. Estes anéis têm suas propriedades tribológicas melhoradas pelo tratamento de nitretação gasosa o qual confere ao aço propriedades superficiais intermediárias entre os materiais metálicos e cerâmicos, com alta resistência ao desgaste adesivo, assim como ao desgaste por abrasão. Esta tecnologia vem sendo aplicada desde os anos 90 com absoluto sucesso e alta penetração de mercado. Com a demanda por redução de emissões crescendo foi introduzido no mercado os motores de ciclo Otto bicombustíveis, mais conhecidos como motores flex. O princípio de funcionamento destes motores é a utilização de gasolina e etanol em qualquer mistura. A taxa de compressão do Pistão é otimizada para gasolina e não otimizada para o Etanol, pois este último não possui limitações para o fenômeno de detonação e este fato faz com que ocorra mais injeção de Etanol na câmara de combustão proporcionando uma indevida lavagem de combustível não queimado na parede do cilindro. A consequência foi a criação de um tribo sistema diferente na região de funcionamento dos Anéis onde a camada nitretada começou a sofrer um destacamento. Este trabalho visou buscar uma solução para este destacamento, onde a camada nitretada foi alterada. A alteração consistiu em diminuir a precipitação de carbonetos nas fronteiras dos grãos através da migração do carbono para o núcleo do anel deixando-o mais robusto à nucleação de trincas e menos susceptível a fragilização por hidrogênio. Foram criados dois estágios de nitretação, sendo o primeiro estágio mais rico em nitrogênio o qual confere ao anel a resistência ao desgaste necessária para a aplicação, e o segundo estágio faz com que o carbono fique mais concentrado no núcleo. O problema de destacamento foi resolvido onde houve uma diminuição na dureza da camada nitretada sem a deterioração da resistência ao desgaste do anel, criando uma solução única e estendendo a vida desta tecnologia sem aumento de custos.

Made available in DSpace on 2016-03-15T19:37:01Z (GMT). No. of bitstreams: 1 Eva Paganini Martins.pdf: 2852717 bytes, checksum: 4c8bb41c27d4434bc48bef3b6484ab0f (MD5) Previous issue date: 2010-03-05 / This paper deals with the effects of cold work on the nitriding kinetics and surface micro-hardness of the 3XX family of austenitic stainless steels. Nitriding is a thermo-chemical treatment based on the nitrogen diffusion and, under some specific circumstances, carbon in lower quantities, in to a ferrous matrix. The nitriding process improves particularly high cycle fatigue resistance, wear resistance, and corrosion resistance for carbon steels. To study the cold work effect on the material, samples of 304 and 316 were strained in tension tests to conventional deformation of 10%, 25% and up to rupture point prior to the nitriding process. A sample without deformation was kept for reference. It is possible to verify, based on the test performed, that the AISI 304 has smaller deformation capacity when compared to the 316 in terms of elongation on strain test presenting a higher degree of cold work deformation. Also the 304 presents a reduction on nitrided layer thickness and a smaller percentage of nitrogen in the nitrided layer after the cold work (difference of 1% point versus 0,5 for the 316) It is also possible to observe the smaller density on the 304 after the cold work which can be attributed, according to the literature, to the formation of cold work martensite during the cold work process. / O presente trabalho apresenta uma avaliação dos efeitos de encruamento na cinética do processo de nitretação das ligas de aço inoxidável austeníticos da série 3XX e no perfil de dureza das superfícies nitretadas. Nitretação é um tratamento termoquímico baseado na difusão de nitrogênio, em algumas circunstancias carbono em pequenas quantidades, na matriz ferrosa. Para estudar os efeitos do encruamento no material, amostras de 304 e 316 foram encruadas em ensaio de tração convencional, em 10%, 25% e até a ruptura e posteriormente nitretadas. Ainda manteve-se uma a mostra sem deformação para fins de comparação. Com base nos ensaios avaliados é possível verificar que o AISI 304 tem menor capacidade de deformação que o AISI 316 em termos de alongamento no ensaio de tração apresentando maior taxa de encruamento em relação ao 316. Além disso o 304 apresenta redução na camada nitretada proporcional ao grau de deformação plástica a frio e menor percentual de nitrogênio na camada após deformação (queda de aproximadamente 1 ponto percentual enquanto no 316 a diferença mantém-se em torno de 0,5 pontos). Ainda é possível observar a diminuição da densidade no 304, o que pode ser atribuído, segundo a literatura, a formação de martensita e deformação durante o processo de deformação plástica a frio.

O processo de injeção sob pressão de ligas de alumínio é empregado para a produção de peças diversas, destinadas principalmente à indústria automobilística. Dentre as principais vantagens deste processo, destaca-se a possibilidade de produção de peças complexas, com seções delgadas, e a alta velocidade de produção. Apesar desses pontos positivos, o reduzido tempo de ciclo e as elevadas temperaturas (~ 700°C) envolvidas promovem danos por fadiga térmica na superfície de trabalho das matrizes. Após milhares de peças produzidas, surgem trincas em regiões críticas, que crescem com o aumento da produção até atingirem condições que inviabilizam o uso da matriz, levando ao seu fim de vida. Na última década, novos aços de alta tenacidade e melhor resistência a quente, bem como tratamentos termoquímicos como a nitretação sob plasma vêm sendo aplicados em tais matrizes, retardando significativamente o fim de vida. Neste contexto, o presente trabalho visou estudar o fim de vida de matrizes de fundição sob pressão, relacionando-o aos aspectos microestruturais da superfície nitretada, tensões residuais inseridas durante processo de nitretação e as condições do processo de fundição. Para o estudo, os aços AISI H13, AISI H11 com redução do teor de Si e AISI H10 modificado, foram temperados e revenidos para dureza na faixa de 44 a 46 HRC e posteriormente nitretados sob plasma em diversas condições de temperatura, tempo e composição da atmosfera gasosa. Foram feitos ensaios de medições de tensões residuais, perfis de dureza, metalografia e difração de Raios-X. Para o estudo de fadiga térmica, foi utilizado o software DEFORM 3DTM para simular os danos ocasionados pelos mecanismos de fadiga térmica nas superfícies das matrizes com a presença e ausência de camada nitretada. Os resultados obtidos mostraram que a variação dos parâmetros de nitretação, tais como: tempo, temperatura e percentual de nitrogênio, afetam o perfil de dureza e de tensões residuais presentes na camada nitretada, bem como os microconstituintes da camada nitretada. Também foi verificado que a variação dos teores de elementos de liga de aços ferramenta para trabalho a quente em relação ao H13, mudam o perfil de dureza e de tensões residuais de compressão das camadas nitretadas. O material nitretado, após ser submetido em temperatura elevada, apresenta redução no nível de tensões residuais de compressão, ocorrendo processo de alívio de tensões. O mesmo efeito não é tão fortemente verificado no perfil de dureza do material. Deste modo, foi possível verificar que nos primeiros ciclos de injeção de alumínio, os mecanismos responsáveis por retardar a nucleação das trincas térmicas são a presença de tensões residuais de compressão na superfície do material e maior dureza local, dada pela maior dureza a quente existente no perfil de dureza da camada nitretada. Para estágios mais avançados de ciclagem térmica, apenas a maior dureza local será responsável por retardar a nucleação das trincas térmicas. A simulação demonstrou que o dano gerado durante processo de fadiga térmica é mais intenso no processo em que a matriz permanece exposta por tempos mais longos em elevadas temperaturas. O conhecimento destas características pode auxiliar a retardar o dano na superfície da matriz, via alterações do processo de fundição, ou das características dos aços ferramenta, dada pela tenacidade e resistência a quente da liga empregada na matriz, ou dos tratamentos térmicos e ou dos tratamentos de superfície, como a nitretação sob plasma, aplicados às matrizes. / The process of pressured injection of aluminum alloys is made use of in the production of sundry parts, meant mainly for the automotive industry. Among the main advantages of such process there stands out the possibility of production of complex parts, with thin sections, and at a high output speed. Despite these positive points, the reduced cycle time and high temperatures (~ 700°C) involved cause damage due to the thermal fatigue on the working surface of dies. After a great number of parts made there appear cracks in these areas that grow with the production increase up to reaching conditions that make the use of the die no longer viable, thus leading to its death. In the last decade, new unyielding, better heat resistant steels, as well as thermochemical treatments like plasma nitriding, have been applied to such dies, significantly hindering their death. In this context, the present paper has aimed at studying the death of pressured die casting by relating it to the microstructural aspects of the surface, residual tensions inserted during the nitriding process and the die casting conditions. For the study, AISI H13, AISI H11 with Si content reduction, and DIN WNr. 1.2367 steels were quenched and tempered to hardness in the range of 44 to 46 HRC and later subjected to plasma nitriding in different conditions of temperature, time, and gas atmosphere composition. Measurement tests of residual tensions, hardness profiles, metallography, and X-Ray diffraction have been carried out. For the thermal fatigue study, the software DEFORM 3D has been used to simulate damages caused by the thermal fatigue on the surface of dies in the presence or absence of surface nitriding. Results obtained have shown that the variation of nitriding parameters, such as time, temperature, and nitrogen percent, affect the hardness and residual tension profiles present in the surface nitriding, as well as in its microcomponents. It has also been ascertained that the variation of content of elements of steel tool alloys for heat work in relation to H13 one changes the profile of hardness and residual tensions of compression of nitriding treated surface. The resulting material, after being subjected to high temperature, presents a reduction of level in the residual tensions of compression, bringing about a process of tensions relief. The same effect is not so strongly verified in the material hardness profile. Accordingly, it has been possible to ascertain that in the first cycles of aluminum injection, the mechanisms responsible for slowing down the nucleation of thermal cracks are the presence of residual compression tensions on the material surface and higher spot hardness, given the higher heated hardness existing in the hardness profile of nitriding treated surface. For more advanced thermal cycling stages just the higher spot hardness will account for hindering the nucleation of thermal cracks. The simulation has demonstrated that the thermal fatigue process is more intense in process in which the die is exposed to high temperature for a longer time. The knowledge of these characteristics may help hinder the die surface damage through modifications in the casting process, or in the characteristics of tool steel (given the toughness and heat resistance of the alloy used in the die), or in the thermal treatments, or in the surface treatments, like plasma nitriding applied to dies.

Les turbines aéronautiques et terrestres utilisent comme matériaux de structure les superalliages à base nickel. Ils sont confrontés en utilisation à des environnements agressifs à très hautes températures, conduisant à l'usure et la corrosion, et à des sollicitations mécaniques qui entraînent fatigue et fluage. Pour permettre l'utilisation de ces matériaux dans des conditions toujours plus sévères de fonctionnement et augmenter la durée de vie des pièces, divers traitements de nitruration ont été proposés pour durcir la surface tout en conservant ou en améliorant la tenue mécanique et la résistance chimique. Les modifications induites par la nitruration, leur stabilité et l'influence de la microstructure initiale sont encore mal comprises dans ces matériaux complexes. Au cours de ces travaux, nous avons étudié les effets d'une nitruration assistée plasma en fonction de la microstructure et de la composition chimique des alliages. Différents types de superalliages à base nickel ont été choisis, de microstructures variées, comprenant éventuellement des précipités de type Ni3(Al,Ti,Nb) et/ou Ni3 (Nb). Nous avons alors caractérisé les modifications induites par l'introduction de l'azote dans les matériaux suite à un traitement de nitruration à basse température (400°C) : expansion de la maille, génération de contraintes résiduelles, comportement des précipités, formation de nitrures, plasticité, anisotropies... Les résultats obtenus suggèrent des effets différents selon la composition des précipités. Ces modifications structurales et leurs évolutions ont ensuite été étudiées lors d'un recuit à plus haute température (650°C) afin d'étudier la stabilité des couches formées. / Nickel-based superalloys are commonly used in pressurized water heat exchangers or in the hottest sections of aeroengines or industrial gas turbines, where they are subjected to high temperature and severe mechanical solicitations (fatigue, creep). To allow use of those materials in more and more difficult operating conditions and to improve their duration, different nitriding treatments have been proposed to harden the surface while maintaining or improving their mechanical strength and chemical resistance. However, modifications induced by nitriding, resulting stability in time and influences of the initial microstructure are still poorly understood in these complex materials. In this work, we investigated the behavior of plasma nitriding on superalloys according to their initial microstructure and chemical composition. Thus, different types of Nickel-based superalloys were selected with various microstructures, possibly including precipitates like Ni3(Al, Ti, Nb) and/or Ni3(Nb). Then, we have characterized the modifications induced by nitrogen introduction in the materials after nitriding treatment at low temperature (400°C): lattice expansion, generation of residual stress, precipitates behavior, nitrides formation, plasticity, anisotropy... The results suggest different behaviors depending on the composition of precipitates. Finally, these structural modifications and their evolutions have been studied during an annealing at higher temperature (650°C) in order to study the stability of the nitrided layers.

L’ouverture du marché de l’aéronautique civil aux matériaux composites à matrice céramique impose le développement de nouveaux procédés d’élaboration compatibles avec les cadences de production et les coûts de fabrication du secteur.À cette fin, des travaux expérimentaux ont été menés pour élaborer une matrice à base d’oxynitrure de silicium (Si2N2O) par procédé SHS, ou synthèse par combustion, à partir d’un mélange de poudres réactives.L’oxynitrure de silicium est une céramique thermostructurale prometteuse, caractérisée par de bonnes propriétés mécaniques, mais également par une résistance à l’oxydation supérieure à celle du carbure de silicium.Le procédé SHS est un procédé d’élaboration rapide dont le moteur est une réaction chimique suffisamment exothermique pour s’entretenir sans apport d’énergie extérieur.Les poudres sont préalablement broyées, mises en suspension, puis imprégnées dans une préforme fibreuse composée de fibres en carbure de silicium de dernière génération (Hi-Nicalon S). La réaction SHS est ensuite réalisée dans un réacteur spécialement conçu et dédié à cette étude.Une attention particulière a été portée sur l’optimisation des paramètres d’élaboration pour la synthèse d’une matrice à base Si2N2O. La synthèse s’effectue par la nitruration sous pression d’un mélange dans les bonnes proportions d’une poudre de silicium et d’une poudre de silice. La réaction chimique s’amorce à la température de fusion du silicium. La pression d’élaboration et la vitesse de montée en température constituent les paramètres principaux régissant la composition et la microstructure de la matrice. Ces paramètres ont fait l’objet d’une étude expérimentale approfondie pour parvenir à une matrice homogène, composée à plus de 90% d’oxynitrure de silicium et assurant un taux de porosité résiduelle du composite inférieur à 10%. Ce travail a été complété par le calcul des propriétés élastoplastiques de la matrice, par la caractérisation mécanique à l’échelle du composite, et par un test de vieillissement en température sous air humide. / The opening of the civil aviation market to ceramic matrix composite materials requires the development of new methods of producing compatible with the production rates and manufacturing costs of the sector.For this purpose, experimental work was conducted to develop a silicon oxynitride matrix (Si2N2O) by combustion synthesis (or SHS), from reactive powders. In recent years, Si2N2O has emerged as a promising new high-temperature ceramic material, characterized by not only good mechanical properties, but also by a higher oxidation resistance than silicon carbide. The underlying basis of SHS relies on the ability of highly exothermic reactions to be self-sustaining and, therefore, energetically efficient. Powders are first milled, dispersed and stabilized in aqueous media, and then impregnated into a fibrous preform composed of the latest generation of silicon carbide fibers (Hi-Nicalon S). SHS reaction is then carried out in a reactor specially designed and dedicated to this study. Particular attention was focused on the optimization of experimental parameters for the synthesis of a Si2N2O based matrix. Silicon metal in a mixture with silica powder was combusted under pressurized nitrogen gas into silicon oxynitride. The pressure and the temperature rise rate were the principal parameters for the composition and microstructure of the matrix. These parameters have been the subject of extensive experimental work to reach a homogeneous matrix with a very high formation rate for silicon oxynitride (more than 90wt%) and with a level of residual porosity lower than 10%. This work was completed by the calculation of the physical properties of the matrix, by the mechanical characterization of the composite material, and finally by a temperature aging test under moist air.

Orientador: Fernando Alvarez / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-08T01:14:15Z (GMT). No. of bitstreams: 1 OchoaBecerra_ErikaAbigail_M.pdf: 6414208 bytes, checksum: be25f7cebf36f2d96cfd208deecb449a (MD5) Previous issue date: 2003 / Resumo: Apresente tese trata sobre a implantação de nitrogênio em sistemas baseados em ferro. Duas técnicas de nitretação são utilizadas, plasma pulsado e feixe iônico por canhão de íons. Os parâmetros de nitretação são otimizados com a finalidade de obter um melhoramento na dureza superficial destes sistemas, isto é, em algumas dezenas de mícron. Tal melhoramento é relacionado com a concentração de nitrogênio em profundidade correspondente a uma sucessão de nitretos formados. A estabilidade destas fases é observada qualitativamente pela dependência com os processos de nitretação. A formação de camadas de nitretos é estudada a partir de um modelo de difusão e determinadas através de caracterização por raios-X, microscopia eletrônica de varredura (MEV) e espectroscopia de fotoelétrons de raios-X (XPS). A dureza em profundidade, de amostras submetidas a diferentes processos de implante de nitrogênio, foi determinada mediante nanoindentação. Amostras portadoras de um alto grau de dureza foram empregadas: aço AISI 4140. O polimento destas amostras, para caracterização em diferentes profundidades, foi processado mediante iesputteringl, com íons de argônio. Os efeitos da erosão foram estudados com auxilio de um perfilômetro. Coeficientes de difusão de nitrogênio em diferentes tipos de nitretos foram determinados e a uma correlação entre a dureza e concentração de nitrogênio em profundidade foi verificada explicitamente / Abstract: This thesis deals about the nitrogen implantation in iron - based systems. Two techniques to nitriding were used, either pulsed plasma or ionic beam by use of a cannon. The nitriding parameters were optimized with the purpose to get an improvement in the superficial hardness of these systems; this is, in a few dozen of micrometers. Such improvement is related with the in-depth nitrogen concentration corresponding to a set of layered phases. The stability of these phases is observed qualitatively because the dependece with the processes of nitriding. The layered phases containing nitrides is studied from a difusion model and determined through X-ray, scanning electron microscopy (SEM) and photoelectron spectroscopy (XPS). The hardness in depth, of samples subjected to different processes of nitrogen implantation, was determined by means of nano-indentation. Samples showing a high degree of hardness were used: steel AISI 4140. The polishment of these samples, for characterization in different depths, was processed by means of sputtering with argon ions. The effect of erosion had been studied by means of a perfilometer. Difusion coefficients of nitrogen in the different types of layered nitrides had been determined and a correlation between hardness and nitrogen concentration in depth was verified explicitly / Mestrado / Física da Matéria Condensada / Mestre em Física

Au cours des procédés de mise en forme du verre creux, les outillages de verrerie sont soumis à des conditions extrêmes avec des températures pouvant dépasser largement 650 °C. De plus, ces derniers sont exposés à des phénomènes d'abrasion sévères et à des réactions physico-chimiques complexes avec le verre fondu. Ceci est particulièrement accentué par les cycles thermiques dus aux contacts répétés avec le verre. L'objectif de ce travail de thèse est de proposer des solutions innovantes de dépôts de superalliages et/ou traitements de surface destinés à augmenter la durée de vie des outillages. Trois axes d'innovation sont présentés dans ce mémoire. Le premier concerne l'étude du dépôt de poudre composite Co/NiB par soudure PTA (Plasma Transfered Arc) sur des moules en alliage cuivreux. Le second est dédié à l'étude de la faisabilité technique d'un dépôt PVD (Physical Vapor Deposition) multicouche à gradient fonctionnel, présentant des caractéristiques intéressantes pour des applications verrières en termes de dureté et de stabilité thermique, sur des poinçons en acier AISI 431. Enfin, le troisième axe de recherche fait l'objet d'une analyse plus approfondie et concerne l'étude de la nitruration par implantation d'ions azotes multichargés, également sur un acier AISI 431. On observe après implantation une augmentation significative de la dureté (+ 240 %). Une approche multi-expérimentale et multi-échelle est alors proposée afin d'étudier la microstructure du matériau implanté ainsi que son évolution après un recuit de 1h à 650 °C de manière à anticiper le comportement du matériau en production, et de corréler ceci aux propriétés de dureté / Glass moulds have to withstand very high temperatures which can far exceed 650 °C during the glass forming process. They are exposed to very tough conditions such as abrasive wear and physico-chemical reactions, accentuated by thermal shocks due to high speed contact with hot glass melt. The aim of this work is to find innovative solutions for superalloy coating or surface treatments in order to increase the service life of glass tools. Three innovation projects are presented in this report. The first one is dedicated to PTA (Plasma Transferred Arc) welded coating of composite Co/NiB powder on copper alloy moulds. The second one is about technical feasibility of a multilayer PVD (Physical Vapor Deposition) coating with properties congruent to glass production in term of hardness and thermal stability, on AISI 431 plunger stainless steel. Last but not least, the third innovative project is about nitriding by ion implantation with multicharged nitrogen ions on AISI 431 stainless steel. We notice after ion implantation a significant hardness increase (+ 240 %). A multi-experimental and multi-scale approach was carried out in order to study the implanted material microstructure and its evolution after annealing at 650 °C during 1h to predict the material behavior during production and correlate it to hardness properties

Direct Reduced Iron (DRI) is used as an alternative feedstock in electric arc furnaces, making up 50% or more of the total iron charge. DRI produced with coal based reductants (for example in rotary kilns) make up roughly 25% of DRI produced in the world. It was found that SL/RN DRI samples from a kiln cooler had high nitrogen contents (50-250ppm, depending on particle size), higher than DRI from gas-based reduction. The higher nitrogen content of SL/RN DRI would increase the levels of nitrogen of liquid steel produced in the EAFs. The problem is exacerbated by the fact that the SL/RN DRI contains virtually no carbon (which would aid in preventing nitrogen pickup). The proposed mechanism of nitrogen pick-up by the SL/RN DRI is one where nitrogen present within the atmosphere of the rotary cooler (where hot DRI, discharged at 1000°C from the rotary kiln, is cooled to approximately 100 °C in ca. two hours) penetrates the solids bed and nitrides DRI particles. Possible rate-determining steps for nitriding in the cooler have been evaluated. Nitriding of DRI particles is predicted to be rapid: the most plausible location for rapid nitrogen pickup is the first 5 meters of the rotary cooler, where the high temperature, nitrogen-rich gas atmosphere and rapid solids bed mixing are conducive to nitriding; solid-state and pore diffusion of nitrogen into DRI particles are predicted to be rapid too. The most plausible rate determining step for nitriding of DRI particles is that of nitrogen dissociation on the DRI surface, which can be further retarded by the presence of sulphur. A strong correlation was found between the amount of “melt-in” carbon in the liquid steel and the final tap nitrogen content, with 0.3% C resulting in nitrogen levels as low as 50 ppm (80 ppm or less is desired on the plant in question) at tap, even with DRI material that is high in nitrogen and contains virtually no carbon. Proposals to increase the melt-in carbon are included. / Dissertation (MEng)--University of Pretoria, 2013. / gm2014 / Materials Science and Metallurgical Engineering / unrestricted

[pt] O nitreto de gálio (GaN) é um dos mais interessantes e promissores materiais para aplicação em dispositivos óptico- eletrônicos. GaN pode ser usado para a fabricação de diodos e lasers azuis. O desenvolvimento deste tipo de material está relacionado com três campos principais: 1) deposição de camadas de GaN cristalino; 2) produção de nano- filamentos a partir de reações confinadas no interior de nanotubos de carbono; 3) síntese de GaN em pó por diferentes métodos químicos. Recentemente, novas técnicas de deposição adotaram a sublimação de pós de GaN como fonte de gálio para a produção de nanofilamentos de GaN, filmes finos ou cristais. Estes métodos de sublimação mostram a necessidade do emprego de pós de GaN. No presente trabalho, é apresentada uma nova rota para a produção de pós de GaN a partir da reação gás-sólido entre Ga2O3 e NH3(g) utilizando o carbono como agente redutor no interior de um novo tipo de reator, disposto verticalmente. A partir desta rota obteve-se pós de GaN com conversões aproximadamente de 100% e com estrutura cristalina hexagonal. A quantidade de GaN obtida variou de acordo com os parâmetros experimentais adotados. Através de uma análise estatística foi possível determinar a influência da temperatura, razão molar de carbono/Ga2O3 e do tempo experimental sobre a taxa de produção de GaN. / [en] It is well known that gallium nitride (GaN) is one of the most interesting and promising materials for optoelectronic devices. GaN can be used for manufacturing blue light- emitting diodes and lasers. Development of this material is concerned with three main areas 1) deposition of GaN crystalline layers onto different substrates; 2) manufacturing of GaN nanorods from chemical reactions in the confined spaces provided by carbon nanotubes; 3) synthesis of GaN powders by different chemical methods. Recently, new deposition techniques have adopted sublimation of GaN powders as gallium source to produce GaN nanorods, thin films or bulk crystals. These sublimation methods rely on the supply of GaN powders. This thesis presents a new route to produce GaN powder from gas-solid chemical reaction between Ga2O3 and NH3 using carbon as reducing agent in a new reactor design. The GaN powder obtained from this route possesses a hexagonal crystal structure and was found to correspond to almost 100% conversion of Ga2O3. The amount of GaN present in the powders varied with experimental parameters. A statistical analysis showed the influence of temperature, carbon/Ga2O3 ratio and experimental time on the production of GaN powder.

Rost- und säurebeständige Stähle, wie z.B. der Austenit 1.4404, zeichnen sich durch eine hervorragende Korrosionsbeständigkeit aus. Der Einsatz dieser Stähle war aber aufgrund ihrer schlechten Verschleißeigenschaften bisher eher eingeschränkt. Um diesen Anforderungen gerecht zu werden, ist es notwendig, eine Oberflächenmodifizierung vorzunehmen. Dies kann besonders mit Nitrier- und Carburierverfahren bzw. einer Kombination aus beiden erreicht werden, wobei das im Mischkristall gelöste Chrom nicht zur Ausscheidung als Chromnitrid bzw. Chromcarbid gebracht werden darf. Dazu wurde bereits Mitte der 80-er Jahre das Verfahren der so genannten Tieftemperaturnitrierung entwickelt. Mit Hilfe dieses Verfahrens ist es möglich, auf rost- und säurebeständigen Stählen eine Schicht mit hohem Verschleißwiderstand zu erzeugen, ohne dass es zum Verlust der Korrosionsbeständigkeit kommt. Die werkstoffwissenschaftliche Forschung hat mit dieser überwiegend technologischen Entwicklung nicht Schritt gehalten. Verallgemeinerungsfähige Aussagen über das Korrosionsverhalten dieser verschleißbeständigen Randschichten in Abhängigkeit von ihrer Zusammensetzung und Struktur sind gegenwärtig noch nicht möglich. Die Zielstellung der im Rahmen dieser Arbeit durchzuführenden Untersuchungen besteht deshalb in der Ermittlung vertiefter Kenntnisse über den Zusammenhang zwischen den Behandlungsbedingungen, der Struktur und der chemischen Zusammensetzung der dabei entstehenden Randschichten und ihrem Korrosionsverhalten.