<p>This study reports on the changes in the structural properties of a tungsten-filament when exposed to a methane / hydrogen ambient for different durations at various filament-temperatures.</p>

<p>This study reports on the changes in the structural properties of a tungsten-filament when exposed to a methane / hydrogen ambient for different durations at various filament-temperatures.</p>

A systematic in-depth study has been undertaken to establish the corrosion mechanism of a Model 25Cr-35Ni-Fe alloy and four commercial alloys HP40Nb, AISI314, HP40Al and Alloy 800H in low oxygen, high sulphur and carbon containing environments typically found in coal gasification and fluidised bed combustion processes. A review of present knowledge of corrosion processes in purely oxidizing, sulphidizing and carburizing environments and multiple reactant carburizing/ oxidizing, carburizing/sulphizing and oxidizing/sulphidizing environments is given. The experimental programme was designed to establish the role of sulphur on the corrosion process by studying corrosion mechanisms in a sulphurfree H2-7%C0-1.5%H2o gas, a low sulphur H2-7%C0-1.5%H20-0.2%H 2 S gas (pS2_8= 10 bar), and a high sulphur H 2 -7%C0-1.5%H 2 0-0.6%H 2 S gas (pS = lO bar) at 800'C. All_21j_hree environments had a constant partiaf pressure of oxygen (po2 = 10 bar) and carbon activity (ac = 0.3). In the sulphur-free gas the Model alloy formed a thin uniform cr 2 o 3 layer which grew at a constant parabolic rate throughout the exposure period of 0 - 5000 hours. Surface working increased the growth rate and thickness of the Cr 2 o 3 layer but created a large number of cracks and pores which allowed carbon containing gaseous species to diffuse through the oxide to form carbide precipitates in the alloy substrata. Alloying additions of Si promoted the formation of an inner SiO layer which reduced the corrosion rate by cutting off the outward diffusion of Cr, Mn and Fe. Alloying additions of Mn promoted the formation of an additional outer (Mn, Fe )Cr 2o 4 layer. The 3. 5% Al content of the HP40Al was insufficient to form a complete Al 2 o3 layer. Alloy 800H was susceptible to localised internal oxidation. Adding a low level of sulphur (0.2% H 2 S) to the gas increased the corrosion rate of the Model alloy in the 1nitial stages. This rate gradually slowed down before becoming parabolic after 1000 - 2000 hours. This was due to the nucleation of sulphides in addition to oxides. The oxides and sulphides grew side by side until the oxides overgrew the sulphides to form a complete Cr 2o3 layer which cut off further ingress of sulphur from the gas. The entrapped sulphides promoted localized thickening of the oxide layer. Eventually the sulphur redistributed from the sulphides in the scale to internal sulphide precipitates in the alloy with the corrosion rate returning to that of the sulphur-fre,e gas for the rest of the exposure period (5000 hours total). In the commercial alloys the internal sulphide precipitates prevented the inner Si02 layer becoming complete. Sulphur doped the (Mn, Fe) Cr 2 0 4 outer layer ana the intermediate Cr 2o3 layer formed from the spinal layer, increasing the number of cation . vacancies and the growth rate of the scale. These factors caused a massive Cr depletion of the alloy substrata after several thousand hours. The internal carbides became unstable which led to a massive amount of internal attack and a dramatic increase (breakaway) in the corrosion rate. Due to its thickness and the presence of Si02 inner layer the external scale became susceptible to spallation. If this occurred the oxides and sulphides nucleated on the alloy surface again but sulphides. protective alloy. insufficient Cr was available for the oxides to overgrow the The sulphides therefore grew to form a fast growing nonsulphide scale which soon led to catastrophic failure of the Increasing the level of sulphur in the gas to 0.6% H2S caused oxides and sulphides to nucleate on the surface, but in this case the sulphides overgrew the oxides to form thick fast growing non-protective sulphide scales on all the alloys.

Magister Scientiae - MSc / This study reports on the changes in the structural properties of a tungsten-filament when exposed to a methane / hydrogen ambient for different durations at various filament-temperatures. / South Africa

[pt] Nos últimos anos, esforços vêm sendo empreendidos no sentido de aumentar o conteúdo de carbono no ferro-esponja, com o intuito de utilizá-lo como fonte energética e como agente redutor dos óxidos residuais na operação dos fornos elétricos a arco - FEA. O presente trabalho, fruto de um projeto cooperativo da Samarco Mineração SA com o Grupo de Siderurgia da PUC-Rio, apresenta os resultados de experimentos realizados, nos laboratórios de ambas as Instituições simulando as condições operacionais de um forno Midrex. Para a simulação o reator foi dividido em três zonas: Redução, Transição e Resfriamento. Para cada uma delas foi concebido um conjunto de experimentos, estatisticamente planejados, de forma a permitir a mensuração cinética da carburização. Os experimentos envolvendo a redução e a carburização das pelotas de minério de ferro utilizaram similaridades fluidodinâmicas das escalas. Adicionalmente, um método para análise química dos teores de carbono grafítico e livre foi empregado com sucesso. Em seguida foram realizados os testes de carburização das zonas de transição e resfriamento e levantadas as curvas e equações cinéticas. Na zona de transição o agente carburizante foi o gás metano sendo a sua injeção feita nas temperaturas de 300, 600, 700 e 850 graus Celsius . O modelo cinético utilizado foi uma equação linear de fluxo mássico. O valor da energia de ativação aparente encontrada para a carburização do DRI na zona de transição foi de 12,31 kJ/mol indicando um controle cinético difusional. A carburização do DRI para esta região situou-se na faixa de 0.1 por cento C (300 graus Celsius ) a 3 por cento C (850 graus Celsius ) , para um tempo de residência típico de 0,7 horas. Na zona de resfriamento o principal agente carburizante depende da temperatura: acima de 400 graus Celsius , foi o gás metano, enquanto nas temperaturas abaixo de 500oC foi o gás CO. Nesta zona a carburização do DRI, nas temperaturas de 250 a 600 graus Celsius , foi suposta ser uma reação de primeira ordem em relação ao carbono. O resultado obtido para a energia de ativação aparente na zona de resfriamento foi 5,31 kJ/mol, consistente com um mecanismo controlado por difusão. Considerando os resultados experimentais obtidos, a carburização final do DRI nesta zona, tomando-se um tempo médio de residência de (2,15h) esteve na faixa de 2,0 por cento C ( periferia / 600 graus Celsius ) a 3,0por cento C ( centro / 250 graus Celsius ). / [en] In later years efforts are being made aiming at the increase in the carbon content in the DRI, this to enable it to act as energy source and reducing agent for the residual oxides in the operation of the electric arc furnaces – EAFs. The present work, product of a cooperative project between the Samarco Mining Co. and the Iron and Steelmaking Group from the University PUC-Rio, presents the obtained results for the experiments on DRI carburization, made at the laboratories of both institutions, under simulated conditions occurring in MIDREX reactors. To mimic the reactor operation, it was divided in three zones, quoting: Reduction, Transition and Cooling. For each of these zones a set of experiments were conceived and statistically planned to permit the carburization kinetic determination. It must be also added that fluidynamic scale similarity were respected in those same experiments. Further, a special chemical method was successfully employed to access the graphitic and free carbon DRI contents for the carburization tests performed for the Transition and Cooling zones. Based on the obtained results, sets of curves for carburization versus time were composed and kinetic equations, for various temperatures and gaseous atmospheres, were proposed. For the Transition zone the carburizing agent was the methane gas, being its injection made under the temperatures of 300, 600, 700 e 850oC. The kinetic model utilized for the carburization in this zone was that of a mass flux linear equation. From this formalism, an apparent activation energy of 12.3 kJ/mol was calculated indicating a difusional control. The total DRI carburization in this zone ranged from 0.1 per cent C (300oC) to 3 per cent C (850oC) for a typical residence time of 0.7 hours. In the Cooling Zone there was a temperature dependency ruling the carburizing agent role, above 400oC the gas methane is the main carburizing gas, but below 500oC the CO act as such. In this zone, the DRI carburization was fitted with a kinetic equation of the first order with respect to carbon. The obtained result for the apparent activation energy for this equation rated 5.31 kJ/mol, consistent with a difusional mechanism. Considering the experimental results for a residence time of 2.15 hours, the final carburization for the DRI in the Cooling Zone ranged from 2.0 per centC ( furnace peripheral conditions / 600oC ) to 3.0 per cent C ( core conditions / 250oC ).

The primary intention with this Doctoral thesis is to fillin the knowledge gaps and raise the level of understandingregarding the different metal dusting mechanisms in general andexplain the process in detail for high alloyed materials.Considerable effort is put into identifying the driving forcesand elucidating the diffusional processes in metal dusting. The results are based on a series of long-term laboratory exposures of stainless steels and high-performance commercial alumina-forming Fe- and Ni-base alloys in synthesis gasmixtures, plus a separate shorter study on ultra pure iron. ANi-base alloy was also investigated after a two years field exposure in a methanol plant. Post exposure metallographic examinations and analysis aswell as thermodynamic calculations were made in order toidentify and describe the operating metal dusting mechanisms.Two main mechanisms were previously used to explain metaldusting, one on the basis of decomposition of metastable carbides (Type I) the other on graphite formation (TypeII). A new metal dusting mechanism has been identified in this Thesis which appears on high alloyed steels and Ni-base alloys,an active corrosion induced by carbon and oxygen, denoted TypeIII. Both the mechanisms and the type of corrosion products were consistent with the thermodynamic conditions of the material under the influence of a carbon and oxygen gradient.It was shown that this mechanism not only accelerates the metaldusting process, in fact, it determines the overall metaldusting kinetics on stainless steels and Ni-base alloys. Another feature, which may occur at temperatures where metalbulk and even static grain boundary diffusion is too slow forexplaining the metal dusting corrosion process, was identifiedon a Ni-base alloy. It involves a fast growing cellular structure with discontinuous precipitated carbides whichprovides fast metal dusting kinetics by the Type IIImechanism. A Type IV metal dusting mechanism, continued fragmentationby graphitization until nano-sized particles are formed andcatalyse carbon nanotube formation is also described. Thesteady state process and the driving force for metal dusting onpure iron was identified and described. With these additional processes it is now possible to extendour understanding of the metal dusting processes to a widerange of engineering alloys. / QC 20100825

L’allègement des structures pour l’aéronautique pose, entre autres, la problématique del’usinage des matériaux composites et multi-matériaux. Le challenge réside dans la conceptiond’outils répondant aux conditions spécifiques d’usinage de ces matériaux et à leur extrêmeabrasivité. Une solution est de faire appel aux performances du diamant comme revêtementrésistant à l’usure. Dans le cadre de ce manuscrit, nous proposons d’étudier les cinétiques deformation du diamant microcristallin, sur des couches minces de nitrure de tantale (TaN). Cenitrure cristallise sous deux structures distinctes : une phase stable, hexagonale, h-TaN, et unephase métastable, cubique faces centrées, fcc-TaN. Des paramètres d’élaborationméticuleusement optimisés ont rendu possible la synthèse de ces deux structures sous forme decouches minces monophasées et la proposition de mécanismes de stabilisation. Leur potentiel entant que couche de germination du diamant a été évalué et quantifié grâce à une méthodologieoriginale, alliant expériences et modélisation. La contribution de la modélisation a permis nonseulement d’interpréter précisément les résultats obtenus expérimentalement, mais aussid’identifier les grandeurs influentes. Les coefficients de diffusion du carbone et flux de carbonetransférés dans h-TaN et fcc-TaN ont ainsi été déterminés. Les résultats obtenus, en termesd’interactions entre le TaN et le carbone, au cours du procédé d’élaboration du diamant, ouvrentdes perspectives intéressantes en termes de contrôle de la formation du diamant par CVD. / Weight reduction of aeronautic devices raises composite and multi-materialsmachining issues. The challenge lies in designing cutting tools able to resist to the specificmachining conditions of these materials and their abrasivity. One solution is to use diamond as awear resistant coating. In this work, we propose to study the kinetic of formation ofmicrocrystalline diamond onto a tantalum nitride (TaN) thin film. TaN exhibits two crystallographicstructures: the hexagonal stable one, h-TaN, and the metastable one with a face centered cubiclattice, fcc-TaN. An accurate control of deposition conditions allows us to isolate both structuresas single-phased thin films and to propose two stabilization mechanism scenarios. The influenceof each TaN structure on diamond formation has been gauged thanks to the inventivemethodology we developed and which combines experiments and modeling. The contribution ofmodeling relies on an accurate interpretation of the experimental results and the identification ofthe key parameters. Thus, carbon diffusion coefficients and carbon transfers into h-TaN and fcc-TaN phases could be determined. Our results, in terms of TaN/carbon interactions, open up newhorizons for diamond nucleation and growth in CVD conditions.

[pt] A produção e o uso de DRI (Direct Reduction Iron) são cada vez maiores hoje em dia nos países desenvolvidos, essencialmente pela redução do preço do gás natural e do sucesso da tecnologia de extração de gás de xisto. Além disso, o menor teor de elementos contaminantes em DRI do que nas sucatas de aço, levou-o a ser considerado uma boa alternativa como carga metálica para o Forno Elétrico a Arco (FEA) e o processo no conversor LD /BOF. Os custos operacionais e os problemas ambientais, são atualmente dois fatores tecnológicos importantes a serem considerados na otimização da produção de DRI, afetando à produtividade, sustentabilidade e competitividade do processo industrial. O teor de carbono do DRI, por exemplo, tem se tornado cada vez mais importante, devido à sua capacidade de gerar energia química nas aciarias, complementando o uso de energia elétrica nos FEA e os inputs energéticos no LD. Este trabalho foi uma das partes do programa de cooperação entre a Companhia de Mineração Samarco e o Grupo de Siderurgia da Pontifícia Universidade Católica do Rio de Janeiro / PUC-Rio, que tratou especificamente do modelo cinético para a metalização e carburização simultâneas em fornos RD tipo cuba. No âmbito deste objetivo o reator foi dividido em três zonas: Redução, Transição e Resfriamento. Foram também consideradas mais três camadas concêntricas: periférica, media e central. Com base nos resultados obtidos em experiências que abrangeram diferentes tipos de pelotas, empregando misturas gasosas semelhantes às presentes nos processos industriais e obedecendo às suas correspondentes semelhanças fluidodinâmicas, foi desenvolvido um software, denominado METCARB, que incluiu na sua elaboração todas as equações e modelos cinéticos desenvolvidos experimentalmente nas três zonas do reator RD. A parte experimental foi, portanto, uma das partes principais do presente trabalho, conjuntamente com a concepção do modelo computacional e suas validações industriais. Com o METCARB, as previsões acerca da metalização e carburização simultâneas, em qualquer região interna do forno, se tornou possível, utilizando como entradas as dimensões do forno, medidas de temperaturas, composições dos gases, etc. Os resultados de metalização e carburização, também em formato gráfico, são gerados pelo sistema computacional, bem como as curvas cronométricas e tabelas de resultados. Estudos sobre dois casos reais foram realizados, a fim de validarem a ferramenta computacional desenvolvida. Constatou-se que a carburização do ferro metálico sempre ocorre simultaneamente com a redução dos óxidos de ferro e que, dependendo da temperatura e composição dos gases, pode ocorrer precipitação de finos de carbono. As simulações realizadas com o modelo METCARB mostraram que na periferia da ZR é gerado um DRI mais metalizado que na região do centro. Fenômeno contrário foi, entretanto, verificado com a carburização; Nas condições experimentais empregadas neste trabalho, os valores médios obtidos para a carburização e a metalização, no final da ZR, variam entre 0,4 - 0,7 por cento C, e 92 por cento - 97 por cento, respectivamente; Constatou-se não ocorrer progresso do grau de redução nas zonas de Transição (ZT) e de Arrefecimento (ZA), ou seja, mantiveram-se ao longo dessas zonas os valores de metalização obtidos no fundo da ZR; A influência do vapor de água no processo da carburização no caso estudado (0 - 4.25 por cento H2O) leva menor porcentagem de carburização (2,7 por cento C – 2,35). / [en] The production and the use of DRI (Direct Reduction Iron) are increasing today in developed countries, mainly by reducing the price of natural gas and the success of shale gas extraction technology. In addition, the lower level of contaminants in DRI than in metal scraps, led it to be considered a good alternative as metallic charge for the Electric Arc Furnace (EAF) and the process in LD / BOF converter. This work was one part of the cooperation program between Samarco Mining Company and Steel Group of the Pontifical Catholic University of Rio de Janeiro / PUC-Rio, which specifically dealt with the kinetic model for the metallization and carburization simultaneous in RD shaft furnaces. Under this purpose the reactor was divided into three zones: Reduction, Transition and Cooling. There were also three concentric regions considered: peripheral, media and center. Based on the results from experiments covering different types of pellets, using gas mixtures similar to those present in the industrial processes and obeying their corresponding fluid dynamic similarities, it developed a software called METCARB, which included in its preparation all kinetic equations and models developed experimentally in the three reactor zones of RD. The experimental part was therefore a major part of this work, together with the design of computational model and its industrial validations. With METCARB predictions about the simultaneous metallization and carburization in any internal region of the furnaces, it became possible, using as inputs the dimensions of the furnace, temperature measurements, compositions of gases, etc. The results of metallization and carburization also in graphic format are generated by the computer system, and the chronometric curves and results tables. Studies on two real cases were performed in order to validate the developed computational tool. It was found that the carburization always occurs simultaneously with the reduction of iron oxides and, depending on the temperature and composition of the gases; precipitation of fine carbon may occur. The simulations with METCARB model showed that the periphery of the ZR generated more DRI metallized than the center area. A contrary phenomenon has been verified with the carburization; With the experimental conditions used in this study, averages values obtained for the metallization and carburization in the final ZR vary between 0.4 - 0.7 percent C and 92 percent - 97 percent, respectively; It was not found that the progress of reduction degree occurred in the transition (ZT) and cooling (ZA) regions, in other words, it remained along these zones of the metallization values obtained at the bottom of ZR; The influence of water vapor in the carburization process in the case studies (0 - 4.25 percent H 2 O) takes a smaller percentage of carburization (2.7 percent C - 2.35).

During the last 10 years, low pressure carburizing and high pressure gas quenching has become more popular since it is a “new” process and researchers reports that the distortion characteristics gained from these processes is improved in relation to conventional processes. The aim of this work was to investigate the distortions gained from three different heat treatment processes on main shaft gears and crown wheels. Experiments with atmospheric carburization with oil quenching and low pressure carburization with nitrogen gas quenching or oil quenching were made and distortion characteristics gained from these processes were then measured and compared. It was found that components treaded in the relatively new LPC-HPGQ process are similar and often even better than the conventional method. The larger main shaft gear improves the most with newer method but instead gets a lower core hardness and systematic diametrical shrinkage. Some measurements on the crown wheel were also improved but others were affected negatively.

No description available.