[pt] Ligas ferrosas são importantes insumos nos processos de obtenção de aços especiais. A obtenção de ligas Fe-Cr se dá principalmente por meio de dois processos, empregando-se como agentes redutores C ou Si, sendo o primeiro associado à síntese de ligas FeCrAC, e o segundo às ligas FeCrBC. Neste contexto, ligas do sistema Fe-Cr, com teor de Cr típico variando entre 45 a 95 por cento em massa, apresentam destaque, principalmente na fabricação de aços inoxidáveis. Durante processo de obtenção das referidas ligas, há considerável produção de finos, os quais podem ser reaproveitados mediante tratamento químico (piro e hidrometalúrgico) apropriado. No presente trabalho investigouse a extração de cromo de finos gerados durante a produção de uma liga Fe-Cr com alto teor de C. Para tanto foram realizadas ustulações nas temperaturas de 700, 800, 900 e 1000 graus Celsius com excessos de 100, 200, 300 e 400 graus Celsius NaOH e estequiométrico, 125, 150 e 200 graus Celsius de excesso de Mg(OH)2 em atmosfera oxidante, seguida de solubilização em meio aquoso e redução com H2O2 em diferente valores de pH, seguido-se da precipitação com NaOH em pH alcalino. Matéria prima, intermediários e produtos foram caracterizados por MEV/EDS, FTIR, DRX e ICP-OES. As recuperações de Cr em solução máximas alcançadas foram da ordem de 98 por cento, e a etapa de redução e precipitação em aproximadamente 95 por cento sugerindo que a rota de processamento químico proposta foi satisfatória no que tange à extração do cromo inicialmente presente. / [en] Ferrous alloys are important inputs in the process of obtaining special steels. The obtained Fe-Cr alloy is mainly by two processes, employing reducing agents such as C or Si, the first being associated with the synthesis of FeCrAC alloy and the second alloy to FeCrBC. In this respect, alloys of Fe-Cr system with varying Cr content typically between 45 to 95 percent by weight show prominence, particularly in the manufacture of stainless steel. During the process of obtaining these alloys, there is considerable production of fines which can be reused by appropriate chemical treatment (hydro-and pyro). In the present work we investigated the extraction of chrome fines generated during the production of a Fe-Cr alloy with high content of C. For both ustulações were performed at temperatures of 700, 800, 900 and 1000 Celsius degrees in excess of 100, 200, 300 and 400 percent stoichiometric NaOH and 125, 150 and 200 percent excess of Mg (OH) 2 in an oxidizing atmosphere, followed by solubilization in an aqueous medium and in H2O2 reduction with different pH values was followed by precipitation with-NaOH alkaline pH. Raw materials, intermediates and products were characterized by MEV/ EDS, FTIR, XRD and ICP-OES. The recoveries of Cr on maximal solution achieved were of the order of 98 percent, and the stage of reduction and precipitation by about 95 percent suggesting that the route of chemical processing proposal was satisfactory with regard to the extraction of chromium initially present.

Nióbio e suas ligas são utilizados atualmente em muitas aplicações industriais por oferecerem excelente resistência à degradação em diversos meios corrosivos. Estes meios incluem atmosferas gasosas em temperaturas elevadas, como as encontradas em plantas de gaseificação de carvão existentes em usinas termelétricas para geração de energia. As atmosferas encontradas nestes meios são misturas gasosas complexasque contêm, entre outros compostos, oxigênio e enxofre. Os sulfetos são compostos menos estáveis, possuem pontos de fusão mais baixos e apresentam, freqüentemente, maiores desvios de estequiometria em relação ao óxido correspondente. Apesar de existirem estudos relacionados à aplicação de metais refratários em atmosferas sulfetantes a temperaturas elevadas, o uso de compostos de nióbio ainda não foi devidamente avaliado como revestimento protetor, havendo poucos dados disponíveis na literatura. O objetivo deste trabalho foi avaliar o efeito proporcionado por um filme de nióbio, obtido por pulverização catódica,sobre o comportamento de sulfetação isotérmica das ligas Fe-20Cr e Fe-20Cr-1Y.Os testes de sulfetação foram realizados a 500, 600 e 700°C pelo período de 2h em atmosfera H2/2%H2S. A avaliação da resistência à sulfetação foi feita por meio do ganho de massa por unidade de área exposta. Observou-se que o comportamento de sulfetação a 500ºC das ligas FeCr e FeCrY sem e com revestimento é similar. Nesta condição, nenhuma das ligas sofreu escamação. A 700ºC a liga FeCr sofreu leve escamação na forma de um pó fino, enquanto que o produto de reação formado sobre a liga FeCrY escamou na forma de placas. O efeito do nióbio se torna pronunciado a 700ºC. A camada de produto de reação formada sobre as ligas revestidas é mais fina e plástica que na liga sem revestimento. O ganho de massa por unidade de área diminuiu sensivelmente para as ligas recobertas, que não sofreram escamação. / Niobium and niobium based alloys are currently used in many industrial applications because they offer excellent resistance to degradation in various corrosive environments. These media include gaseous atmospheres at high temperatures such as those found in existing coal gasifying plants in power plants for energy generation. These atmospheres are complex gas mixtures that contain sulfur and oxygen, among other compounds. Sulphides are thermodynamically less stable, have lower melting points and often have larger deviations from stoichiometry compared to the corresponding oxides. Although there are studies regarding the use of refractory metals in high temperature sulphidizing atmospheres, the use of niobium compounds has not been adequately evaluated and there is very little studies available in the literature about its use as a protective coating. The aim of this study was to evaluate the effect of a niobium film, deposited by magnetron sputtering on the isothermal sulphidation behavior of Fe-20Cr and Fe-20Cr-1Y alloys. The sulphidation tests were carried out at 500, 600 and 700° C for 2h in H2/2% H2S atmosphere. The sulphidation resistance was determined by mass gain per unit area. The sulphidation behavior of the coated and uncoated alloys was similar at 500ºC, and none of the alloys spalled. At 700ºC FeCr alloy scalled in the form of a fine powder, while the reaction product formed on the alloy FeCrY scalled in the form of plates. The effect of niobium became pronounced at 700°C. The reaction product layer formed on the coated alloy was thinner andmore plastic than that formed on the uncoated alloy. The mass gain per unit area of the coated alloys decreased significantly and they did not scaled.

Nióbio e suas ligas são utilizados atualmente em muitas aplicações industriais por oferecerem excelente resistência à degradação em diversos meios corrosivos. Estes meios incluem atmosferas gasosas em temperaturas elevadas, como as encontradas em plantas de gaseificação de carvão existentes em usinas termelétricas para geração de energia. As atmosferas encontradas nestes meios são misturas gasosas complexasque contêm, entre outros compostos, oxigênio e enxofre. Os sulfetos são compostos menos estáveis, possuem pontos de fusão mais baixos e apresentam, freqüentemente, maiores desvios de estequiometria em relação ao óxido correspondente. Apesar de existirem estudos relacionados à aplicação de metais refratários em atmosferas sulfetantes a temperaturas elevadas, o uso de compostos de nióbio ainda não foi devidamente avaliado como revestimento protetor, havendo poucos dados disponíveis na literatura. O objetivo deste trabalho foi avaliar o efeito proporcionado por um filme de nióbio, obtido por pulverização catódica,sobre o comportamento de sulfetação isotérmica das ligas Fe-20Cr e Fe-20Cr-1Y.Os testes de sulfetação foram realizados a 500, 600 e 700°C pelo período de 2h em atmosfera H2/2%H2S. A avaliação da resistência à sulfetação foi feita por meio do ganho de massa por unidade de área exposta. Observou-se que o comportamento de sulfetação a 500ºC das ligas FeCr e FeCrY sem e com revestimento é similar. Nesta condição, nenhuma das ligas sofreu escamação. A 700ºC a liga FeCr sofreu leve escamação na forma de um pó fino, enquanto que o produto de reação formado sobre a liga FeCrY escamou na forma de placas. O efeito do nióbio se torna pronunciado a 700ºC. A camada de produto de reação formada sobre as ligas revestidas é mais fina e plástica que na liga sem revestimento. O ganho de massa por unidade de área diminuiu sensivelmente para as ligas recobertas, que não sofreram escamação. / Niobium and niobium based alloys are currently used in many industrial applications because they offer excellent resistance to degradation in various corrosive environments. These media include gaseous atmospheres at high temperatures such as those found in existing coal gasifying plants in power plants for energy generation. These atmospheres are complex gas mixtures that contain sulfur and oxygen, among other compounds. Sulphides are thermodynamically less stable, have lower melting points and often have larger deviations from stoichiometry compared to the corresponding oxides. Although there are studies regarding the use of refractory metals in high temperature sulphidizing atmospheres, the use of niobium compounds has not been adequately evaluated and there is very little studies available in the literature about its use as a protective coating. The aim of this study was to evaluate the effect of a niobium film, deposited by magnetron sputtering on the isothermal sulphidation behavior of Fe-20Cr and Fe-20Cr-1Y alloys. The sulphidation tests were carried out at 500, 600 and 700° C for 2h in H2/2% H2S atmosphere. The sulphidation resistance was determined by mass gain per unit area. The sulphidation behavior of the coated and uncoated alloys was similar at 500ºC, and none of the alloys spalled. At 700ºC FeCr alloy scalled in the form of a fine powder, while the reaction product formed on the alloy FeCrY scalled in the form of plates. The effect of niobium became pronounced at 700°C. The reaction product layer formed on the coated alloy was thinner andmore plastic than that formed on the uncoated alloy. The mass gain per unit area of the coated alloys decreased significantly and they did not scaled.

The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

Este trabalho investigou a influência do tipo de erodente à base de alumina na incrustação em um revestimento metálico à base de FeCr, aspergido por arco elétrico, empregados em ensaios de desgaste erosivo, tanto à temperatura ambiente como a 400°C, com ângulo de incidência entre o erodente e a superfície de 30° e 90° e velocidade de projeção de 25 m/s. Como erodente, utilizou-se alumina eletrofundida com faces anguladas e irregulares e também alumina calcinada com formando aglomerados esferoides. O revestimento dos corpos-de-prova foi caracterizado quanto à morfologia (MEV), porosidade, densidade aparente, análise térmica, espessura da camada depositada, taxa de erosão e mapeamento de elementos por espectrometria de energia dispersiva (EDS). Os erodentes foram caracterizados quanto a sua morfologia (MEV), distribuição granulométrica e área superficial (BET). Os resultados mostraram que à temperatura ambiente os ensaios realizados com alumina calcinada com ângulo de 30° e alumina eletrofundida a 90° foram os que apresentaram maiores quantidades de alumínio incrustado no revestimento para uma mesma área de análise. Os ensaios realizados com a alumina eletrofundida com ângulo de 30° foi a que apresentou a maior taxa de erosão. Já a distribuição granulométrica e área superficial dos erodentes após ensaio de erosão apresentaram uma diminuição em relação aos valores de antes do ensaio. Os ensaios realizados a 400°C de temperatura mostraram que a alumina calcinada, para os dois ângulos de ensaio, resultou em maior incrustação no revestimento ensaiado, sendo maior para o ângulo de 90° do que para o ângulo de 30°. Para essa temperatura de ensaio, a maior taxa de erosão ocorreu para o ensaio conduzido com ângulo de 30°, utilizando alumina calcinada. Ainda para os ensaios a 400°C, os resultados para o tamanho médio de partícula na distribuição granulométrica indicaram uma redução nos valores iniciais para todos os ensaios realizados. No entanto, a área superficial de ambos erodentes permaneceu com valores muito próximos ao de antes do ensaio. / This work investigated the influence of the kind of erodent based on alumina embedded in a metallic coating based on FeCr, sprayed by arc electric technique, used in erosive wear test at room temperature and 400°C with angle of incidence between the erodent and the surface of 30° and 90° and erodent velocity of 25 m/s. As erodent was used fused alumina that showed angled and irregular surfaces and also calcined alumina forming spheroids agglomerates. The coating of the samples was characterized morphology (SEM), porosity, density, thermal analysis, the layer thickness, erosion rate and mapping of elements by energy dispersive spectrometry (EDS). The erodent was characterized by their morphology (SEM), particle size distribution and surface area (BET). The results showed that the room temperature tests performed with alumina calcined with angle of 30° and fused alumina with angle of 90° were those with larger amounts of aluminum embedded in the coating to the same area of analysis. Tests performed with the electro alumina with angle of 30° were presented the highest rate of erosion. Already the particle size distribution and surface area of erodent after testing erosion showed a decrease compared to the values before the test. The tests performed at 400°C temperature showed that the calcined alumina for the both angles test resulted in greater embedded of aluminum in the tested coating, being higher for the 90° angle than the angle of 30°. For this test temperature, the higher erosion rate occurred for the experiment with 30° angle using calcined alumina. Also for the tests at 400°C, the results for the average particle size in the particle size distribution showed a reduction in initial values for all tests. However, the surface area of erodent remained with both values very close to that of before the test.

Este trabalho investigou a influência do tipo de erodente à base de alumina na incrustação em um revestimento metálico à base de FeCr, aspergido por arco elétrico, empregados em ensaios de desgaste erosivo, tanto à temperatura ambiente como a 400°C, com ângulo de incidência entre o erodente e a superfície de 30° e 90° e velocidade de projeção de 25 m/s. Como erodente, utilizou-se alumina eletrofundida com faces anguladas e irregulares e também alumina calcinada com formando aglomerados esferoides. O revestimento dos corpos-de-prova foi caracterizado quanto à morfologia (MEV), porosidade, densidade aparente, análise térmica, espessura da camada depositada, taxa de erosão e mapeamento de elementos por espectrometria de energia dispersiva (EDS). Os erodentes foram caracterizados quanto a sua morfologia (MEV), distribuição granulométrica e área superficial (BET). Os resultados mostraram que à temperatura ambiente os ensaios realizados com alumina calcinada com ângulo de 30° e alumina eletrofundida a 90° foram os que apresentaram maiores quantidades de alumínio incrustado no revestimento para uma mesma área de análise. Os ensaios realizados com a alumina eletrofundida com ângulo de 30° foi a que apresentou a maior taxa de erosão. Já a distribuição granulométrica e área superficial dos erodentes após ensaio de erosão apresentaram uma diminuição em relação aos valores de antes do ensaio. Os ensaios realizados a 400°C de temperatura mostraram que a alumina calcinada, para os dois ângulos de ensaio, resultou em maior incrustação no revestimento ensaiado, sendo maior para o ângulo de 90° do que para o ângulo de 30°. Para essa temperatura de ensaio, a maior taxa de erosão ocorreu para o ensaio conduzido com ângulo de 30°, utilizando alumina calcinada. Ainda para os ensaios a 400°C, os resultados para o tamanho médio de partícula na distribuição granulométrica indicaram uma redução nos valores iniciais para todos os ensaios realizados. No entanto, a área superficial de ambos erodentes permaneceu com valores muito próximos ao de antes do ensaio. / This work investigated the influence of the kind of erodent based on alumina embedded in a metallic coating based on FeCr, sprayed by arc electric technique, used in erosive wear test at room temperature and 400°C with angle of incidence between the erodent and the surface of 30° and 90° and erodent velocity of 25 m/s. As erodent was used fused alumina that showed angled and irregular surfaces and also calcined alumina forming spheroids agglomerates. The coating of the samples was characterized morphology (SEM), porosity, density, thermal analysis, the layer thickness, erosion rate and mapping of elements by energy dispersive spectrometry (EDS). The erodent was characterized by their morphology (SEM), particle size distribution and surface area (BET). The results showed that the room temperature tests performed with alumina calcined with angle of 30° and fused alumina with angle of 90° were those with larger amounts of aluminum embedded in the coating to the same area of analysis. Tests performed with the electro alumina with angle of 30° were presented the highest rate of erosion. Already the particle size distribution and surface area of erodent after testing erosion showed a decrease compared to the values before the test. The tests performed at 400°C temperature showed that the calcined alumina for the both angles test resulted in greater embedded of aluminum in the tested coating, being higher for the 90° angle than the angle of 30°. For this test temperature, the higher erosion rate occurred for the experiment with 30° angle using calcined alumina. Also for the tests at 400°C, the results for the average particle size in the particle size distribution showed a reduction in initial values for all tests. However, the surface area of erodent remained with both values very close to that of before the test.

Este trabalho investigou a influência do tipo de erodente à base de alumina na incrustação em um revestimento metálico à base de FeCr, aspergido por arco elétrico, empregados em ensaios de desgaste erosivo, tanto à temperatura ambiente como a 400°C, com ângulo de incidência entre o erodente e a superfície de 30° e 90° e velocidade de projeção de 25 m/s. Como erodente, utilizou-se alumina eletrofundida com faces anguladas e irregulares e também alumina calcinada com formando aglomerados esferoides. O revestimento dos corpos-de-prova foi caracterizado quanto à morfologia (MEV), porosidade, densidade aparente, análise térmica, espessura da camada depositada, taxa de erosão e mapeamento de elementos por espectrometria de energia dispersiva (EDS). Os erodentes foram caracterizados quanto a sua morfologia (MEV), distribuição granulométrica e área superficial (BET). Os resultados mostraram que à temperatura ambiente os ensaios realizados com alumina calcinada com ângulo de 30° e alumina eletrofundida a 90° foram os que apresentaram maiores quantidades de alumínio incrustado no revestimento para uma mesma área de análise. Os ensaios realizados com a alumina eletrofundida com ângulo de 30° foi a que apresentou a maior taxa de erosão. Já a distribuição granulométrica e área superficial dos erodentes após ensaio de erosão apresentaram uma diminuição em relação aos valores de antes do ensaio. Os ensaios realizados a 400°C de temperatura mostraram que a alumina calcinada, para os dois ângulos de ensaio, resultou em maior incrustação no revestimento ensaiado, sendo maior para o ângulo de 90° do que para o ângulo de 30°. Para essa temperatura de ensaio, a maior taxa de erosão ocorreu para o ensaio conduzido com ângulo de 30°, utilizando alumina calcinada. Ainda para os ensaios a 400°C, os resultados para o tamanho médio de partícula na distribuição granulométrica indicaram uma redução nos valores iniciais para todos os ensaios realizados. No entanto, a área superficial de ambos erodentes permaneceu com valores muito próximos ao de antes do ensaio. / This work investigated the influence of the kind of erodent based on alumina embedded in a metallic coating based on FeCr, sprayed by arc electric technique, used in erosive wear test at room temperature and 400°C with angle of incidence between the erodent and the surface of 30° and 90° and erodent velocity of 25 m/s. As erodent was used fused alumina that showed angled and irregular surfaces and also calcined alumina forming spheroids agglomerates. The coating of the samples was characterized morphology (SEM), porosity, density, thermal analysis, the layer thickness, erosion rate and mapping of elements by energy dispersive spectrometry (EDS). The erodent was characterized by their morphology (SEM), particle size distribution and surface area (BET). The results showed that the room temperature tests performed with alumina calcined with angle of 30° and fused alumina with angle of 90° were those with larger amounts of aluminum embedded in the coating to the same area of analysis. Tests performed with the electro alumina with angle of 30° were presented the highest rate of erosion. Already the particle size distribution and surface area of erodent after testing erosion showed a decrease compared to the values before the test. The tests performed at 400°C temperature showed that the calcined alumina for the both angles test resulted in greater embedded of aluminum in the tested coating, being higher for the 90° angle than the angle of 30°. For this test temperature, the higher erosion rate occurred for the experiment with 30° angle using calcined alumina. Also for the tests at 400°C, the results for the average particle size in the particle size distribution showed a reduction in initial values for all tests. However, the surface area of erodent remained with both values very close to that of before the test.

abstract: The passivity of metals is a phenomenon of vast importance as it prevents many materials in important applications from rapid deterioration by corrosion. Alloying with a sufficient quantity of passivating elements (Cr, Al, Si), typically in the range of 10% - 20%, is commonly employed to improve the corrosion resistance of elemental metals. However, the compositional criteria for enhanced corrosion resistance have been a long-standing unanswered question for alloys design. With the emerging interest in multi-principal element alloy design, a percolation model is developed herein for the initial stage of passive film formation, termed primary passivation. The successful validation of the assumptions and predictions of the model in three corrosion-resistant binary alloys, Fe-Cr, Ni-Cr, and Cu-Rh supports that the model which can be used to provide a quantitative design strategy for designing corrosion-resistant alloys. To date, this is the only model that can provide such criteria for alloy design.The model relates alloy passivation to site percolation of the passivating elements in the alloy matrix. In the initial passivation stage, Fe (Ni in Ni-Cr or Cu in Cu-Rh) is selectively dissolved, destroying the passive network built up by Cr (or Rh) oxides and undercutting isolated incipient Cr (Rh) oxide nuclei. The only way to prevent undercutting and form a stable protective passive film is if the concentration of Cr (Rh) is high enough to realize site percolation within the thickness of the passive film or the dissolution depth. This 2D-3D percolation cross-over transition explains the compositional dependent passivation of these alloys. The theoretical description of the transition and its assumptions is examined via experiments and kinetic Monte Carlo simulations. The initial passivation scenario of the dissolution selectivity is validated by the inductively coupled plasma mass spectrum (ICP-MS). The electronic effect not considered in the kinetic Monte Carlo simulations is addressed by density functional theory (DFT). Additionally, the impact of the atomic configuration parameter on alloy passivation is experimentally measured, which turns out to agree well with the model predictions developed using Monte Carlo renormalization group (MC-RNG) methods. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

La croissance de couches minces d'oxydes sur les alliages métalliques et les métaux purs est un phénomène ayant fait l'objet d'un grand nombre d'études expérimentales. Les structures des couches d'oxydes sont bien connues, ainsi que les modèles mathématiques servant à modéliser les aspects macroscopiques de la croissance. Cependant, les détails des mécanismes de germination de la couche d'oxyde dans les premiers stades de la corrosion ainsi que sa croissance ultérieure demeurent peu ou mal connus. La simulation atomistique apparaît comme une alternative pour évaluer les différents mécanismes proposés et appréhender l'influence des différents paramètres physico-chimiques. Le développement d'un tel outil de simulation a démarré au LPCS avec la thèse de M. Legrand. En se basant sur l'exemple de l'alliage FeCr, un modèle informatique tridimensionnel dit "modèle de Legrand", permettant de simuler la dissolution sélective et la passivation des alliages binaires a été réalisé. L'évolution dynamique est basée sur une technique de type Monte Carlo classique. Le logiciel permet de simuler l'évolution d'un alliage quelconque, d'une composition et d'une structure cristallographique donnée. Il prend en compte la diffusion des atomes sur la surface, leur dissolution et le blocage de la dissolution par formation d'une couche de passivation. Cet outil était adapté pour la simulation des premiers stades de la corrosion. L'objectif de ce travail est d'améliorer ce modèle existant, afin de simuler l'évolution de la couche passive sur une échelle de temps plus longue. A l'issue de ce travail, de nombreux apports ont été effectués. Ainsi, l'introduction d'un champ de force MEAM (Modified Embedded Atom Method) pour le calcul des barrières de diffusion et de dissolution, a permis de remplacer les probabilités de diffusion empiriques par des probabilités calculées, et de mettre en évidence la diffusion préférentielle des Cr vers leurs semblables. L'introduction d'une dynamique de simulation Monte Carlo Cinétique (KMC) a permis une prise en compte réaliste de l'évolution cinétique du modèle avec des temps de simulation reliés au temps réel. Enfin Un second réseau cristallographique RVO (réseau virtuel d'oxyde) tridimensionnel, correspondant à celui de la couche passive (Cr2O3) a été implémenté, ainsi qu'une interface graphique pour un meilleur suivi de la simulation. Les résultats obtenus lors des simulations sont en accord avec les observations expérimentales: passivation totale à partir du Fe-16Cr, enrichissement en Cr de la couche passive, allures des courbes cinétiques, influence du champ électrique, mise en évidence l'apparition de cavités sous la couche passive.