Pesquisas sobre a tenacidade à fratura dos aços ferríticos mostram uma grande dispersão dos resultados quando avaliados na região de transição dúctil-fragil. Esta dispersão é fortemente influenciada pela temperatura de ensaio, dimensões e geometria dos corpos-de-prova e também pelo nível de restrições plástica na ponta da trinca. Tais fatores dificultam a previsão, a partir de valores experimentais, de valores de tenacidade à fratura de aços ferríticos para aplicações em casos práticos. Uma forma de contornar essa dificuldade é através do uso das curvas de referencia, descritas no Código ASME. Estas curvas representam envoltórias inferiores de tenacidade à fratura obtida a partir de ensaios envolvendo diversos tipos de aços. Portanto os valores de tenacidade estabelecidos por essas curvas são, em geral, muito conservadores. Então foi proposta pela ASTM uma nova metodologia, chamada curva Mestra, que trata estatisticamente o comportamento à fratura dos aços ferríticos na região de transição e caracteriza um material em particular, através de um parâmetro denominado Temperatura de Referencia (T0). Nesta pesquisa, avaliou-se a influencia da sensibilidade dos parâmetros: Kmin, m e M envolvidos no procedimento do calculo de um parâmetro denominado temperatura de referencia. (T0). A metodologia da curva mestra foi aplicada através dos dados (experimentos) do euro-teste , para as temperaturas: -91 ºC, -60°C, -40°C e 20°C . Em análises de sensibilidade aos parâmetros com os seguintes valores kmin = 0, 10, 30; m= (3), (3,5), (4,5), (5,0) e M = 40, 50, 60. Os resultados apresentados são compatíveis comprovando a eficiência da metodologia para avaliação da tenacidade à fratura dos aços ferríticos na região de transição. Portanto, nestas condições, podemos afirmar que o conceito da curva mestra foi, realmente validado. / The caracterization of the fracture behavior in the ductile-to-brittle transition for ferritic steels is a hard task because fracture toughness is a strong function of temperature in the transition, with the toughness values increasing rapidly over a relatively narrow temperature baud/range and therefore cannot be easily used to evaluate integrity in structural components because of the uncertainty in how to handle these teste results. To overcome this problem in practice, the ASME code has provided reference curves that give estimates of toughness versus temperature. These curves represent lower envelopes to a large set of fracture toughness experimental data for several heats of steel . Therefore, the fracture toughness values obtained from these curves are in general too conservative. In the last decade, a new methodology, formalized in the ASTM standard method E1921-97, has revolutionized the approach used to caracterize transition fracture behavior and has given a rationale for treating the several factors that influence the scatter in the results. Statistical models are used to define a transition curve, called Master Curve, and the transition temperature of a given material is stated by a parameter called reference temperature (T0). In this research, it was evaluated the sensitivity influence of the parameter: Kmin, m and M, involved in the to measurement procedure. The master curve methodology was applied over the data (experiments) of EuroTest for the following temperatures: - 91°C, -60°C, -40°C and -20°C. A parameters sensitivity analysis was made with following values: Kmin=0, 10, 30; m=(3), (3,5), (4,5), (5,0) and M=40, 50, 60. The results are compatible, which confirm the efficiency of the methodology for evaluating the toughness to ferritic steel fracture in the transition region. Therefore, in these conditions, we can state the master curve concept has indeed been validated.

AgÃncia Nacional do PetrÃleo / Os elevados teores de enxofre dos petrÃleos processados nas unidades de refino atacam o âcladâ de aÃo AISI 405 ou 410S, expondo o aÃo estrutural ao meio corrosivo. A recuperaÃÃo da regiÃo desgastada à feita pela aplicaÃÃo de um âliningâ de aÃo AISI 316L. Embora o aÃo AISI 316L garanta uma boa resistÃncia à corrosÃo naftÃnica, surgem trincas na zona afetada pelo calor da solda ( ZAC) apÃs um determinado perÃodo de operaÃÃo da unidade, associadas a problemas metalÃrgicos na ZAC e aos esforÃos de dilataÃÃo e contraÃÃo do conjnto âliningâ e parede da torre. Uma alternativa seria a aplicaÃÃo de um âliningâ de aÃo AISI 444 que tem resistÃncia à corrosÃo comparÃvel à do aÃo AISI 316L e coeficiente de expansÃo tÃrmica mais prÃximo do coeficiente do prÃprio material da torre. Contudo, ainda nÃo sÃo conhecidos os efeitos sobre o desempenho deste aÃo nas condiÃÃes de operaÃÃo da torre. Assim, neste trabalho estudou-se a viabilidade da aplicaÃÃo de um âliningâ de aÃo AISI 444 para a recuperaÃÃo da torre de destilaÃÃo em substituiÃÃo ao aÃo AISI 316L. Para tanto, foram avaliadas as condiÃÃes de fragilizaÃÃo do aÃo AISI 444 na temperatura mÃxima da torre ( em torno de 400ÂC) e na temperatura de 475ÂC, atravÃs da mediÃÃo da dureza Brinell e do ensaio de impacto Charpy-V. Corpos de prova de aÃo AISI 444 e AISI 316L soldados sobre chapas de aÃo ASTM A516 Gr60 foram submetidos a ciclos de Fadiga TÃrmica e, apÃs cada ciclo (20 ao todo), passaram por uma inspeÃÃo para verificar a existÃncia de trincas. Logo apÃs foi feita a caracterizaÃÃo microestrutural da ZAC. TambÃm foram retiradas amostras apÃs os ensaios de Fadiga TÃrmica para serem submetidas a tratamentos em petrÃleo na temperatura de 300 C. ApÃs o tratamento em petrÃleo, as amostras passaram por uma avaliaÃÃo no microscÃpio eletrÃnica de varredura. Foram medidas as massas dos corpos de prova antes e apÃs o tratamento em petrÃleo para determinar a perda de massa provocada pelo ambiente corrosivo. Os resultados indicam que a submissÃo do aÃo AISI 444 ao tratamento tÃrmico, nas temperaturas de 400 a 475ÂC, causa a fragilizaÃÃo do mesmo e um aumento da temperatura de transiÃÃo dÃctil frÃgil para valores acima de 30 C, mas abaixo de 60 C. Os aÃos AISI 316L e AISI 444 nÃo apresentam trincas apÃs os ensaios de Fadiga TÃrmica e nem apÃs o tratamento em petrÃleo. O uso do aÃo AISI 444 pode representar uma reduÃÃo nos custos nas paradas das torres de destilaÃÃo uma vez que este apresentou menores taxas de corrosÃo que o aÃo AISI 316L. / Os elevados teores de enxofre dos petrÃleos processados nas unidades de refino atacam o âcladâ de aÃo AISI 405 ou 410S, expondo o aÃo estrutural ao meio corrosivo. A recuperaÃÃo da regiÃo desgastada à feita pela aplicaÃÃo de um âliningâ de aÃo AISI 316L. Embora o aÃo AISI 316L garanta uma boa resistÃncia à corrosÃo naftÃnica, surgem trincas na zona afetada pelo calor da solda ( ZAC) apÃs um determinado perÃodo de operaÃÃo da unidade, associadas a problemas metalÃrgicos na ZAC e aos esforÃos de dilataÃÃo e contraÃÃo do conjnto âliningâ e parede da torre. Uma alternativa seria a aplicaÃÃo de um âliningâ de aÃo AISI 444 que tem resistÃncia à corrosÃo comparÃvel à do aÃo AISI 316L e coeficiente de expansÃo tÃrmica mais prÃximo do coeficiente do prÃprio material da torre. Contudo, ainda nÃo sÃo conhecidos os efeitos sobre o desempenho deste aÃo nas condiÃÃes de operaÃÃo da torre. Assim, neste trabalho estudou-se a viabilidade da aplicaÃÃo de um âliningâ de aÃo AISI 444 para a recuperaÃÃo da torre de destilaÃÃo em substituiÃÃo ao aÃo AISI 316L. Para tanto, foram avaliadas as condiÃÃes de fragilizaÃÃo do aÃo AISI 444 na temperatura mÃxima da torre ( em torno de 400ÂC) e na temperatura de 475ÂC, atravÃs da mediÃÃo da dureza Brinell e do ensaio de impacto Charpy-V. Corpos de prova de aÃo AISI 444 e AISI 316L soldados sobre chapas de aÃo ASTM A516 Gr60 foram submetidos a ciclos de Fadiga TÃrmica e, apÃs cada ciclo (20 ao todo), passaram por uma inspeÃÃo para verificar a existÃncia de trincas. Logo apÃs foi feita a caracterizaÃÃo microestrutural da ZAC. TambÃm foram retiradas amostras apÃs os ensaios de Fadiga TÃrmica para serem submetidas a tratamentos em petrÃleo na temperatura de 300 C. ApÃs o tratamento em petrÃleo, as amostras passaram por uma avaliaÃÃo no microscÃpio eletrÃnica de varredura. Foram medidas as massas dos corpos de prova antes e apÃs o tratamento em petrÃleo para determinar a perda de massa provocada pelo ambiente corrosivo. Os resultados indicam que a submissÃo do aÃo AISI 444 ao tratamento tÃrmico, nas temperaturas de 400 a 475ÂC, causa a fragilizaÃÃo do mesmo e um aumento da temperatura de transiÃÃo dÃctil frÃgil para valores acima de 30 C, mas abaixo de 60 C. Os aÃos AISI 316L e AISI 444 nÃo apresentam trincas apÃs os ensaios de Fadiga TÃrmica e nem apÃs o tratamento em petrÃleo. O uso do aÃo AISI 444 pode representar uma reduÃÃo nos custos nas paradas das torres de destilaÃÃo uma vez que este apresentou menores taxas de corrosÃo que o aÃo AISI 316L. / The high sulfur content of oil processed in the refining units attack the "clad" steel AISI 405 or 410S, exposing the structural steel to the corrosive medium. The recovery of the eroded region is made by applying a "lining" of AISI 316L steel. Although steel AISI 316L ensure good corrosion resistance naphthenic, cracks appear in the heat affected zone of the weld (HAZ) after a certain period of operation of the unit, metallurgical problems associated with the HAZ and the efforts of expansion and contraction of conjnto " lining "of the tower and wall. An alternative would be the application of a "lining" of AISI 444 steel having corrosion resistance comparable to the AISI 316L steel and the thermal expansion coefficient closer to the coefficient of the material itself of the tower. However, are not yet known effects on the performance of the steel in the conditions of operation of the tower. In this work we studied the feasibility of applying a "lining" steel AISI 444 for the recovery of the distillation tower to replace the steel AISI 316L. Thus, we evaluated the conditions of embrittlement of AISI 444 in the maximum temperature of the tower (about 400  C) and temperature of 475  C, by measuring the Brinell hardness and Charpy impact test-V. Specimens of AISI 444 and AISI 316L welded onto steel plates ASTM A516 Gr60 were subjected to thermal fatigue cycles and after each cycle (20 in all), passed an inspection to check for cracks. Soon after it was made microstructural characterization of ZAC. Also samples were taken after the thermal fatigue tests in order to undergo treatment in oil at a temperature of 300  C. After treatment in oil, the samples underwent an evaluation in the scanning electron microscope. Were measured masses of the samples before and after treatment in oil to determine the weight loss caused by the corrosive environment. The results indicate that the subjection of the AISI 444 steel to thermal treatment at temperatures 400-475  C, causes embrittlement of the same and increasing the temperature of transition ductile brittle to values ​​above 30  C but below 60  C. The AISI 316L and AISI 444 do not exhibit cracks after the tests and Thermal Fatigue or after treatment in oil. The use of steel AISI 444 may represent a cost savings in the charts of distillation towers since it showed the lowest corrosion rates than steel AISI 316L. / The high sulfur content of oil processed in the refining units attack the "clad" steel AISI 405 or 410S, exposing the structural steel to the corrosive medium. The recovery of the eroded region is made by applying a "lining" of AISI 316L steel. Although steel AISI 316L ensure good corrosion resistance naphthenic, cracks appear in the heat affected zone of the weld (HAZ) after a certain period of operation of the unit, metallurgical problems associated with the HAZ and the efforts of expansion and contraction of conjnto " lining "of the tower and wall. An alternative would be the application of a "lining" of AISI 444 steel having corrosion resistance comparable to the AISI 316L steel and the thermal expansion coefficient closer to the coefficient of the material itself of the tower. However, are not yet known effects on the performance of the steel in the conditions of operation of the tower. In this work we studied the feasibility of applying a "lining" steel AISI 444 for the recovery of the distillation tower to replace the steel AISI 316L. Thus, we evaluated the conditions of embrittlement of AISI 444 in the maximum temperature of the tower (about 400  C) and temperature of 475  C, by measuring the Brinell hardness and Charpy impact test-V. Specimens of AISI 444 and AISI 316L welded onto steel plates ASTM A516 Gr60 were subjected to thermal fatigue cycles and after each cycle (20 in all), passed an inspection to check for cracks. Soon after it was made microstructural characterization of ZAC. Also samples were taken after the thermal fatigue tests in order to undergo treatment in oil at a temperature of 300  C. After treatment in oil, the samples underwent an evaluation in the scanning electron microscope. Were measured masses of the samples before and after treatment in oil to determine the weight loss caused by the corrosive environment. The results indicate that the subjection of the AISI 444 steel to thermal treatment at temperatures 400-475  C, causes embrittlement of the same and increasing the temperature of transition ductile brittle to values ​​above 30  C but below 60  C. The AISI 316L and AISI 444 do not exhibit cracks after the tests and Thermal Fatigue or after treatment in oil. The use of steel AISI 444 may represent a cost savings in the charts of distillation towers since it showed the lowest corrosion rates than steel AISI 316L.

Abstract Stabilized ferritic stainless steel grades are attractive alternatives to common austenitic grades in sheet metal applications. Compared with older unstabilized ferritic grades, the mechanical and corrosion properties are usually improved. The impurity level, mainly the amount of interstitial carbon and nitrogen, plays an important role in these steels. There are notable issues in the welding of these steels, the most apparent difference to austenitic steels is the susceptibility to brittle failure. This research focused on the influence of minor elements, especially aluminium, calcium, silicon, titanium, niobium, nitrogen and oxygen, on the weldability of modern intermediate purity level stabilized ferritic stainless steels. The research proceeded in several stages. At first, the general characteristics and performance data about the welds in currently manufactured 11 to 21 mass percent chromium ferritic stainless steels in Europe was obtained. The research then focused on novel high chromium stabilized ferritic stainless steels. Lastly, the influence of various steelmaking practices on weldability were investigated. The results showed that in stabilized ferritic stainless steels, slag islands are frequently seen in the molten weld pools. These islands can have many origins, e.g. deoxidation, calcium treatment and stabilization practices, and they can be roughly assessed from the chemical composition of the steel. The nature and the influence of these slags varies and can be related to irregularities in the weldability and molten metal fluid flow. Large grain size and titanium carbonitride particles impair the toughness of the heat-affected zone. Generally, stabilization with niobium is preferred. However, solely niobium stabilized steel welds run the risk of forming coarse columnar grains in welds deteriorating some of the properties. A breakdown of the columnar grains is possible to achieve in autogenous welds with minor titanium and aluminium alloying, provided that small amounts of nitrogen and oxygen are induced from the shielding gas. However, grain refinement may not improve the properties, if it is accomplished with an increase in the total interstitial content. / Tiivistelmä Stabiloidut ferriittiset ruostumattomat teräkset soveltuvat korvaamaan tavanomaisia austeniittisia ruostumattomia teräksiä ohutlevysovelluksissa. Näillä teräksillä keskeiset mekaaniset ja korroosio-ominaisuudet ovat usein paremmat kuin varhaisilla, stabiloimattomilla ferriittisillä teräksillä. Hiili ja typpi ovat näissä teräksissä kuitenkin epäpuhtauksia. Toisin kuin austeniittiset teräkset, ferriittiset teräkset ovat alttiita haurasmurtumalle, erityisesti hitsatuissa rakenteissa. Tässä väitöstutkimuksessa keskityttiin mikroseosaineiden ja epäpuhtauksien vaikutukseen keskipuhtaiden stabiloitujen ferriittisten teräslajien hitsauksessa. Tutkimus kohdistui erityisesti alumiinin, kalsiumin, piin, titaanin, niobin, typen ja hapen vaikutuksiin. Aluksi tutkittiin kaupallisten terästen hitsien keskeisiä ominaisuuksia. Tämän jälkeen tutkittiin uusia ns. korkeakromisia stabiloituja ferriittisiä teräslajeja. Lopuksi tutkittiin teräksen valmistuksen vaikutuksia stabiloitujen ferriittisten ruostumattomien terästen hitsattavuuteen. Tutkituilla teräksillä hitsauksen aikana muodostui runsaasti kuonalauttoja. Näillä kuonilla on monta alkuperää, esim. deoksidointi, kalsiumkäsittely ja stabilointiaineet. Hitsien kuonaisuutta voidaan karkeasti arvioida teräksen kemiallisen koostumuksen perusteella. Muodostuvilla kuonilla on useita vaikutuksia hitsauksessa, mm. epäjatkuvuuksiin ja sulan virtauksiin. Hitsauksessa muodostuva suuri raekoko ja stabiloinnin titaanikarbonitridipartikkelit heikentävät oleellisesti hitsin muutosvyöhykkeen sitkeyttä. Stabilointi käyttäen pääasiassa niobia on toivottavaa, mutta jos stabilointiin käytetään vain niobia, tulee hitsin mikrorakenteesta karkea ja hitsin ominaisuudet voivat heikentyä. Karkean mikrorakenteen hienontaminen on mahdollista käyttäen suojakaasuna argonia, jossa on hieman typpeä ja happea, mikäli teräkseen on seostettu hieman alumiinia ja titaania. Raerakenteen hienontaminen ei kuitenkaan yksiselitteisesti paranna hitsin ominaisuuksia, mikäli hienontaminen saavutetaan kasvattamalla epäpuhtauspitoisuutta tarpeettoman korkeaksi.

Orientador: Prof. Dr. Renato Altobelli Antunes / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2016. / Os aços inoxidáveis são susceptíveis à corrosão por pite quando expostos à ambiente contendo íons agressivos. Esse fenômeno ocorre devido à quebra do filme passivo. O material estudado neste trabalho foi o aço inoxidável AISI 409. O comportamento de corrosão e a estabilidade do filme passivo foram investigados por ensaios eletroquímicos, utilizando as técnicas de espectroscopia de impedância eletroquímica, polarização potenciodinâmica, análise de Mott-Schotky e cronoamporometria. Os testes foram realizados em solução de 0,1 M de NaCl. Os pites formados foram visualizados por microscopia confocal a laser e tiveram suas dimensões medidas. Análise com MEV da amostra antes e após o ensaio de polarização foi realizado e locais de ocorrência dos pites foi registrado. Foram analisadas amostras na condição como-recebida e na condição solubilizada. O tratamento de solubilização foi realizado na temperatura de 1100 °C por 30 minutos, com o objetivo de homogeneizar a microestrutura dos materiais. Os resultados obtidos foram analisados e discutidos, dando ênfase para a compreensão do processo de corrosão por pite do aço inoxidável AISI 409 nas condições comorecebida e solubilizada. Foi verificada a presença de precipitados ricos em titânio nas amostras. Na amostra como-recebida, os precipitados compostos por Ti (C,N) colaboraram para o início da corrosão localizada. Na amostra solubilizada os precipitados foram identificados como TiN e a ocorrência da corrosão por pite foi dificultada. / Stainless steels are susceptible to pitting corrosion when exposed to environment containing aggressive ions. This phenomenon occurs due to the breakdown of the passive film. Stainless steel AISI 409 was studied in this work. The corrosion behavior and the stability of the passive film were investigated by electrochemical tests, using electrochemical impedance spectroscopy, potentiodynamic polarization, Mott-Shottky analysis and choronoamperometry measurements. The tests were carried out in NaCl 0.1 M solution. The pits formed were observed and measured by confocal laser scanning microscopy. SEM images were carried out before and after the potentiodynamic polarization and the regions associated with pitting formation were recorded. Samples were analyzed in the as-received and solutionized conditions. The solution annealing treatment was performed at 1100 °C for 30 minutes in order to homogenize the microstructure of the materials. The results obtained were analyzed and discussed, giving emphasis to the understanding of the pitting corrosion behavior of the AISI 409 stainless steel in the as-received and solutionized states. The presence of titanium-rich precipitates in the samples was checked. In the as-received state, Ti (C,N) precipitates have contributed to the onset of pitting corrosion. For the solution annealed samples the precipitates were identified as TiN and the occurrence of pitting corrosion was difficult.

Les aciers inoxydables ferritiques sont actuellement les meilleurs candidats pour répondre au cahier des charges des matériaux destinés aux interconnexions de piles à combustibles à oxyde solide (SOFC acronyme anglo-saxon pour Solid Oxide Fuel Cell). Cependant, du coté du compartiment cathodique de ces piles, le phénomène de sublimation du chrome à haute température conduit à des dégradations importantes, réduisant ainsi la durée de vie en service des SOFC. Les objectifs de ce travail de thèse sont (i) d'étudier le phénomène de sublimation du chrome sur l'acier inoxydable ferritique AISI 441 et (ii) de rechercher le ou les moyen(s) d'atténuer cette même sublimation. Sur le deuxième point, des méthodes de protection ont été mises en œuvre, en particulier avec le dépôt de films minces de spinelle Mn-Co obtenues via un procédé de galvanoplastie ou bien encore en procédant à des pré-oxydations des alliages dans des atmosphères contrôlées de type argon impur ou mélanges gazeux équimolaires CO / CO2 (250 ° C et 850 ° C, pour une durée totale de 3 h).Concernant l'étude de la sublimation du chrome, des essais d'oxydation simulant les conditions de service ont été conduites dans des mélanges gazeux : 5% de O2 dans H2O à 800 °C pendant 96 h. A vitesse de gaz oxydants faible, de 1 à 3 cm / s, la sublimation du chrome est limitée par un phénomène de diffusion dans la phase gazeuse de l'espèce volatile oxo-hydroxyde de chrome. A vitesse plus élevée, de 3 à 10 cm / s, la sublimation du chrome semble limitée par un phénomène interfacial. La vitesse de sublimation apparait indépendante de la rugosité de surface des échantillons, elle même variant selon la préparation des échantillons. Du point de vue de la caractérisation morphologique des couches d'oxydation thermiques obtenues, sur les surfaces de plus forte rugosité (surface industrielle), nous avons noté le développement de nodules riches en titane et en niobium avec une partie externe et une autre interne. Dans le substrat, des phases de lave de type Fe2Nb ont été observées le long des joints de grain métalliques.Dans une deuxième partie, la sublimation du chrome a été étudiée sur échantillons revêtus ou pré-oxydés. Les films minces de spinelle Mn-Co ne conduisent pas à l'abaissement de la vitesse de sublimation du chrome et sont donc pas protecteurs. L'adhérence de ces revêtements est de mauvaise qualité. Les couches présentent de nombreuses fissures. La pré-oxydation conduit quant à elle à une réduction considérable (jusqu'à un facteur 10) de la vitesse de sublimation du chrome (sauf dans le cas de la pré-oxydation dans l'argon à 850 °C). La formation d'un film riche en fer obtenu à basse température (250 °C) peut expliquer cette réduction par l'établissement d'une barrière de diffusion. Cette même réduction est cependant surprenante sur les films riches en chrome obtenus par pré-oxydation à 850 °C dans CO / CO2. Nous proposons dans ce travail une interprétation originale basée sur les différences de nature semi-conductrice des films de chromine formées à haute pression d'oxygène (proche de l'atmosphère) et identifiés comme étant de type p par rapport à ceux obtenus à basse pression (dans CO/CO2) qui sont connu pour être de type n. Après l'oxydation à haute température de 96 heures, tous les échantillons préalablement pré-oxydés ont été observés comme étant composés d'oxyde de chrome et d'un spinelle Mn-Cr.Au terme de ce travail de thèse, il peut être conclu que la pré-oxydation de l'alliage 441 à basse température (250 °C) dans l'argon ou le mélange CO/CO2 ou encore à plus haute température (850 °C) dans le mélange CO/CO2 sont des traitements qui conduisent à l'abaissement de la vitesse de sublimation du chrome et par voie de conséquence à l'amélioration de la tenue de cet alliage en condition d'oxydation dans le compartiment cathodique des SOFC. / Ferritic stainless steels are the most attractive materials that are able to fulfil SOFC(Solid Oxide Fuel Cell) interconnect properties. However, in cathodic SOFC condition, Crvolatilisation from ferritic steels leads to degradations of interconnect and cathode materialsand shorter service lifetime of SOFC. The objectives of this work are (i) to study Crvolatilisation from AISI 441 ferritic stainless steel and (ii) to find the way out to suppress Crvolatilisation. The Cr volatilisation protective methods used in this work were coating withMn-Co spinel by an electroplating method and preoxidation in the condition of Ar or CO/CO2at either 250°C or 850°C, for 3 h. Cr volatilisation experiments were performed in 5%H2O inO2 at 800°C for 96 h. According to the results, it can be concluded that the preoxidation ofthe AISI 441 in Ar or CO/CO2 at low temperature (250°C) or in the CO/CO2 at a highertemperature (850°C) are treatments that lead to lowering the sublimation rate of the Cr andimprovement in the oxidation resistance of this alloy in the cathodic compartment of theSOFC.

Os aços inoxidáveis ferríticos são susceptíveis à corrosão intergranular após resfriamento rápido a partir de 950°C. A teoria de empobrecimento no teor de cromo nas vizinhanças do carboneto e/ou nitreto, precipitados nos contornos de grão, é o mecanismo mais aceito para descrever este fenômeno. O presente trabalho avalia o efeito dos tratamentos isotérmicos na resistência à corrosão intergranular do aço inoxidável ferrítico UNS S43000, utilizando o método de reativação eletroquímica potenciodinâmica na versão ciclo duplo (DL-EPR). As amostras foram solubilizadas a 1200°C e posteriormente tratadas isotermicamente a temperaturas entre 500°C e 700°C, por tempos de 5 minutos a 16 horas. O ensaio DL-EPR foi realizado em solução 0,5M H2SO4 com velocidade de varredura de 1,67 mV/s. As amostras foram examinadas em microscópio óptico e microscópio eletrônico de varredura após ensaio DL-EPR, Práticas W e X da norma ASTM A763 e ataque metalográfico com reagente Vilella. Foram obtidos diferentes valores de grau de sensitização em função do tempo de tratamento isotérmico. Análises por difração de raios X, sobre resíduos extraídos quimicamente identificaram precipitação de nitretos e de carbonetos de cromo, Cr2N e Cr23C6, respectivamente. As temperaturas de 550°C e 600°C mostraram dois máximos de grau de sensitização em função do tempo, por isso este processo de sensitização foi denominado de dupla sensitização. A partir dos resultados obtidos: grau de sensitização DL-EPR, exame microestrutura e difração de raios X, o presente trabalho propõe o seguinte mecanismo para explicar a dupla sensitização: (Etapa 1) no resfriamento da temperatura de solubilização são precipitados nos contornos de grão fases ricas em cromo; (Etapa 2) os tratamentos isotérmicos geram uma fina precipitação de Cr2N nos contornos de grão sobre os precipitados formados na Etapa 1; (Etapa 3) esses precipitados são posteriormente dissolvidos o que permite (Etapa 4) uma nova precipitação de Cr2N e Cr23C6 nos contornos de grão e (Etapa 5) finalmente temse o processo de crescimento, coalescimento e recuperação final. A recuperação total da resistência à corrosão intergranular foi obtida após tratamentos isotérmicos realizados a 650°C por tempos maiores que 20 minutos e a 700°C a partir de 5 minutos. O trabalho confirma que tanto os fenômenos de precipitação, sensitização e recuperação são controlados 5 pela difusão do cromo na ferrita. Tal confirmação foi possível a partir de análises da solução da segunda lei de Fick e gráficos de Arrhenius, construídos a partir do ensaio DL-EPR e dos exames microestruturais, os quais indicaram uma energia de ativação de precipitação com valor de 255 kJ/mol (219 kJ/mol é o valor da energia de ativação para difusão do cromo na ferrita encontrado em literatura (ARAI; TAKEDA; ARATA, 1987; WOLFE; PAXTON, 1964)). / Ferritic stainless steels are prone to intergranular corrosion following quick cooling from 950°C. The explanation based on chromium impoverishment near the carbides and/or nitrides precipitated in the grain boundaries is the most accepted to describe the observations. This work study the effects of heat treatments on the resistance to intergranular corrosion of the UNS S43000 ferritic stainless steel, using the Double Loop Electrochemical Potentiodynamic Reactivation test (DL-EPR). Specimens have been solution annealed at 1200oC followed by isothermical holding at temperatures between 500°C and 700°C, for times of 5min up to 16h. The DL-EPR test was made in a 0,5M H2SO4 solution using scan rate of 1,67 mV/s. The specimens were observed by optical microscope and scanning electron microscope after DLEPR test, Practices W and X (ASTM A763) and metallographic etch with Vilella reagent. Different degrees of sensitization were obtained for different isothermal holding time. X rays diffraction of extracted precipitates identified chromium nitrides and chromium carbides, Cr2N and Cr23C6. The temperatures of 550°C and 600°C produced two maxima in the curves of degree of sensitization as function of time; the process was named double sensitization. From the results of degree of sensitization DL-EPR, microstructural examination and X rays diffraction, this work proposes the following mechanism to explain double sensitization: (1st stage) during cooling from the solution annealing temperature there is grain boundary precipitation of chromium rich phases; (2nd stage) the isothermal treatments produce a fine grain boundary precipitation of Cr2N on the precipitates formed in the 1st stage; (3rd stage) increasing the time, these precipitates are dissolved, allowing for a (4th stage) new grain boundary precipitation of Cr2N e Cr23C6; finally (5th stage) there is growth, coalescence and recovery. Total recovery of intergranular corrosion resistance was achieved, isothermically at 650°C for times longer than 20min and at 700°C for times longer then 5min. Precipitation, sensitization and recovery are controlled by diffusion of chromium in ferrite. This conclusion was based on analysis of solution of Fick’s second law and Arrhenius plots constructed with DL-EPR data and microstructural observations. The calculus of the experimental energy of activation for precipitation produced a value of 255kJ/mol (energy of activation for chromium 7 diffusion in the ferrite reported by Arai, Takeda and Arata (1987) and Wolfe and Paxton (1964) is 219kJ/mol).

Pesquisas sobre a tenacidade à fratura dos aços ferríticos mostram uma grande dispersão dos resultados quando avaliados na região de transição dúctil-fragil. Esta dispersão é fortemente influenciada pela temperatura de ensaio, dimensões e geometria dos corpos-de-prova e também pelo nível de restrições plástica na ponta da trinca. Tais fatores dificultam a previsão, a partir de valores experimentais, de valores de tenacidade à fratura de aços ferríticos para aplicações em casos práticos. Uma forma de contornar essa dificuldade é através do uso das curvas de referencia, descritas no Código ASME. Estas curvas representam envoltórias inferiores de tenacidade à fratura obtida a partir de ensaios envolvendo diversos tipos de aços. Portanto os valores de tenacidade estabelecidos por essas curvas são, em geral, muito conservadores. Então foi proposta pela ASTM uma nova metodologia, chamada curva Mestra, que trata estatisticamente o comportamento à fratura dos aços ferríticos na região de transição e caracteriza um material em particular, através de um parâmetro denominado Temperatura de Referencia (T0). Nesta pesquisa, avaliou-se a influencia da sensibilidade dos parâmetros: Kmin, m e M envolvidos no procedimento do calculo de um parâmetro denominado temperatura de referencia. (T0). A metodologia da curva mestra foi aplicada através dos dados (experimentos) do euro-teste , para as temperaturas: -91 ºC, -60°C, -40°C e 20°C . Em análises de sensibilidade aos parâmetros com os seguintes valores kmin = 0, 10, 30; m= (3), (3,5), (4,5), (5,0) e M = 40, 50, 60. Os resultados apresentados são compatíveis comprovando a eficiência da metodologia para avaliação da tenacidade à fratura dos aços ferríticos na região de transição. Portanto, nestas condições, podemos afirmar que o conceito da curva mestra foi, realmente validado. / The caracterization of the fracture behavior in the ductile-to-brittle transition for ferritic steels is a hard task because fracture toughness is a strong function of temperature in the transition, with the toughness values increasing rapidly over a relatively narrow temperature baud/range and therefore cannot be easily used to evaluate integrity in structural components because of the uncertainty in how to handle these teste results. To overcome this problem in practice, the ASME code has provided reference curves that give estimates of toughness versus temperature. These curves represent lower envelopes to a large set of fracture toughness experimental data for several heats of steel . Therefore, the fracture toughness values obtained from these curves are in general too conservative. In the last decade, a new methodology, formalized in the ASTM standard method E1921-97, has revolutionized the approach used to caracterize transition fracture behavior and has given a rationale for treating the several factors that influence the scatter in the results. Statistical models are used to define a transition curve, called Master Curve, and the transition temperature of a given material is stated by a parameter called reference temperature (T0). In this research, it was evaluated the sensitivity influence of the parameter: Kmin, m and M, involved in the to measurement procedure. The master curve methodology was applied over the data (experiments) of EuroTest for the following temperatures: - 91°C, -60°C, -40°C and -20°C. A parameters sensitivity analysis was made with following values: Kmin=0, 10, 30; m=(3), (3,5), (4,5), (5,0) and M=40, 50, 60. The results are compatible, which confirm the efficiency of the methodology for evaluating the toughness to ferritic steel fracture in the transition region. Therefore, in these conditions, we can state the master curve concept has indeed been validated.

Made available in DSpace on 2016-03-15T19:36:36Z (GMT). No. of bitstreams: 1 Mariana Zicari Di Monte.pdf: 2990505 bytes, checksum: f99d9fee76550db83998b21ad7b7873b (MD5) Previous issue date: 2012-08-02 / Proact Empreendimentos Tecnológicos S/C Ltda / This paper presents an evaluation of the effects of strain hardening on the kinetics of nitriding thermochemical treatment of alloys of ferritic steels AISI 430 and AISI 439 for different degrees of plastic deformation. The technique used to apply the plastic deformation level was increased by a universal tensile machine. Then we proceeded to apply the processes of gas nitriding, in salt baths and plasma, the alloys in the annealed condition and for different degrees of hardening. The samples were characterized by optical microscopy, scanning electron microscopy, hardness tests and examination of the microhardness profile of the layers. It also employed the technique of X-ray diffraction in order to determine the phases present in the nitrided layer. As a result of this study, it was found that the hardening has no effect on the kinetics of nitriding processes, nor levels of hardness achieved in the nitrided layer. The layer thickness was raised to a gas nitriding process, which besides the exposure time at temperature was held at temperature higher than the other processes studied. This study also presents the results of microstructure and curves of the percentage of nitrogen and carbon depending on the depth of the nitrided layer. Note that the nitrogen concentration decreases with depth as approaching the base metal. Carbon, in turn, is pushed into the sample, providing a decarburization in the region enriched in nitrogen and carbon accumulation in the regions just below the nitrided layer. The spectra of X-ray diffraction corresponding to the nitrided layers of steels 430 and 439 indicated the presence of CrN precipitate rich in nitrogen. The alloy 430 suffered heavy attack to a depth of about 30 Um on the other hand the alloy 439 had the region with little predominance of attack, with small volume fractions of more intense attack. The hardness levels of light and dark regions were similars, around 1000 HV, indicating an efficient mechanism of precipitation hardening. It concluded that the chromium nitride is present in both regions, and the highest attack can be related to a discontinuous precipitation process, probably due to iron nitride Fe3N, contrary to what was found in the literature. / O presente trabalho apresenta uma avaliação dos efeitos de encruamento na cinética do tratamento termoquímico de nitretação em ligas de aços inoxidáveis ferríticos AISI 430 e AISI 439 para diferentes graus de deformação plástica. A técnica empregada para se aplicar a deformação plástica em nível crescente foi por meio de uma máquina universal de tração. Em seguida procedeu-se a aplicação dos processos de nitretação gasosa, em banhos de sais e por plasma, nas ligas no estado recozido e para os diferentes graus de encruamento. As amostras foram caracterizadas por microscopia óptica, microscopia eletrônica de varredura, ensaios de dureza e levantamento do perfil de microdureza das camadas. Foi empregada também a técnica de difração de raios-X, com o objetivo de se determinar quais as fases presentes na camada nitretada. Como resultado principal deste estudo, concluiu-se que o encruamento não apresentou nenhum efeito na cinética dos processos de nitretação, nem tão pouco nos níveis de dureza atingidos nas camadas nitretadas. A espessura da camada foi maior para o processo de nitretação a gás, que além do tempo em exposição em temperatura, foi realizada em temperatura superior aos outros processos estudados. Este estudo também apresenta os resultados de microestrutura e as curvas de percentual de nitrôgenio e carbono em função da profundidade de camada nitretada. Nota-se que a concentração de nitrogênio diminui com a profundidade à medida que se aproxima do metal base. O carbono, por seu turno, é empurrado para dentro da amostra, promovendo uma descarbonetação na região enriquecida em nitrogênio, e um acúmulo de carbono nas regiões logo abaixo da camada nitretada. Os espectros de difração de raios-X correspondentes às camadas nitretadas dos aços 430 e 439, indicaram a presença do precipitado rico em nitrogênio CrN. A liga 430 sofreu ataque intenso até uma profundidade da ordem de 30 Um; já a liga 439 apresentava predominância de região com pouco ataque, com pequena fração volumétrica de ataque mais intenso. Os níveis de dureza da região clara e escura eram similares, por volta de 1000 HV, indicando um eficiente mecanismo de endurecimento por precipitação. Infere-se que o nitreto de cromo se faz presente nas duas regiões, sendo que o maior ataque pode estar relacionado a um processo de precipitação descontínua, provavelmente associado ao nitreto de ferro Fe3N, contrariamente ao que se encontrou na literatura.

Slat-band chains are used as conveyors by the food industry, breweries and bottling plants. The operating conditions require abrasion resistance and strength which are at the limit of the capabilities of the current material of choice, cold worked type 430. In an unconventional way of strengthening this material, Mintek developed a process in which the cold worked material is aged between 450°C and 500°C. The present work aims to elucidate the strengthening mechanism, using type 430 stainless steel containing 16.42% Cr and 0.036% C, in the cold-rolled condition (38% reduction in area), with and without prior solution heat treatment. The Cr-rich precipitate α" may form in the 450°C to 500°C range (due to the miscibility gap in the Fe-Cr system), resulting in the increased hardness and lowered ductility. Mossbauer studies confirmed that the α", at this composition and temperature, forms through the process of nucleation and growth. Hardening due to α" precipitation was only observed after aging for 64 hours or more, however. After increasing the dissolved interstitial content by solution heat treatments (in the vicinity of 900°C), increases in Vickers hardness of 30-50 kg/mm2 could be obtained after only 8 minutes at 475°C. This hardness increase corresponds to an increase in tensile strength of more than 100 MPa. The increased hardness does not appear to be caused by strain aging, and presumably results from fine carbide or nitride precipitation. Solution treatment at 930°C also introduced some martensite (α') into the microstructure, which raised the hardness of the unaged cold worked material. Overaging of the carbide and nitride precipitates was observed at 475°C, but not at 450°C, probably due to the lower diffusion rates at the lower temperature. No averaging of the α" precipitates occurred, for aging times up to 2072 hours. Samples aged for selected periods of time at 475°C had low impact strengths - even well before the formation of α" - and revealed predominantly cleavage fracture with some ductile fracture areas, mostly at grain boundaries. Both impact strength and lateral expansion indicated that embrittlement accompanies the increased hardness obtained by aging. Calculation of critical crack lengths from the impact data, however, revealed that a maximum flaw length of 0.8 mm, for specimens solution treated at 880°C, could be tolerated before catastrophic failure. Since it is not expected that flaws of that size would exist in the as manufactured links, fatigue will probably determine the lifetime of the chains, although the lower K1c values indicate that less crack propagation will be tolerated before brittle fracture. During the aging treatment, the strength may be lowered by recrystallisation of the coldworked material. Transmission electron microscopy (TEM) revealed the start of recovery, but no recrystallisation. Some large precipitates (around lμm in diameter) were present. These were identified, through their diffraction patterns, as M23C6; these carbides were present in both aged and unaged material and hence represent precipitates which had not dissolved during the initial solution treatments. The α" precipitates- and the presumed newly formed nitride and carbide precipitates - were too fine for detection by TEM. Potentiodynamic testing of the treated material in a 0.5M H2SO4 solution indicated that, although the probable hardening mechanisms imply localised Cr depletion of the matrix, the general corrosion resistance and passivation behaviour were not affected. It is concluded that the strength of the chain may be increased markedly by short-term heat treatments at 475°C, with lowered toughness, but with no decrease in corrosion resistance. Martensite, work hardening, and precipitation of carbides and nitrides all contribute to the final strength, with α" formation only becoming significant after longer aging times. / Dissertation (MEng)--University of Pretoria, 2013. / Materials Science and Metallurgical Engineering / unrestricted

This master thesis was carried out at Scania CV AB. The focus for this thesis is the prediction of welding distortions that can cause problems in the manufacturing process of Scania's after-treatment system. The after-treatment system is mainly assembled by sheet metal plates of the ferritic stainless steel EN 1.4509. The plates are welded together. When welding, distortions and residual stresses occur, and they also depend on the sequence in the component was welded together. The distortions and residual stresses can cause tolerance related issues and a lower lifetime for the welded components. Experiments are expensive and therefore it is desirable to simulate the welding process, thereby controlling distortions and optimizing welding sequences. To simulate the welding process and predict the welding distortions a thermo-mechanical FE-model was created for two typical welds found on the after-treatment system. The first scenario was two thin plates welded onto each other in an overlap weld joint and the second scenario was a thin plate welded onto a thick plate in a overlap weld joint. After the FE-model was compared to the experiments. An optimization of the welding sequences was also made on a larger component typically found on the after-treatment system. The FE-model can predict the distortion shape with good accuracy for the T-fillet weld, while the model predicted a more symmetric distortion shape on the overlap weld compared to a more asymmetric shape found on the experiments, but the error is still not very large. The Fe-model can also be used to optimize the welding sequence for bigger components on the after-treatment system within a reasonable time span compared to doing the opimization manually in an experiment. / Detta examensarbete gjordes för Scania CV AB. Fokus for detta examensarbete har varit kvarvarande deformationer efter svetsning som kan skapa problem vid tillverkningen av Scanias avgasefterbehandlingssystem. Avgasefterbehandlingssystemet är till mesta dels konstruerat av stålplåtar av det ferritiska rostfria stålet EN 1.4509, plåtarna är svetsade ihop och då uppstår kvarvarande deformationer. När komponenter svetsas samman uppstår deformationer och restspänningar. Dessa deformationer och restspänningar är också beroende på i vilken sekvens komponenterna har svetsats ihop. Deformationerna och restspänningarna kan skapa problem med toleranser och sänka livslängden för komponenterna som sammanfogats. Experiment är kostsamma och därför är det önskvärt att simulera svetsprocessen, och därav kontrollera deformationerna som uppstår och optimera i vilken sekvens som komponenterna ska svetsas ihop. För att simulera svetsprocessen och prediktera de kvarvarande deformationerna efter svetsning så gjordes termo-mekanisk FE-model för två vanliga svetsscenarion för avgasefterbehandlingssystemet. Det ena scenariot är två tunna plåtar som svetsas ihop i en överlappande position och det andra var en tunn plåt som svetsas på en tjockare plåt. Ett experiment gjordes sedan för båda svetstyperna. Efter att svetstyperna hade jämförts med experimentet så gjordes en optimering av svetssekvensen för en större komponent likt komponenter funna på avgasefterbehandlingssystemet. Den termomekaniska FE-modelen kunde prediktera de kvarnvarande deformationerna och deras form med bra noggrannhet jämfört med experimentet med undantag för en deformationsform på de tunna plåtarna som var mer symmetrisk i FE-modellen jämfört med den asymmetriska formen i experimentet. FE-modellen kunde också användas för att optimera svetssekvensen för den större komponenten inom en rimlig tidsrymd.