O Aço Inoxidável Super Duplex UNS S32760 é um aço de alta liga com estrutura composta por uma matriz ferrítica com ilhas austeníticas, em proporções aproximadamente iguais. Esta estrutura lhe confere boas propriedades como: resistência à corrosão, em particular à corrosão por pite e por fresta, excelentes propriedades mecânicas, boa soldabilidade, alta condutividade térmica, baixo coeficiente de expansão térmica e excelente tenacidade. Suas principais aplicações geralmente ocorrem em ambientes com alta concentração de cloreto, como por exemplo, em tubos para transporte de óleo e gás, equipamentos para transporte ou em contato com materiais rico sem cloretos, em tanques e vasos para a indústria química e petroquímica. Estas aplicações tornam importante a determinação da temperatura crítica de pite (TCP). A ASTM normatiza essa determinação com as normas G-150 e G-48, que abrangem aços inoxidáveis austeníticos comuns e ligas à base de níquel, não existindo uma condição especifica para o teste em aços super duplex. O objetivo deste trabalho é a caracterização eletroquímica e o desenvolvimento de uma metodologia para a determinação da temperatura crítica de pite de aços super duplex UNS S32760. Devido à falta de normatização para estes materiais uma combinação das normas ASTM G-48 e G-150 foi empregada neste trabalho. Utilizou-se como meio uma solução contendo FeCl3 6% e HCl 1%, em massa. Foram empregadas como técnicas medidas de potencial de circuito aberto em função do tempo de imersão, curvas de polarização potenciostática anódica, cronoamperometria, espectroscopia de impedância eletroquímica (EIE), microscopia ótica (MO), microscopia eletrônica de varredura (MEV) e espectroscopia por dispersão de energia (EDS). Foram realizados tratamentos dos dados experimentais, abordando-os de maneiras diferentes para que a melhor resposta fosse obtida na determinação da TCP das ligas. Duas amostras diferentes deste material foram estudadas, uma amostra comercial e uma amostra desenvolvida pelo laboratório de pesquisa e desenvolvimento da Villares Metals, com diferentes teores de cromo e molibdênio. Apesar da variação na composição química das amostras, nas análises por MEV e EDS, as mesmas se mostraram semelhantes, quando apenas polidas, apresentando os mesmos tipos de precipitado. A microscopia ótica possibilitou visualizar a diferença na proporção de fases entre as duas ligas e as características morfológicas das mesmas. Analisando mais detalhada e minuciosamente os dados eletroquímicos, foi determinado que o melhor valor de densidade de corrente a ser utilizada como parâmetro na determinação da TCP , é 25±5 µAcm-2. Utilizando este parâmetro foi mostrado que a TCP determinada é menor, quando comparada com a obtida pelas normas convencionais. A combinação das diferentes técnicas permite afirmar que a metodologia empregada determina de maneira bem mais precisa a TCP. / UNS S32760 super duplex stainless steel is a high alloy steel, containing a ferrítica matrix and austenitic islands as structure at equal proportions approximately. This structure results in good properties as high resistance to corrosion, particularly to pitting and crevice corrosion, excellent mechanical properties, good weldability, high thermic conductivity, low thermic expansion coefficient, and excellent tenacity. Their principal applications are in high chloride concentration media, for example in tubes for oil and gas, in transport equipment when in contact with high chloride concentration materials, tanks and vases for chemical and petrochemical industries. Due to these applications the evaluation of the pitting critical temperature is mandatory for these materials. G-150 and G-48 ASTM Standards are recommended for conventional stainless steels and nickel alloys, but there is not any specific standard for super duplex stainless steels. The main of this work is the characterization and the development of a methodology to evaluate the critical pitting temperature for USS S32760 super duplex stainless steels. Due to the absence of standard analyses for this materials, a combination of G-48 and G-150 standards were employed. The medium was 6% FeCl3 by mass and 1% HCl by mass solution. Open circuit potential measurements, anodic potentiostatic polarization curves, chronoamperometry, electrochemical impedance spectroscopy (EIS), optical microscopy (OM), scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS) were used as techniques. Different treatments for the experimental results were used in order to obtain the best value for TCP of these alloys. Two different samples of this material were studied: a commercial sample and a new composition developed at P&D Villares Metals industry, with different contents in chromium and molybdenum. The materials studied presented the same kinds of inclusions, according to SEM and EDS analyses. OM analysis showed the proportionality between the ferritic and austenitic phases and their morphological characteristics. The electrochemical studies suggest the 25 ± 5 µAcm-2 value for current density to be used in the CPT e valuation. The CPT obtained is lower when compared to those one using conventional standards. The combination of different techniques permits to conclude that the proposed methodology evaluates the CPT w ith higher precision.

O Aço Inoxidável Super Duplex UNS S32760 é um aço de alta liga com estrutura composta por uma matriz ferrítica com ilhas austeníticas, em proporções aproximadamente iguais. Esta estrutura lhe confere boas propriedades como: resistência à corrosão, em particular à corrosão por pite e por fresta, excelentes propriedades mecânicas, boa soldabilidade, alta condutividade térmica, baixo coeficiente de expansão térmica e excelente tenacidade. Suas principais aplicações geralmente ocorrem em ambientes com alta concentração de cloreto, como por exemplo, em tubos para transporte de óleo e gás, equipamentos para transporte ou em contato com materiais rico sem cloretos, em tanques e vasos para a indústria química e petroquímica. Estas aplicações tornam importante a determinação da temperatura crítica de pite (TCP). A ASTM normatiza essa determinação com as normas G-150 e G-48, que abrangem aços inoxidáveis austeníticos comuns e ligas à base de níquel, não existindo uma condição especifica para o teste em aços super duplex. O objetivo deste trabalho é a caracterização eletroquímica e o desenvolvimento de uma metodologia para a determinação da temperatura crítica de pite de aços super duplex UNS S32760. Devido à falta de normatização para estes materiais uma combinação das normas ASTM G-48 e G-150 foi empregada neste trabalho. Utilizou-se como meio uma solução contendo FeCl3 6% e HCl 1%, em massa. Foram empregadas como técnicas medidas de potencial de circuito aberto em função do tempo de imersão, curvas de polarização potenciostática anódica, cronoamperometria, espectroscopia de impedância eletroquímica (EIE), microscopia ótica (MO), microscopia eletrônica de varredura (MEV) e espectroscopia por dispersão de energia (EDS). Foram realizados tratamentos dos dados experimentais, abordando-os de maneiras diferentes para que a melhor resposta fosse obtida na determinação da TCP das ligas. Duas amostras diferentes deste material foram estudadas, uma amostra comercial e uma amostra desenvolvida pelo laboratório de pesquisa e desenvolvimento da Villares Metals, com diferentes teores de cromo e molibdênio. Apesar da variação na composição química das amostras, nas análises por MEV e EDS, as mesmas se mostraram semelhantes, quando apenas polidas, apresentando os mesmos tipos de precipitado. A microscopia ótica possibilitou visualizar a diferença na proporção de fases entre as duas ligas e as características morfológicas das mesmas. Analisando mais detalhada e minuciosamente os dados eletroquímicos, foi determinado que o melhor valor de densidade de corrente a ser utilizada como parâmetro na determinação da TCP , é 25±5 µAcm-2. Utilizando este parâmetro foi mostrado que a TCP determinada é menor, quando comparada com a obtida pelas normas convencionais. A combinação das diferentes técnicas permite afirmar que a metodologia empregada determina de maneira bem mais precisa a TCP. / UNS S32760 super duplex stainless steel is a high alloy steel, containing a ferrítica matrix and austenitic islands as structure at equal proportions approximately. This structure results in good properties as high resistance to corrosion, particularly to pitting and crevice corrosion, excellent mechanical properties, good weldability, high thermic conductivity, low thermic expansion coefficient, and excellent tenacity. Their principal applications are in high chloride concentration media, for example in tubes for oil and gas, in transport equipment when in contact with high chloride concentration materials, tanks and vases for chemical and petrochemical industries. Due to these applications the evaluation of the pitting critical temperature is mandatory for these materials. G-150 and G-48 ASTM Standards are recommended for conventional stainless steels and nickel alloys, but there is not any specific standard for super duplex stainless steels. The main of this work is the characterization and the development of a methodology to evaluate the critical pitting temperature for USS S32760 super duplex stainless steels. Due to the absence of standard analyses for this materials, a combination of G-48 and G-150 standards were employed. The medium was 6% FeCl3 by mass and 1% HCl by mass solution. Open circuit potential measurements, anodic potentiostatic polarization curves, chronoamperometry, electrochemical impedance spectroscopy (EIS), optical microscopy (OM), scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS) were used as techniques. Different treatments for the experimental results were used in order to obtain the best value for TCP of these alloys. Two different samples of this material were studied: a commercial sample and a new composition developed at P&D Villares Metals industry, with different contents in chromium and molybdenum. The materials studied presented the same kinds of inclusions, according to SEM and EDS analyses. OM analysis showed the proportionality between the ferritic and austenitic phases and their morphological characteristics. The electrochemical studies suggest the 25 ± 5 µAcm-2 value for current density to be used in the CPT e valuation. The CPT obtained is lower when compared to those one using conventional standards. The combination of different techniques permits to conclude that the proposed methodology evaluates the CPT w ith higher precision.

En raison de leurs excellentes propriétés mécaniques, couplées à une bonne résistance à la corrosion par piqûres et à un coût modéré (basse teneur en nickel et en molybdène), les aciers inoxydables austéno-ferritiques (dits aciers inoxydables duplex) sont largement utilisés dans de nombreux secteurs industriels. Les aciers inoxydables duplex ont une microstructure complexe composée à proportion équivalente d’austénite et de ferrite. L’austénite ayant une composition chimique différente de celle de la ferrite, un film hétérogène se forme à la surface des aciers inoxydable duplex. Par ailleurs, les deux phases métalliques ayant des propriétés mécaniques différentes, un champ de contraintes hétérogènes est généré dans les grains. Sous certaines conditions, l’existence de gradients de contraintes peut conduire à des hétérogénéités du film passif. Dans cette étude, l’effet d’un vieillissement de longue durée dans un milieu contenant des chlorures sur la composition chimique du film passif a été tout d’abord étudié. Le comportement en corrosion de certains alliages duplex a été ensuite déterminé à partir d’essais TCP (détermination de la température critique de piqûration). Les résultats ont été analysés en tenant compte des informations obtenues précédemment. Après vieillissement, l’épaisseur du film passif et le rapport Cr/Fe ont significativement augmenté. La distribution des chlorures dans le film passif est hétérogène. Cette distribution a été reliée à la microstructure du matériau et au champ de contraintes résiduelles. Il a été montré qu’elle influence le comportement électrochimique du matériau. Le comportement en corrosion est ensuite analysé à l’aide des courbes de polarisation locales. Des critères métallurgiques ont été proposés pour l’amorçage de piqûres. / Duplex stainless steels (DSS) are highly important engineering materials, due to their generally high corrosion resistance combined with high strength and moderate alloy cost (lower nickel and molybdenum content). They are widely used in various industrial sectors. DSS have a complex microstructure with comparable volume of austenite and ferrite. Due to differences in chemical composition between austenite and ferrite, a heterogeneous passive film is formed on both phases. In addition, due to differences in mechanical properties, a heterogeneous stress field may be generated in metallic grains. Under certain conditions, these differences may also yield formation of a heterogeneous passive film. In this work, the influence of long-term ageing in chloride-containing media by on the chemical composition of the passive film was first studied by means of XPS and Auger at the microscale. The corrosion behaviour of some duplex stainless steels was then determined from CPT tests (determination of the critical pitting temperature). Results were analysed taking into account information obtained previously. After ageing, the thickness and the ratio Cr/Fe are significantly increased. The chloride distribution in the passive film was heterogeneous. It was related to the microstructure and the residual strain field. It was shown that this distribution modifies the electrochemical behaviour of samples. The corrosion behaviour was then analysed from local polarization curves and CPT tests. Metallurgical criteria for pitting were proposed.

Les aciers inoxydables duplex (DSS) sont caractérisés par une structure biphasée comprenant un mélange de ferrite et d’austénite. La proportion entre les deux phases est d'habitude environ 50 %. Ils sont de plus en plus employés dans les industries chimiques, pétrochimiques, nucléaires, marines et de papier, principalement en raison de leurs excellentes propriétés mécaniques couplées à une bonne résistance à la corrosion par piqûre (basse teneur en nickel et molybdène). L’austénite ayant une composition chimique différente de celle de la ferrite, un film hétérogène se forme à la surface des aciers inoxydable duplex. Par ailleurs, les deux phases métalliques ayant des propriétés mécaniques différentes, un champ de contrainte hétérogène est généré dans les grains. Sous certaines conditions, l’existence de gradients de contraintes peut conduire à des hétérogénéités du film passif. Dans ce travail , on étudie l’effet des éléments d’alliages sur les propriétés physico-chimiques du film passif et le comportement en corrosion par piqures avant et après vieillissement en milieu chlorurés, pour une surface de référence respectant certains critères à savoir une surface lisse exempt de tout défauts (pas de couche écrouie, rugosité faible..). Les propriétés physico- chimiques du film sont étudiés à l’aide des analyses Auger et XPS à l’échelle locale et globale. Le comportement en corrosion des alliages duplex a été ensuite déterminé à partir d’essais TCP (détermination de la température critique de piqûration). Les résultats avant vieillissement ont montré que le film passif est homogène à l’échelle macroscopique et que l’amorçage des piqûres semblent être liée à la taille des grains et à la texture cristallographique décrit par le GOS. Après vieillissement de longue durée en milieu représentatif, les analyses de surface montrent un renforcement de la passivité par un épaississement du film passif, une augmentation significative du rapport Cr/Fe ce qui ont pour effet d’améliorer le comportement en corrosion par piqures des alliages. Des critères métallurgiques ont été proposés pour expliquer l’amorçage de piqûres pour ces alliages. / Duplex stainless steels (DSS) are characterized by a two-phase structure comprising a mixture of ferrite and austenite. The proportion between the two phases is usually about 50%. They are increasingly used in the chemical, petrochemical, nuclear, marine and paper, mainly because of their excellent mechanical properties coupled with good resistance to pitting corrosion (low grade nickel and molybdenum). The austenite having a different chemical composition than the ferrite, a heterogeneous film is formed on the surface of duplex stainless steels. Furthermore, the two metallic phases having different mechanical properties, a field of heterogeneous stress is generated in the grains. Under certain conditions, these differences may also yield formation of a heterogeneous passive film. In this work, we study the effect of alloying elements on the physico-chemical properties of the passive film and behavior pitting corrosion before and after ageing in chloride media for a reference surface that meet certain criteria ie a smooth surface free from any defects (no hardened layer .. low roughness). The physicochemical properties of the film are studied using Auger and XPS analysis at the microscale. The corrosion behavior of duplex alloys was then determined from CPT tests (determination of the Critical Pitting Temperature). The results before ageing have shown that the passive film is homogeneous on a macroscopic scale and that pitting corrosion appear to be related to the grain size and crystallographic texture described by GOS. After ageing, surface analysis shows a strengthening of passivity by thickening of the passive film and the ratio Cr/Fe are significantly increased which has the effect of improving behavior pitting alloys. Metallurgical criteria for pitting were proposed.

This research extended the knowledge of the solid phase transformation and the resulting influence on impact toughness and pitting corrosion resistance in super austenitic stainless steel (SASS) SANICRO® 35. A time-temperature-transformation diagram (TTT diagram) was assembled by performing isothermal heat treatments in the temperature range of 650-1050 °C for different periods of time, ranging from 5 min to 500 min. Microstructural analysis via LOM-DIC, SEM-EDS shows that the nose temperature of dominating σ phase is located in between 900-950 °C. Minor nitrides including π phase and Cr2N with the nose temperature of 900 °C and 850 °C, respectively, were detected after prolonged heat treatment times. Area fraction of precipitates was calculated by analyzing micrographic images in the software ImageJ. Charpy impact tests indicate that the impact toughness degrades with increasing area fraction of precipitates but at a higher rate at the early stage of precipitation. Despite a much-lessened area fraction, fine precipitates decorating the grain boundaries in a continuous pattern impose significant negative effect on impact toughness. Pitting corrosion resistance was indicated by critical pitting temperature (CPT) as per ASTM G150mod (3M MgCl2). Pitting corrosion resistance deteriorated with increasing amount of σ phase due to the Cr- and Mo-depleted surrounding area, but it is more dependent on the distribution pattern of precipitates, as well as the secondary phase type. The lowest CPTs were measured after heat treatment for 500 min at 800 °C and 850 °C where nitrides including Cr2N and π phase were formed and the small precipitates were distributed on grain boundaries continuously. Auxiliary simulation of TTT diagram via TC PRISMA shows drastic variation from experimental results in regard of time scale. The enhancement pre-factor for the interfacial mobility and interfacial energy can be modified to approach the experimental results. / Detta arbete utfördes för att undersöka fasomvandlingar och dess inflytande på slagsegheten och gropfrätningsmotståndet för det superaustenitiska rostfria stålet (SASS) SANICRO® 35. Ett tid-temperatur-transformationsdiagram (TTT-diagram) har tagits fram genom att utföra isotermiska värmebehandlingar mellan 650-1050 °C med olika hålltider från 5-500 minuter. Mikrostrukturanalys genom LOM-DIC, SEM-EDS undersökning visar att nosen för den dominerande σ-fasen ligger mellan 900-950 °C. Mindre nitrider, som π-fas och Cr2N, med nosarna vid 900 °C respektive 850 °C observerades vid längre hålltider. Areafraktionen av utskiljningar beräknades genom analys av mikrobilder med programmet ImageJ. Slagprovning visade att slagsegheten minskar med ökande fraktion utskiljningar men med en tydligare försämring i början av fastransformationen. Trots att de utgör en betydligt mindre areafraktion så kan mindre utskiljningar som följer korngränserna också påverka materialet signifikant negativt. Gropfrätningsmotståndet testades genom att mäta Critical Pitting Temperature (CPT) enligt ASTM G150mod (3M MgCl2). CPT minskade med ökande andel σ-fas p.g.a. den Cr- och Mo-utarmade zon som omger de utskilda partiklarna. Det finns även en stark koppling mellan lägre CPT och distributionen av utskiljningarna samt andra typer av faser. Lägst CPT uppmättes efter 500 minuter vid 800 °C och 850 °C då små nitrider inklusive Cr2N och π-fas bildats längs med stora delar av korngränserna. Simulering av TTT-diagram i TC PRISMA visade en drastisk skillnad i tiden till utskiljning/mängden utskiljningar jämfört med de experimentella resultaten. Diffusionförstärkningsfaktorn (eng. “mobility enhancement pre-factor”) och ytenergin kan minskas för att bättre överensstämma med de experimentella resultaten.