Stress-corrosion cracking of austenitic alloys in an oxygen-free carbon dioxide environment containing chloride ions was studied under static conditions. Stiffness and X-ray measurements supported results obtained from SEM photomicrographs indicating that the CT specimens loaded to a stress intensity of 22 ksi-in^.5 were not susceptible to SCC in this environment. These alloys were also evaluated for their SCC resistance in boiling MgCl₂ and NaCl solutions. Results of this study indicated that alloys containing higher nickel contents were more resistant to chloride SCC. / Master of Science

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L’objectif de cette étude e est de comprendre le processus de déalliage de l’acier inoxydable austénitique 304L avec l’intention de transcrire ce raisonnement aux aciers duplex. Des essais ont été réalisés au sein d’une solution aqueuse désaérée d’hydroxyde de sodium à 50%, portés à une température de 80°C sous pression atmosphérique et à potentiel libre. - L’alliage 304L se dissout en formant une couche nanoporeuse riche en nickel métallique sur sa surface. - L’alliage 2202 se dissout et présente deux comportements différents : o la ferrite s’appauvrit en nickel o l’austénite se recouvre d’une couche nanoporeuse constituée de nickel métallique. o les deux phases ont des vitesses de dissolution distinctes, l’austénite se dissolvant plus rapidement que la ferrite. Les cinétiques de dissolution des deux alliages sont différentes : l’alliage 2202 présente une meilleure résistance à la corrosion que l’alliage 304L. Cependant l’austénite de l’alliage 2202 se comporte de manière identique à l’alliage 304L et présente les mêmes caractéristiques. La ferrite semble conférer à l’alliage duplex une protection contre la corrosion caustique au détriment de l’austénite.La mise en évidence de la couche du nickel métallique presque pur est confrontée avec des modèles existants de déalliage. Des expériences complémentaires ont prouvées la simultanéité des étapes de dissolution de l'alliage, de la redéposition des atomes de Ni et de leur réarrangement sur la surface. / The aim of this study is to understand the process of dealloying of austenitic stainless steel 304L with the intention to put this reasoning to the duplex steels. Tests were conducted in a deaerated aqueous solution of sodium hydroxide at 50%, heated to a temperature of 80°C at atmospheric pressure and free potential. • The alloy 304L is dissolved to form a nanoporous layer rich in nickel metal on its surface. • The alloy 2202 is dissolved and has two different behaviors: o Ferritic phase is depleted in nickel o Austenite is covered by a nanoporous layer consists of metallic nickelo The two phases have different dissolution rates: austenite dissolves faster than ferrite. Kinetic dissolution of two alloys is different: alloy 2202 has better corrosion resistance than alloy 304L. However, the behavior of the austenite of the alloy 2202 is identical to the alloy 304L and has the same characteristics. The ferrite appears to give the duplex alloy corrosion protection against caustic at the expense of austenite. The identification of the layer of almost pure metallic nickel is confronted with existing models of dealloying. Additional experiments proved the simultaneous steps of dissolution of the alloy, redeposition of Ni atoms and their rearrangement on the surface.

Les aciers inoxydables lean duplex, à faible teneur en nickel et sans molybdène, représentent une alternative économique pour les usines de dessalement et l’industrie pétrolière. Celles-ci ont la particularité d’être exposées à des milieux très agressifs dont la présence de chlorure, de sulfure d’hydrogène, de hautes températures ou encore d’acides peut provoquer des phénomènes de fissuration sous contrainte.Cette étude est divisée en deux parties, la première se consacre aux milieux purement chlorurés et la seconde aux milieux contenant du sulfure d’hydrogène. Dans les deux parties, la compréhension des phénomènes liés à la fissuration sous contrainte des lean duplex est effectuée sur la nuance S32304, puis est comparée aux comportements des nuances S32202 et S32101. L’influence des milieux bouillants sur la résistance à la fissuration des aciers inoxydables, les mécanismes de dépassivation et de dissolution sélective des lean duplex, les différents modes de fissuration en présence de sulfure d’hydrogène ou encore l’amorçage de la corrosion sous contrainte assistée par le sulfure d’hydrogène sont abordés dans ce rapport. / Lean duplex stainless steels, with low content of nickel and without molybdenum, represent an economic alternative for desalting plants and petroleum industry. For these uses, steel have the particularity to be exposed to very aggressive environments inducing phenomenon of Stress Corrosion Cracking as chlorides, hydrogen sulphur, high temperatures or acids.This study is divided in two parts dedicated to two different environments. The first part is devoted to chloride middles and the second to hydrogen sulphur middles. In both parts, the understanding of phenomenon linked to the stress corrosion cracking of lean duplex is studied on the grade steel S32304, then is compared to the behaviour of grade steels S32202 and S32101. The topics treated in this report are notably the influence of boiling environments on the cracking resistance of stainless steels, the mechanism of unpassivation and selective dissolution of lean duplex, the different modes of cracking in presence of hydrogen sulphur, and the initiation of stress corrosion cracking assisted by hydrogen sulphur

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / As ligas de Níquel são amplamente utilizadas na construção de diversos componentes de reatores à água pressurizada PWR. Estes materiais foram selecionados por possuírem elevada resistência mecânica e a corrosão generalizada e compatibilidade com os materiais do reator. No entanto, alguns reatores têm apresentado trincamento causado por corrosão sob tensão em soldas dissimilares efetuadas com a liga de Inconel 182, isto têm ocorrido principalmente no circuito primário. O trabalho aqui apresentado é um estudo para calcular a taxa de propagação de trincas causada por corrosão sob tensão em soldas dissimilares, efetuadas com a liga de Inconel 182 com sobrecamada de solda de Inconel 52 em ambiente simulado do circuito primário de reatores PWR. Este estudo é fundamental para determinar o tempo de vida em serviço dos equipamentos e estabelecer intervalos de inspeção, evitando-se assim acidentes catastróficos. / Nickel alloys are widely used in the construction of several components of the pressurized water reactors (PWR).These materials were selected due to their high mechanical and corrosion resistance as well as its compatibility to the reactor materials. However, some reactors have shown cracking caused by stress corrosion cracking (SCC) in dissimilar metals weld made with alloy Inconel 182, mainly in the primary circuit. The purpose of the present study was to calculate the crack growth rate caused by primary water SCC in dissimilar metals weld made with alloy Inconel 182 and Weld Overlay of Inconel 52.This study is essential to determine the lifetime of the equipments and establish inspection intervals, avoiding catastrophic accidents.

Re-processed oxide fuel product from the Thermal Oxide Reprocessing Plant (THORP) is stored in Type 316L stainless steel, using a design of several nested cans, with the outer can providing the safety case containment barrier. The research reported in this PhD thesis aims to support the safety case related to these storage cans, by identifying and characterising susceptible microstructure sites and associated material surface conditions. The overarching goal of this project is to understand the propensity of THORP storage cans towards localised corrosion and Environment Assisted Cracking (EAC) in HCl and chloride-bearing atmospheric environments. The investigation focused on two possible corrosion cases: (1) understanding the effect of surface finishing on material performance in chloride-containing atmospheric environments, and (2) characterising the effects of the HCl aqueous solutions inside the can, with potential formation of HCl vapour. Microstructure investigations were carried out on surface-treated type 316L coupon specimens. The application of aqua blasting resulted in a deformed near-surface microstructure, containing compressive residual stresses to a depth of 100-120 micrometres. Subsequent laser engraving produced a recrystallized surface layer with tensile residual stresses reaching to a depth of 200 micrometres. Changes of surface roughness topography were accompanied by the development of a thick oxide/hydroxide film after laser engraving. Atmospheric exposure revealed similar corrosion attack for all samples, with laser engraving exhibiting the lowest number of corrosion sites, but with the largest average depth of attack. In addition, laser engraving led to atmospheric-induced stress corrosion cracking (AISCC) within two weeks of exposure to 386 ug/cm2 MgCl2-laden droplet deposits, with crack growth rates similar to ground U-bend samples. Strategies to reduce the likelihood of AISCC of laser-engraved components are discussed. The influence of HCl concentration and exposure temperature on the corrosion type and rate of annealed and cold rolled type 316L stainless steel has also been investigated. Cold rolling of up to 20 % reduction was introduced, with potentio-dynamic polarization measurements conducted in 0.01 - 3 M HCl aqueous solution. Results are compared to microstructures immersed under open circuit conditions, and to HCl-laden droplet deposits at temperatures up to 80C. Corrosion type diagrams are introduced to describe the transition between uniform corrosion, mixed-mode uniform with pitting corrosion, and pitting corrosion only, as a function of temperature, HCl concentration, and cold deformation. SCC tests of type 316L stainless steel have been carried out at 110C, by exposing U-Bend samples to HCl-laden droplets and HCl vapour. The humidity of the environment was controlled using defined volume fractions of H2O in a sealed environmental chamber. HCl-laden droplets with chloride deposition densities exceeding 1.5 ug/cm2 led to SCC after 90 minutes of exposure, whereas no corrosion attack was observed for samples with exposure to 0.15 ug/cm2 HCl. Increasing HCl concentrations resulted in fewer, but longer cracks, reaching up-to several hundreds of micrometres in length. HCl vapour exposure was carried out by adding various volumes of HCl solution in a beaker to the sealed test chambers. These HCl vapour tests confirmed a change of corrosion type with HCl concentration, from pitting corrosion with SCC, to the occurrence of uniform corrosion.

Primary Water Stress Corrosion Cracking (PWSCC) of Alloy 600 and similar Ni-Cr-Fe alloys is regarded as one of the most important challenges to nuclear power plant operation. During the past decades the majority of research has focused on PWSCC crack growth rate measurements in order to assess the lifetime of real components and to develop empirical models for crack propagation. However, the incubation and initiation stages of PWSCC have the same or even greater importance than the propagation stage, particularly because SCC can be undetected for more than 20 years before the occurrence of a rapid and catastrophic failure. There is, therefore, the scientific need to understand the mechanisms playing a fundamental role in the formation and development of intergranular cracks embryo, the so-called SCC initiation "precursor events", in order to be able to predict and mitigate the occurrence of PWSCC. Amongst all the models proposed for SCC initiation, the internal oxidation mechanism proposed by Scott and Le Calvar in 1992 appears to be the most comprehensive. Although the internal oxidation mechanism is widely accepted, it still requires further elucidation, especially in terms of enhanced grain boundary diffusivity and the role of intergranular carbides on the oxidation mechanism. The present work has focused on the initial stages of intergranular oxidation of solution-annealed (SA) and thermally-treated (TT) Alloy 600 with the aim of understanding the active mechanism responsible for the enhanced intergranular oxide penetration kinetics. The material was tested in simulated PWR primary water at 320°C, high-pressure hydrogenated-steam at 400°C and low-pressure H2-steam environment at 480°C at potential more reducing than the Ni/NiO equilibrium. The detailed microstructural characterization was conducted using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and analytical transmission electron microscopy (ATEM) and demonstrated that Alloy 600SA is susceptible to diffusion-induced grain boundary migration (DIGM), preferential intergranular oxidation (PIO) and localised Cr and Fe depletions at the grain boundaries. The similar analyses performed on Alloy 600TT demonstrated reduced susceptibility to PIO and grain boundary migration. Further, detailed analyses confirmed that intergranular carbides were readily oxidized/consumed in all 3 environments and acted as Cr reservoir/O trap. These results shed additional light on the "precursor events" for PWSCC of Alloy 600, especially on the mechanism responsible for the enhanced Cr and O diffusivity and on the mechanism responsible for the enhanced Alloy 600TT SCC initiation resistance. Moreover, the strong similarities in the Alloy 600 oxidation behaviour observed for the 3 different environments and at the 3 different temperatures suggested that the same PIO mechanism is active in both steam and water and at temperatures between 320°C and 480°C. These results strongly support the possibility of using the low-pressure H2-steam environment as a substitute environment to accelerate PWSCC initiation without changing the mechanism.

Os aÃos inoxidÃveis austenÃticos tÃm sido bastante utilizados em equipamentos de utilidades de dessulfurizaÃÃo de petrÃleo devido à sua boa resistÃncia à corrosÃo em temperatura elevada.Contudo, esses materiais estÃo sujeitos a sensitizaÃÃo (deficiÃncia em cromo na regiÃo vizinha ao contorno de grÃo) quando expostos a temperaturas de 425 a 815ÂC, durante a operaÃÃo ou processos de fabricaÃÃo. A sensitizaÃÃo torna o equipamento suscetÃvel à corrosÃo sob tensÃo causada por aÃos politiÃnicos, formados pela interaÃÃo de compostos sulforoso, umidade e ar em temperatura ambiente. A resistÃncia à corrosÃo sob tensÃo de amostras de aÃo inoxidÃvel austenÃtico AISI 321 e 347, removidas de um tubo, foi investigada atravÃs do procedimento ASTM 262 Pr. E â ensaio alternativo e de execuÃÃo mais fÃcil do que a simulaÃÃo dos aÃos politiÃnicos. Os corpos de prova foram submetidos aos tratamentos tÃrmicos de estabilizaÃÃo (900ÂC, durante 75 minutos) e de sensitizaÃÃo (600ÂC, durante 20, 40, 80, 120 e 140 horas), apÃs o que foram expostos ao meio corrosivo de CuSO4 + H2SO4 durante 72 horas e depois dobradas, nÃo apresentando trincamento. A agressividade do meio utilizado no ensaio foi verificada atravÃs da utilizaÃÃo de amostras de aÃo AISI 304L sensitizadas (600ÂC, 24, 28 e 72 horas e 677ÂC durante 4, 45 e 72 horas). Neste caso, somente as amostras com acabamento superficial feito com lixa n 100 sofreram um intensivo processo corrosivo. / Os aÃos inoxidÃveis austenÃticos tÃm sido bastante utilizados em equipamentos de utilidades de dessulfurizaÃÃo de petrÃleo devido à sua boa resistÃncia à corrosÃo em temperatura elevada.Contudo, esses materiais estÃo sujeitos a sensitizaÃÃo (deficiÃncia em cromo na regiÃo vizinha ao contorno de grÃo) quando expostos a temperaturas de 425 a 815ÂC, durante a operaÃÃo ou processos de fabricaÃÃo. A sensitizaÃÃo torna o equipamento suscetÃvel à corrosÃo sob tensÃo causada por aÃos politiÃnicos, formados pela interaÃÃo de compostos sulforoso, umidade e ar em temperatura ambiente. A resistÃncia à corrosÃo sob tensÃo de amostras de aÃo inoxidÃvel austenÃtico AISI 321 e 347, removidas de um tubo, foi investigada atravÃs do procedimento ASTM 262 Pr. E â ensaio alternativo e de execuÃÃo mais fÃcil do que a simulaÃÃo dos aÃos politiÃnicos. Os corpos de prova foram submetidos aos tratamentos tÃrmicos de estabilizaÃÃo (900ÂC, durante 75 minutos) e de sensitizaÃÃo (600ÂC, durante 20, 40, 80, 120 e 140 horas), apÃs o que foram expostos ao meio corrosivo de CuSO4 + H2SO4 durante 72 horas e depois dobradas, nÃo apresentando trincamento. A agressividade do meio utilizado no ensaio foi verificada atravÃs da utilizaÃÃo de amostras de aÃo AISI 304L sensitizadas (600ÂC, 24, 28 e 72 horas e 677ÂC durante 4, 45 e 72 horas). Neste caso, somente as amostras com acabamento superficial feito com lixa n 100 sofreram um intensivo processo corrosivo. / Because of their resistance to high temperature corrosion by hydrogen sulfide, austenitic stanless steels are commonly used for equipment in desulfurization process. However, these materials are subject to sensitization (chromium carbide precipitation) from exposure in the temperature range 425 to 815ÂC during fabrication or operation. Sensitization makes the equipment susceptible to failure from intergranular stress corrosion cracking caused by polythionic acid. Polythionic acid is formed by sulfur compounds, moisture, and air at ambient temperature. The main goal of the present work is to investigate the stress corrosion cracking susceptibility of stainless steels AISI 321 and 347 in polythionic acids using an alternative process that is to submit the samples to cooper-cooper sulfate-16% sulfuric acid test (ASTM A262 Pr.E). After the stabilization heat treatment at 900ÂC for 75 minutes, samples were heat treated at 600ÂC during 20, 40, 80, 120 and 140 hours and then exposed to boiling acidified copper sulfate solution for 72 hours. After exposure, the specimens were bent. The appearance of fissures or cracks was not observed in AISI 321 and 347 samples. The effectiveness of the solution has been made by submitting AISI 304L samples to the same environment . The AISI 304L samples with higher finishing have been cracked. The ones with fine-ground finishing have not been attacked. / Because of their resistance to high temperature corrosion by hydrogen sulfide, austenitic stanless steels are commonly used for equipment in desulfurization process. However, these materials are subject to sensitization (chromium carbide precipitation) from exposure in the temperature range 425 to 815ÂC during fabrication or operation. Sensitization makes the equipment susceptible to failure from intergranular stress corrosion cracking caused by polythionic acid. Polythionic acid is formed by sulfur compounds, moisture, and air at ambient temperature. The main goal of the present work is to investigate the stress corrosion cracking susceptibility of stainless steels AISI 321 and 347 in polythionic acids using an alternative process that is to submit the samples to cooper-cooper sulfate-16% sulfuric acid test (ASTM A262 Pr.E). After the stabilization heat treatment at 900ÂC for 75 minutes, samples were heat treated at 600ÂC during 20, 40, 80, 120 and 140 hours and then exposed to boiling acidified copper sulfate solution for 72 hours. After exposure, the specimens were bent. The appearance of fissures or cracks was not observed in AISI 321 and 347 samples. The effectiveness of the solution has been made by submitting AISI 304L samples to the same environment . The AISI 304L samples with higher finishing have been cracked. The ones with fine-ground finishing have not been attacked.

Increased equipment failures and the resultant increase in unplanned downtime as the result of process optimization programs continue to plague pulp mills. The failures are a result of a lack of understanding of corrosion in the different pulping liquors, specifically the parameters responsible for its adjustment such as the role and identification of inorganic and organic species. The current work investigates the role of inorganic species, namely sodium hydroxide and sodium sulfide, on liquor corrosivity at a range of process conditions beyond those currently experienced in literature. The role of sulfur species, in the activation of corrosion and the ability of hydroxide to passivate carbon steel A516-Gr70, is evaluated with gravimetric and electrochemical methods. The impact of wood chip weathering on process corrosion was also evaluated. Results were used to identify black liquor components, depending on the wood species, which play a significant role in the activation and inhibition of corrosion for carbon steel A516-Gr70 process equipment. Further, the effect of black liquor oxidation on liquor corrosivity was evaluated. Corrosion and stress corrosion cracking performance of selected materials provided information on classes of materials that may be reliably used in aggressive pulping environments.

Joints between carbon steel and Alloy 600, containing Alloy 82 weld metal, were exposed to two steam-hydrogen environments considered to simulate exposure to primary water conditions in a Pressurized Water Reactor (PWR) or Canada Deuterium Uranium (CANDU) reactor. The welds were found to have elevated and variable iron contents due to dilution by carbon steel during welding. This gave the Alloy 82 weld, near the inner surface of the component, an iron content approaching that of Alloy 800. A potentially protective external iron oxide film formed on the inner surface of the weld. However, the chromium content throughout the weld is below that which would form an external chromium oxide. The results indicate that low chromium content causes internal oxidation throughout the weld and potentially below the external iron oxide which could lead to Primary Water Stress Corrosion Cracking (PWSCC).