Les aciers inoxydables super martensitiques sont très utilisés dans le secteur pétrochimique, mais ils présentent des ruptures en service en conditions sévères. L'objectif de cette étude est d'apporter une meilleure compréhension du mécanisme de corrosion sous contrainte de ces matériaux en milieu H$_2$S. Pour cela, des coulées laboratoires ont été élaborées avec différentes teneurs en molybdène, élément connu pour améliorer la résistance à la corrosion. Ces ajouts d'éléments d'alliage impliquent alors une caractérisation fine de la microstructure, pour bien appréhender par la suite les mécanismes de rupture. Une attention particulière a été apportée à l'évolution de la fraction d'austénite et de ferrite résiduelle avec les traitements thermiques d'hypertrempe et de revenus qui sont couramment pratiqués sur ces nuances. Puis, par des mesures électrochimiques sans contrainte mécanique, l'ajout de molybdène a été identifiée comme bénéfique pour renforcer la passivité de la nuance dans le milieu H$_2$S. Et pour des teneurs en molybdène inférieures à 2,25%, des produits de corrosion ont été identifiés, principalement des sulfures de nickel, qui sont des inhibiteurs de la recombinaison de l'hydrogène. Par la suite, des essais de corrosion sous contrainte sous charge statique et dynamique couplés à des mesures d'impédance électrochimique montrent un effet bénéfique du molybdène et de l'austénite résiduelle. Le molybdène permet notamment de réduire les défauts du film passif. Un modèle d'éléments finis permet de simuler les essais de traction lente en tenant compte de la fragilisation par hydrogène. Afin de l'alimenter avec des paramètres expérimentaux, une cellule de perméation électrochimique a été montée et a permis de mesurer le coefficient de diffusion de l'hydrogène au sein de nos différentes coulées. Le modèle présente alors une bonne adéquation avec les résultats expérimentaux et une étude paramétrique a été réalisée sur le coefficient de diffusion et sur la concentration interfaciale en hydrogène. Enfin, une synthèse permet la proposition d?un mécanisme de corrosion sous contrainte comportant deux étapes : la résistance du film passif pour limiter l'absorption de l?hydrogène dans la matrice et le piégeage de l'hydrogène par l'austénite résiduelle en fonction de la déformation. / Super martensitic stainless steels are widely used in the oil and gas industry, but failures occurred in service under severe conditions. The aim of this study is to provide a better understanding of the stress corrosion mechanism in H$_2$S medium. For this purpose, laboratory heats have been casted with different molybdenum contents, a component known to improve corrosion resistance. These additions of alloying elements then involve a fine characterization of the microstructure, in order to grasp the mechanisms of rupture. Particular attention has been paid to the evolution of the retained austenite and residual ferrite fraction with the heat treatments of quench and annealing which are commonly practiced on these grades. Then, by electrochemical measurements without mechanical stress, the addition of molybdenum was identified as beneficial for the passivity of the grade in the H$_2$S medium. And for 2.25% molybdenum contents, corrosion products have been identified as mainly nickel sulfides, which are inhibitors of hydrogen recombination. Subsequently, corrosion tests under static and dynamic load coupled to electrochemical impedance measurements show a beneficial effect of molybdenum and residual austenite. In particular, molybdenum reduces the defects of the passive film. A finite elements model simulates the slow strain rate traction tests taking into account the hydrogen embrittlement. In order to use experimental parameters, an electrochemical permeation cell was implemented and used to measure the hydrogen diffusion coefficient within our different heats. A good match with the experimental results was obtained with this model and a parametric study was carried out on the diffusion coefficient and the hydrogen interfacial concentration. Finally, a synthesis provides the proposal of a stress corrosion mechanism divided in two steps: the passive film resistance to limit the hydrogen absorption in the matrix and the trapping of the hydrogen by the residual austenite in function deformation.

According to the National Institute of Occupational Safety and Health (NIOSH), about 100 million rock anchors were installed in the USA mining industry during 1999 (Dolinar, 2000). The rock bolt usage in US coal mining industry fell from 85 million in the year 1988 to 68 million by 2005 (Tadolini, 2006), and is assumed to be close to that number of rock anchors consumed currently since, the tonnage from underground is almost the same. Most underground coal mines have conditions such as moisture in the atmosphere, ground water with different chemical contents that are conducive for corrosion of rock anchors and ancillaries (such as plates), and the effects of this on the performance of the anchors had been researched in the US to an extent from the past research at Southern Illinois University Carbondale (SIUC). In addition to the general corrosion like pitting and crevice, stress corrosion adds to the process a potentially serious threat and results in material failure underground due to stress corrosion cracking (SCC) yet the effects are not fully understood in the USA. The results of this research therefore will have a positive and direct effect on rock related safety. During this research project in situ specific tests were conducted with bolts to try and determine the corrosion potential in a specific coal-mining region. The coal mining areas were divided into three regions and were named as East, Mid-West and West respectively. To enhance the value/importance of the field data collected from the mines, a metal mine and a salt mine (two non-coal mines) were included in the plan and the data analysis proved that the methodology developed for determining the corrosion potential underground is applicable to any underground mines. The Insitu studies include water samples collection and analysis and open circuit potential (OCP/Eoc) testing and analysis. Open Circuit Potential (OCP) data were recorded to estimate probability of active corrosion. Hypothetically, probability of active corrosion is lower if the actual OCP of roof bolts in the mine is less than the characteristic OCP of the steel grade, and vice versa. The effects of certain factors such as the roof condition, reference distance (distance between bolt and reference electrode) on the open circuit potential data during the measurements were studied to ensure its impact on the corrosion potential determination technique developed. The findings from this research helps standardize the corrosion potential determination methodology. The preliminary study of stress corrosion cracking of the subject test sample (Grade 60 rebar roof bolt) was conducted in this research work. The experimental study invloves testing a complete roof bolt in the mine simulated environment. The mine simulated environment in the test cell consists of the roof strata material collected from the mine site with continuous flow of water at slower and varaible flow rate (0 to 3 ml/minute) with pH in the range of 7.5 to 9.0. The results showed that stress corrosion could be very serious problem when it comes to long term mining applications. The stress corrosion test cell developed and tested was proved to be significant in conducting the long term stress corrosion tests. The strength results of the Grade 60 rebar roof bolt tested had a significant strength loss after 3 months of testing in the stress corrosion cell. Hence, more SCC studies are deemed necessary to evaluate the seriousness of the problem and if possible eliminate it.

abstract: This research examines several critical aspects of the so-called "film induced cleavage" model of stress corrosion cracking using silver-gold alloys as the parent-phase material. The model hypothesizes that the corrosion generates a brittle nanoporous film, which subsequently fractures forming a high-speed crack that is injected into the uncorroded parent-phase alloy. This high speed crack owing to its kinetic energy can penetrate beyond the corroded layer into the parent phase and thus effectively reducing strength of the parent phase. Silver-gold alloys provide an ideal system to study this effect, as hydrogen effect can be ruled out on thermodynamic basis. During corrosion of the silver-gold alloy, the less noble metal i.e. silver is removed from the system leaving behind a nanoporous gold (NPG) layer. In the case of polycrystalline material, this corrosion process proceeds deeper along the grain boundary than the matrix grain. All of the cracks with apparent penetration beyond the corroded (dealloyed) layer are intergranular. Our aim was to study the crack penetration depth along the grain boundary to ascertain whether the penetration occurs past the grain-boundary dealloyed depth. EDS and imaging in high-resolution aberration corrected scanning transmission electron microscope (STEM) and atom probe tomography (APT) have been used to evaluate the grain boundary corrosion depth. The mechanical properties of monolithic NPG are also studied. The motivation behind this is two-fold. The crack injection depth depends on the speed of the crack formed in the nanoporous layer, which in turn depends on the mechanical properties of the NPG. Also NPG has potential applications in actuation, sensing and catalysis. The measured value of the Young's modulus of NPG with 40 nm ligament size and 28% density was ~ 2.5 GPa and the Poisson's ratio was ~ 0.20. The fracture stress was observed to be ~ 11-13 MPa. There was no significant change observed between these mechanical properties on oxidation of NPG at 1.4 V. The fracture toughness value for the NPG was ~ 10 J/m2. Also dynamic fracture tests showed that the NPG is capable of supporting crack velocities ~ 100 - 180 m/s. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2014

abstract: Dealloying induced stress corrosion cracking is particularly relevant in energy conversion systems (both nuclear and fossil fuel) as many failures in alloys such as austenitic stainless steel and nickel-based systems result directly from dealloying. This study provides evidence of the role of unstable dynamic fracture processes in dealloying induced stress-corrosion cracking of face-centered cubic alloys. Corrosion of such alloys often results in the formation of a brittle nanoporous layer which we hypothesize serves to nucleate a crack that owing to dynamic effects penetrates into the un-dealloyed parent phase alloy. Thus, since there is essentially a purely mechanical component of cracking, stress corrosion crack propagation rates can be significantly larger than that predicted from electrochemical parameters. The main objective of this work is to examine and test this hypothesis under conditions relevant to stress corrosion cracking. Silver-gold alloys serve as a model system for this study since hydrogen effects can be neglected on a thermodynamic basis, which allows us to focus on a single cracking mechanism. In order to study various aspects of this problem, the dynamic fracture properties of monolithic nanoporous gold (NPG) were examined in air and under electrochemical conditions relevant to stress corrosion cracking. The detailed processes associated with the crack injection phenomenon were also examined by forming dealloyed nanoporous layers of prescribed properties on un-dealloyed parent phase structures and measuring crack penetration distances. Dynamic fracture in monolithic NPG and in crack injection experiments was examined using high-speed (106 frames s-1) digital photography. The tunable set of experimental parameters included the NPG length scale (20-40 nm), thickness of the dealloyed layer (10-3000 nm) and the electrochemical potential (0.5-1.5 V). The results of crack injection experiments were characterized using the dual-beam focused ion beam/scanning electron microscopy. Together these tools allow us to very accurately examine the detailed structure and composition of dealloyed grain boundaries and compare crack injection distances to the depth of dealloying. The results of this work should provide a basis for new mathematical modeling of dealloying induced stress corrosion cracking while providing a sound physical basis for the design of new alloys that may not be susceptible to this form of cracking. Additionally, the obtained results should be of broad interest to researchers interested in the fracture properties of nano-structured materials. The findings will open up new avenues of research apart from any implications the study may have for stress corrosion cracking. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2012

M.Ing. / This dissertation deals with the structural integrity analysis of a low pressure (LP) turbine with transverse cracking. Cracks are initiated in the centre ring keyway of the shaft by a fretting mechanism and propagate during barring operation. The cracks arrest during normal operation when they are still relatively shallow. The aim of the calculations is to predict the transition where cracks start propagating by high cycle fatigue during normal operation of the shaft. Most influencing factors, including continuum mechanics, mathematical modelling, material behaviour, service loads and industry experience, are studied in detail as a precursor to the case study. The calculated results show that the case study is an example where the application of fracture mechanics on the crack-free stress field leads to erroneous results. There is a significant redistribution of stress in the presence of the crack so that the actual stress ratio, as calculated from three dimensional cracked models, varies significantly compared to the crack-free model. Calculated results, together with carefully researched material properties, confirm the postulated crack growth during barring operation and predict limiting crack sizes where high cycle fatigue would ensue during normal operation. The case study concludes that the shaft has a significant remaining life and that it can be returned to service with periodic non-destructive examinations.

La Corrosion Sous Contrainte (CSC) est un des principaux modes de dégradation des composants assemblés par soudage dans Réacteurs à Eau Pressurisée (REP). Le retour d’expérience de 2007 sur les soudures en alliage à base de nickel a présenté 3 cas de fissuration par CSC sur l’Alliage 82 sur les 300 cas recensés dans le circuit primaire. L’objectif de cette étude est alors d’identifier des paramètres microstructuraux et mécaniques à l’échelle de la microstructure impliqués dans l’amorçage de fissures. Les caractérisations du matériau pour identifier ces paramètres sont composées d’une part, d’analyses de la composition chimique et d’analyses EBSD (Electron Back-Scattered Diffraction) pour la morphologie et les orientations cristallographiques des grains pour la microstructure et, d’autre part, de mesures expérimentales de déformation en surface et de calculs numériques de champs de contrainte autour des joints de grains par éléments finis pour le comportement mécanique. La corrélation de ces informations avec les sites d’amorçage de fissures de CSC obtenus avec les essais d’amorçage entrepris sur des éprouvettes U-bend en milieu vapeur d’eau hydrogénée à 400°C, 188 bar a confirmé la sensibilité de l’Alliage 82 en CSC avec une fissuration intergranulaire des joints de grains dont la particularité première est d’être perpendiculaire à la sollicitation (mode I). Les autres paramètres concernent celui de la chimie locale au niveau des joints de grains, de leur nature (généraux ou spéciaux) et du chargement mécanique appliqué à ces derniers (contrainte et différence de déformation). Cette méthodologie, applicable à d’autre matériau, a permis de mieux comprendre quels sont les paramètres microscopiques sensibilisent la cohésion du joint de grains et à quels degré d’importance doivent-il être pris en compte dans le mécanisme d’amorçage de fissures de CSC. / In Pressurize Water Reactors (PWR), Stress Corrosion Cracking (SCC) is the mean degradation mode of components pieced together by welding. Nickel based alloys are, among others, used in dissimilar metal welding (DMW). International report showed only 3 cracking cases in Alloy 82 out of 300 cracking cases concerned on nickel based alloys DMW in primary water circuit. The aim of this study is to identify which microstructural and local mechanism parameters at microstructure scale provide the initiation of SCC cracks. Characterizations performed on specimen surface to identify those parameters are composed ofchemical composition analysis and EBSD analysis (Electron Back-Scattered Diffraction) to know the morphology and the crystallography of grains for microstructure features on one hand, and experimental strain fields measured by Digital Imaging Correlation (DIC) of gold microgrids deposed by electronic lithography on U-bend specimen surface and stress fields calculated along grains boundaries by finite element for local mechanical features on the other hand. The correlation between those characterizations and localization of initiation sites of SCC cracks, obtained on U-bend specimens tested in autoclave in hydrogen steam water at 400°C and 188 bar for 3500 hours, confirmed the susceptibility of the Alloy 82 in SCC conditions with intergranular SCC cracks. The perpendicular position to the loading direction (mode I) is the worst conditions for grains boundary in SCC. The others points concern the chemical composition (precipitation, impurities) around grain boundary and the grain boundary type which is more susceptible when it is a High Angle Grain Boundary. It is following by the mechanical characterization (stress and strain gradient) along grain boundary. This methodology can be used to other material and helped to define which microstructural and mechanical parameter can be define the initiation of SCC cracks.

Plusieurs composants présents dans les réacteurs à eau sous pression (REP) ont été fabriqués en alliage 600, un alliage base nickel contenant environ 16% de chrome. Le retour d’expérience, comme les études de laboratoire, montrent une sensibilité à la corrosion sous contrainte (CSC) de cet alliage en milieu primaire.Des études antérieures ont permis de développer un modèle d’amorçage basé sur une approche macroscopique et dépendant de différents paramètres tels que : la température, la contrainte et la microstructure du matériau. Cependant, ce modèle manque de robustesse car l’effet de la teneur en hydrogène dissous et l’effet de l’histoire de chargement mécanique ne sont pas considérés et les effets microstructuraux ne le sont que partiellement.Ces travaux de thèse ont comme objectif principal de développer un modèle local prévoyant le temps d’amorçage des fissures de CSC en fonction de paramètres locaux liés à la microstructure du matériau (précipitation intergranulaire), à l'environnement (température, et teneur en hydrogène dissous) et aux contraintes locales aux joints des grains. Cette étude comprend donc la caractérisation des matériaux (analyse chimique, microstructure et comportement mécanique) et la réalisation des essais d’oxydation et de corrosion sous contrainte, ainsi que leur interprétation.Le modèle local développé est basé sur des grandeurs physiques et enchaine les différentes étapes de CSC à savoir l’incubation, l’amorçage et la propagation des fissures. Pour construire ce modèle, nous avons considéré la formation de pénétrations d’oxyde aux joints de grains comme une étape-clé dans l’amorçage des fissures de CSC. Pour cela, une cinétique d’oxydation intergranulaire pour l’alliage 600 a été identifiée. De plus, un critère d’amorçage des fissures de CSC a été déterminé en couplant contrainte locale et profondeur d’oxydation intergranulaire critique. Enfin, l’étape de propagation des fissures a été modélisée à partir d’une base de données rassemblant les profondeurs de fissure atteintes en fonction du temps d’essai pour différentes conditions expérimentales. / Several components present in the primary circuit of Pressurized Water Reactors (PWR) of nuclear power plants were manufactured with Alloy 600, a nickel base alloy containing 16 wt.% chromium. Operating experience of PWRs and laboratory tests showed that Alloy 600 is susceptible to stress corrosion cracking (SCC).Previous studies have allowed developing an initiation model based on a macroscopic approach and depending on several parameters such as temperature, applied stress and material microstructure. However, this model suffers from a lack of accuracy: dissolved hydrogen content and mechanical loading history effects are not considered and the microstructure effects (such as intergranular precipitation) are only partially taken into account.The aim of this study is to develop a ‘local’ model predicting stress corrosion cracking initiation time, based on physical mechanisms and local parameters related to the material microstructure (intergranular precipitation), the environment chemistry (temperature and dissolved hydrogen content) and stress concentration at grain boundaries. The local model relies on a cracking scenario with three main steps: incubation, initiation and crack extension.The formation of intergranular oxide penetration was assumed to be a key step in SCC initiation. For this purpose, oxidation tests were performed in simulated primary water. The intergranular oxidation kinetics of Alloy 600 was studied and the effects of intergranular carbide precipitation, dissolved hydrogen content and temperature were investigated. In addition, a cracking criterion coupling a critical local stress and a critical intergranular oxide depth was estimated. Finally, a sigmoid crack growth law was used to simulate both the slow and fast propagation steps. The local model was validated using a database built from the results of SCC tests performed on Alloy 600 and gathering the crack depths reached as a function of test duration for different experimental conditions (material microstructure, loading conditions).

The need to inject treated seawater to enhance reservoir pressure and secondary oil recovery is increasing in the oil field, so also is the reservoir souring potential caused by the activities of Sulphate Reducing Bacteria (SRB) generating H2S in the reservoir. The total cost of SRB mediated corrosion in the United States alone is estimated to be 1-2 billion US dollars per year. In the last few years, a number of potential souring mitigation and prevention tools have been studied. These include: sulphate-reduction using membranes, biocide injection and nitrate injection. Out of all the various methods used for the mitigation and prevention of reservoir souring, the use of nitrate injection in conjunction with waterflood projects is becoming more popular because of its economic benefits and least environmental impact. However, nitrate injection is still widely considered as an emergent technology because there are still many unknowns. One of the major unknowns, of great concern is the susceptibility of subsea hardware components to nitrite, which is a by-product of nitrate anti-souring treatment. Any detrimental effect can compromise the technical integrity of subsea installations. The objective of this research is to study the corrosion susceptibility of CRA (13Cr- Martensitic, 22Cr, and 25Cr super duplex stainless steel) to pitting and stress corrosion cracking in the presence of nitrite. Research hitherto, has investigated corrosion susceptibility of carbon steel to nitrite and found out that nitrite causes pitting in carbon steel. This research work built on previous studies and extensively investigated the effect of nitrite on CRA materials in terms of pitting and stress corrosion cracking. Using electrochemistry techniques in conjunction with C-ring test and slow strain rate test, with variables such as temperature, and nitrite concentration all under anaerobic conditions. Metallographic examination and further evaluation using scanning electron microscopy confirmed pitting and intergranular stress corrosion cracking of 13Cr-L80 and 25Cr due to presence of nitrite.Test data confirmed that sodium nitrite is an anodic inhibitor; it shifts the corrosion potentials to more noble potential and also shifts the anodic curve to lower current, given a net reduction in corrosion rate. A critical concentration of 400ppm is required for inhibition to be effective on 13Cr-L80 and 25Cr. However, below the critical concentration, nitrite significantly increases the corrosion rate. The experimental data generated from this research work provides very valuable information that will tremendously assist the materials selection process for subsea and subsurface hardware components and also serve as a guide in the corrosion management process in existing systems.

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