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The stress corrosion cracking (SCC) behaviour of Mg alloy AZ31B was investigated with respect to surface condition. Salt fog U-bend testing was used to identify changes in SCC as a result of surface conditioning pre-treatments. Six surface conditions were investigated: as-received, mechanically-polished, sulphuric acid (H2SO4)-cleaned, mechanically-polished then H2SO4-cleaned, aged H2SO4-cleaned, and acetic acid (C2H4O2)-cleaned. Results showed that the rate of SCC was accelerated and the SCC mode was intergranular for all surface conditioning treatments involving H2SO4-cleaning. It was found that the accelerated intergranular SCC was a result of three contributing factors: a low pH, the presence of aggressive ions, and a porous film which allowed direct contact between the metal surface and the electrolyte. Characterization of the surfaces using potentiodynamic polarization and cross-sectional images of sample surfaces showed that in the absence of one of these three contributing factors intergranular SCC would not occur. / Thesis / Master of Applied Science (MASc)

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No description available.

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Ce travail de thèse s’intéresse aux alliages à base nickel exposés au milieu primaire des réacteurs à eau pressurisée : ceux-ci, et en particulier, l’alliage 600, contenant environ 16% de chrome, montrent, en service, une sensibilité à un phénomène de corrosion localisée appelé corrosion sous contrainte (CSC). La corrosion sous contrainte aboutit, à terme, au développement de fissures intergranulaires nécessitant le remplacement des matériaux de structure. La compréhension de ces phénomènes constitue donc un enjeu majeur dans le cadre de la sûreté et du prolongement de la durée de vie des réacteurs, avec, également, des aspects économiques évidents. Le rôle de cette étude est d’apporter des éléments de compréhension quant au rôle de l’hydrogène dans ces phénomènes de corrosion sous contrainte. L’objectif de ce travail était double : d’une part, déterminer la source principale de l’hydrogène absorbé par l’alliage lors de exposition au milieu primaire, et d’apporter des éléments permettant de caractériser le mécanisme responsable de son absorption. D’autre part, un second objectif consistait à évaluer dans quelle mesure l’hydrogène absorbé par l’alliage pouvait jouer un rôle dans ces phénomènes de CSC, notamment, en regard de ses interactions possibles avec les défauts de structure du matériau. À cette fin, des techniques de traçage isotopique mises en œuvre lors de la corrosion de ces alliages en milieu primaire ont été utilisées, la pénétration des traceurs étant ensuite analysées par spectrométrie de masse d’ions secondaires. Ces analyses ont permis de montrer que l’hydrogène absorbé provenait principalement de la dissociation de la molécule d’eau lors de l’édification du film d’oxyde passif. Par ailleurs, la création de défauts de structure dans le matériau, et leur étude par annihilation de positons et microscopie électronique en transmission, après création ou après interaction avec l’hydrogène introduit par chargement cathodique, ont permis de caractériser les interactions de cet élément avec les défauts. Ces interactions sont importantes, et mènent à une réorganisation des défauts (coalescence, migration), mais sont transitoires, leur intensité dépendant de l’activité locale de l’hydrogène en solution. Ces résultats ont permis la proposition d’un nouveau modèle d’amorçage et de propagation des fissures de CSC. / Since the late 1960s, a special form of stress corrosion cracking (SCC) has been identified for Alloy 600 exposed to pressurized water reactors (PWR) primary water: intergranular cracks develop during the alloy exposure, leading, progressively, to the complete ruin of the structure, and to its replacement. The main goal of this study is therefore to evaluate in which proportions the hydrogen absorbed by the alloy during its exposure to the primary medium can be responsible for SCC crack initiation and propagation. This study is aimed at better understanding of the hydrogen absorption mechanism when a metallic surface is exposed to a passivating PWR primary medium. A second objective is to characterize the interactions of the absorbed hydrogen with the structural defects of the alloy (dislocations, vacancies…) and evaluate to what extent these interactions can have an embrittling effect in relation with SCC phenomenon. Alloy 600-like single-crystals were exposed to a simulated PWR medium where the hydrogen atoms of water or of the pressuring hydrogen gas were isotopically substituted with deuterium, used as a tracer. Secondary ion mass spectrometry depth-profiling of deuterium was performed to characterize the deuterium absorption and localization in the passivated alloy. The results show that the hydrogen absorption during the exposure of the alloy to primary water is associated with the water molecules dissociation during the oxide film build-up. In an other series of experiments, structural defects were created in recrystallized samples, and finely characterized by positron annihilation spectroscopy and transmission electron microscopy, before or after the introduction of cathodic hydrogen. These analyses exhibited a strong hydrogen/defects interaction, evidenced by their structural reorganization under hydrogenation (coalescence, migrations). However, thermal desorption spectroscopy analyses indicated that these interactions are transitory, and dependent on the local hydrogen activity in the bulk material. Finally, these results allowed a new model describing SCC crack initiation and propagation to be formulated.

Lifetime prediction of components in Alloy 600 is a major concern for nuclear power plants. Alloy 600 components have been shown to be susceptible to stress corrosion cracking (SCC). In the 1990’s, an engineering model was developed in order to predict the life time as a function of the main macroscopic parameters (stress, environment, material), based on laboratory results. This model has since been used to predict the ranking of various Alloy 600 components, using the knowledges of the manufacturing and service conditions for each component. It was applied successfully in the case of forged control rod drive mechanism (CRDM) nozzles. However, it was found necessary to improve this model to account for the strain history of the different components. Predictions using the model, investigated from an array of test results on Alloy 600 in laboratory primary water, have demonstrated that the time for initiation differed significantly according to the strain path applied to the specimen. The present work is dedicated to assess SCC results from samples with different strain paths and different level of cold work in order to better understand the manufacturing conditions on SCC. The samples are machined in three different directions and tested at different durations in order to model the time for transition (transition between slow and fast propagation) as a function of cold work, strain path and stress. Thermomechanical treatments are also applied on two different heats of Alloy 600: forged WF675 (very susceptible to SCC in as received conditions) and rolled 78456/337 (non susceptible to SCC in as-received conditions) in order to transform the forged microstructure into a microstructure close to the rolled microstructure and vice-versa. These microstructures are then tested in primary conditions and the results are compared to the results obtained on as-received material in order to get a better understanding of manufacturing process and microstructure parameters regarding SCC behaviour.

Chloride-induced stress corrosion cracking (CISCC) has been identified as the main degradation mechanism for spent nuclear fuel dry storage canisters. This type of induced cracking is complex and depends on several factors, such as material composition, exposure temperature, relative humidity, applied tensile stress, and atmospheric salt concentration. An accelerated experiment was designed to simulate marine environments in a controlled fogging chamber to examine 304 and 304L stainless steel U-bend and welded U-bend samples. The samples were exposed to chloride rich and humid fogging in a corrosion chamber at 35℃ continuously for 4 weeks, 8 weeks, and 12 weeks. The same experiment was repeated at 50℃ for 4 weeks, 8 weeks, and 14 weeks to study the sensitivity of CISCC to temperature changes. A qualitative evaluation of optical micrographs from a 3D Surface Profiler was performed for 16 corroded samples and compared with 2 reference samples. Cracking was observed on 12 out of 16 samples exposed to 35℃ and 50℃ for durations ranging from 8 to 14 weeks. Likely cracking observations were noted on 4 out of 16 samples. A quantitative statistical analysis was also performed using surface profile depth (valley) data from corroded and reference samples. The quantitative analysis examined the effect of temperature, welding, exposure duration, and material composition. The quantitative results were compared with the qualitative results and literature published in CISCC. / Master of Science / Most nuclear power plants are currently using dry storage canisters (DSCs) which are made of a concrete vault and a stainless steel canister that houses the spent nuclear fuel (SNF) assemblies. Multiple conditions must be present simultaneously for chloride-induced stress corrosion cracking (CISCC) to develop, such as the presence of a susceptible alloy, high relative humidity, high temperature, high atmospheric salt concentrations, and applied tensile stresses. DSCs are typically made from 300-series austenitic stainless steels which are susceptible to this type of corrosion during long-term storage near marine environments. Therefore, understanding of the factors leading to CISCC is critically important for proper management and mitigation and to estimate the service life of DSCs for the safe long-term storage of SNF. An accelerated experiment was designed to examine the effects of temperature, exposure duration, and welding on pitting and cracking for 304 and 304L U-bend samples. The experimental results concluded that stainless-steel grades 304 and 304L are susceptible to CISCC when exposed for 8 weeks or longer to fogging at temperatures between 35℃ and 50℃, 95% relative humidity, and 5% salt concentration. This study also concluded that increasing exposure duration from 8 to 12 weeks or the temperature from 35℃ to 50℃ had no significant effect on the acceleration of CISCC. Also, unwelded samples were deemed more susceptible to CISCC than welded samples and the susceptibility of 304 and 304L grades were relatively similar.

This study investigated localized corrosion behavior of austenitic stainless steels under stressed and unstressed conditions, as well as corrosion of metallic thin films. While austenitic stainless steels are widely used in corrosive environments, they are vulnerable to pitting and stress corrosion cracking (SCC), particularly in chloride-containing environments. The corrosion resistance of austenitic stainless steels is closely tied to the alloying elements chromium, nickel, and molybdenum. Polarization curves were measured for five commercially available austenitic stainless steels of varying chromium, nickel, and molybdenum content in 3.5 wt.% and 25 wt.% NaCl solutions. The alloys were also tested in tension at slow strain rates in air and in a chloride environment under different polarization conditions to explore the relationship between the extent of pitting corrosion and SCC over a range of alloy content and environment. The influence of alloy composition on corrosion resistance was found to be consistent with the pitting resistance equivalent number (PREN) under some conditions, but there were also conditions under which the model did not hold for certain commercial alloy compositions. Monotonic loading was used to generate SCC in in 300 series stainless steels, and it was possible to control the failure mode through adjusting environmental and polarization conditions. Metallic thin film systems of thickness 10-200 nm are being investigated for use as corrosion sensors and protective coatings, however the corrosion properties of ferrous thin films have not been widely studied. The effects of film thickness and substrate conductivity were examined using potentiodynamic polarization and scanning vibrating electrode technique (SVET) on iron thin films. Thicker films undergo more corrosion than thinner films in the same environment, though the corrosion mechanism is the same. Conductive substrates encourage general corrosion, similar to that of bulk iron, while insulating substrates supported only localized corrosion.