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The environmentally-assisted fatigue crack growth behaviour of austenitic stainless steels in deoxygenated high temperature water at low strain rates has been reported to be greatly affected by the sulphur (S) content of the specimen, with high S specimens exhibiting significant reduced crack growth rates (retardation) when compared to low S specimens. To further the understanding of the mechanistic behaviour, fatigue crack growth experiments have been performed on high and low sulphur Type 316 austenitic stainless steel specimens tested in high temperature water and evaluated via microstructural characterisation techniques. At high strain rates the enhanced crack growth for both specimens appeared to be crystallographic and associated with slip localization. Furthermore, matching fracture surface analysis indicated discrepancy of the slip steps and micro-cleavage cracks between the matching surfaces, suggesting that slip steps and micro-cleavage cracking occurred after the crack-tip had advanced. It was also postulated that their formation may involve cathodically-produced hydrogen and shear deformation on the fracture surface. However, when the loading frequency was decreased, the high S specimens retarded the crack growth and the path was no longer crystallographic. Significant differences in the crack-tip opening displacements were observed in both materials, with blunt crack-tips in the high sulphur specimen and sharp tips in the low sulphur specimen when the strain rate was low. EBSD analysis at the crack-tips of both specimens showed that the strain was more localised at the crack-tip of the low sulphur specimen whist the strain ahead of the high sulphur specimen was more homogenous. It is thus postulated that retardation occurs when slip localisation is no longer the dominant factor. The localised deformation during enhancement is believed to have been caused by hydrogen enhanced localised plasticity (HELP) which causes the crack-tip to sharpen. The diffused strain distribution during crack growth retardation is believed to have been caused by hydrogen enhanced creep (HEC) which causes the crack-tip to blunt. It is also believed that both enhancement and retardation mechanisms are associated with contrasting effects deriving from hydrogen enhanced plasticity. Oxide induced crack closure was excluded as a mechanism responsible for retardation of fatigue crack growth when the stress ratio is high. Effects of hydrogen induced alpha' and ε martensite phases on oxidation behaviour of austenitic stainless steels in deoxygenated high temperature water have also been studied. Microstructural characterisation shows that hydrogen induced alpha' martensite enhances oxidation of austenitic stainless steels in deoxygenated high temperature water. The implications of this finding on environmentally assisted cracking of austenitic stainless steels in deoxygenated high temperature water is discussed.

The majority of UK’s intermediate level radioactive waste is currently stored in 316L and 304L austenitic stainless steel containers in interim storage facilities for permanent disposal until a geological disposal facility has become available. The structural integrity of stainless steel canisters is required to persevere against environmental degradation for up to 500 years to assure a safe storage and disposal scheme. Hitherto existing severe localised corrosion observances on real waste storage containers after 10 years of exposure to an ambient atmosphere in an in-land warehouse in Culham at Oxfordshire, however, questioned the likelihood occurrence of stress corrosion cracking that may harm the canister’s functionality during long-term storage. The more corrosion resistant duplex stainless steel grade 2205, therefore, has been started to be manufactured as a replacement for the austenitic grades. Over decades, the threshold stress corrosion cracking temperature of austenitic stainless steels has been believed to be 50-60°C, but lab- and field-based research has shown that 304L and 316L may suffer from atmospheric stress corrosion cracking at ambient temperatures. Such an issue has not been reported to occur for the 2205 duplex steel, and its atmospheric stress corrosion cracking behaviour at low temperatures (40-50°C) has been sparsely studied which requires detailed investigations in this respect. Low temperature atmospheric stress corrosion cracking investigations on 2205 duplex stainless steel formed the framework of this PhD thesis with respect to the waste storage context. Long-term surface magnesium chloride deposition exposures at 50°C and 30% relative humidity for up to 15 months exhibited the occurrence of stress corrosion cracks, showing stress corrosion susceptibility of 2205 duplex stainless steel at 50°C.The amount of cold work increased the cracking susceptibility, with bending deformation being the most critical type of deformation mode among tensile and rolling type of cold work. The orientation of the microstructure deformation direction, i.e. whether the deformation occurred in transverse or rolling direction, played vital role in corrosion and cracking behaviour, as such that bending in transverse direction showed almost 3-times larger corrosion and stress corrosion cracking propensity. Welding simulation treatments by ageing processes at 750°C and 475°C exhibited substantial influences on the corrosion properties. It was shown that sensitisation ageing at 750°C can render the material enhanced susceptible to stress corrosion cracking at even low chloride deposition densities of ≤145 µm/cm². However, it could be shown that short-term heat treatments at 475°C can decrease corrosion and stress corrosion cracking susceptibility which may be used to improve the materials performance. Mechanistic understanding of stress corrosion cracking phenomena in light of a comprehensive microstructure characterisation was the main focus of this thesis.