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Boisson, Marylou
Universite de Toulouse, Ecole doctorale Sciences de la Matiere - SDM, Institut National Polytechnique de Toulouse - INP Toulouse, Centre Interuniversitaire de Recherche et d'Ingenierie des Materiaux - C.I.R.I.M.A.T. (France); EDF R et D, Moret sur Loing (France)2018
Universite de Toulouse, Ecole doctorale Sciences de la Matiere - SDM, Institut National Polytechnique de Toulouse - INP Toulouse, Centre Interuniversitaire de Recherche et d'Ingenierie des Materiaux - C.I.R.I.M.A.T. (France); EDF R et D, Moret sur Loing (France)2018
AbstractAbstract
[en] Core internals of Pressurized Water Reactors (PWRs) are made of austenitic stainless steel (304L or 316L). These materials are exposed to the primary medium under irradiation and undergo mechanical stresses. Under these conditions, degradation of the components by Irradiation-Assisted Stress Corrosion Cracking (IASCC) is likely to occur. This complex phenomenon can have a significant influence on the maintenance time and cost of the internal components of PWRs. The understanding of the oxidation mechanisms at IASCC crack tip is therefore essential to better apprehend IASCC. From a practical point of view, this goes through that of the holding of the passive layer during the corrosion first stages. The aim of this work is to better understand the role of irradiation on the oxide films formation. To limit the experimental complexity associated with the activation generated by neutrons, the effect of neutron irradiation was simulated by synthetic proton pre-irradiations. The TEM observations carried out have shown that synthetic irradiations reproduce defects as well as intra and inter-granular segregation. Short time oxidations in simulated primary medium (between 5 min and 96 h) were performed to study the oxidation first stages. Thus, this study focused on the understanding of the phenomena governing the initial stages of formation and growth of the oxide layers formed on 316L alloy. The oxidations were designed to obtain, on a same sample, an irradiated and non-irradiated zone in order to decorrelate the effect of irradiation under identical oxidation conditions. The crystallographic orientation of the underlying metal grains was taken into account and its effect was evaluated. The influence of some surface inhomogeneities (cold-work and inclusions) has also been studied. In addition, a sample was oxidized under proton flux for 24 hours to study the influence of Irradiation-Assisted Corrosion. Finally, the oxides formed at the IASCC crack tip taken from a bolt extracted from a French nuclear power plant were studied and compared to those formed on the samples oxidized in simulated PWR medium. The oxides were studied from the macroscopic scale down to the nanoscopic scale (optical microscopy, Grazing Incidence X-ray Diffraction, Raman spectroscopy, Scanning and Transmission Electron Microscopy). The morphology, thickness, structure and composition of the oxides have been analyzed. The oxides are, in all cases, duplex and of spinel structure. Outer crystallites are iron-rich while the inner oxide is rich in chromium, iron and nickel. The comparison of irradiated and unirradiated samples revealed that the nature and density of defects near the metal/oxide interface play a role in the morphology, thickness and composition of the oxides. The oxides are similar to those formed at the IASCC crack tip taken from the extracted component. This work demonstrates that the crystallographic orientation of the substrate influences the oxidation kinetics and that an epitaxial relationship is established between the oxides and the underlying metal grains. Moreover, it has been found that cold-work and the presence of inclusion affect the oxides formed. All these results have brought new elements of understanding relating to the formation and growth of oxides formed on austenitic stainless steels exposed to primary water. This work also highlights the effect of irradiation defects on the oxides formed and the alternative represented by synthetic pre-irradiations to emulate neutron microstructures. A corrosion mechanism taking into account the crystallographic orientation, the surface state of the material and the irradiation defects has been proposed. (author)
[fr]
Les internes de cuve des Reacteurs a Eau sous Pression (REP) sont fabriques en acier inoxydable austenitique (304L ou 316L). Ces materiaux sont exposes au milieu primaire sous irradiation et subissent des contraintes mecaniques. Dans ces conditions, une degradation des composants par le phenomene de corrosion sous contrainte assistee par l'irradiation (IASCC) est susceptible de se produire. Ce phenomene complexe peut avoir une influence significative sur le temps et le cout de maintenance des composants internes des REP. La comprehension des mecanismes d'oxydation en pointe de fissure d'IASCC est donc essentielle pour mieux apprehender l'IASCC. D'un point de vue pratique, cela passe par celle de la tenue de la couche passive lors des premieres etapes de corrosion. L'objectif de ce travail est de mieux apprehender le role de l'irradiation sur la formation des films d'oxydes. Pour limiter la complexite experimentale liee a l'activation engendree par les neutrons, l'effet de l'irradiation neutronique a ete simule par des pre-irradiations synthetiques aux protons. Les observations MET realisees ont montrees que les irradiations synthetiques reproduisent aussi bien les defauts que la segregation intra et intergranulaire. Des oxydations aux temps courts en milieu primaire simule (entre 5 min et 96 h) ont ete realisees pour etudier les premiers stades d'oxydation. Ainsi, cette etude est focalisee sur la comprehension des phenomenes regissant les stades initiaux de formation et de croissance des couches d'oxydes sur l'alliage 316L. Les oxydations ont ete concues pour obtenir, sur un meme echantillon, une zone irradiee et non irradiee afin de decorreler l'effet de l'irradiation pour des conditions d'oxydation identiques. L'orientation cristallographique des grains de metal sous jacents a ete prise en compte et son effet evalue. L'influence de quelques inhomogeneites de surface (ecrouissage et inclusions) a aussi ete etudiee. De plus, un echantillon a ete oxyde sous flux de proton durant 24 heures afin d'etudier l'influence de la corrosion assistee par l'irradiation. Enfin, les oxydes formes en pointe de fissure d'IASCC prelevee sur une vis extraite d'une centrale nucleaire francaise ont ete etudies et compares a ceux formes sur les echantillons oxydes en milieu REP simule. Les oxydes ont ete etudies de l'echelle macroscopique jusqu'a l'echelle nanoscopique (microscopie optique, Rayons X par incidence Rasantes, spectroscopie Raman, Microscopie Electronique a Balayage et en Transmission). La morphologie, l'epaisseur, la structure et la composition des oxydes ont ete analysees. Les oxydes sont dans tous les cas duplex et de structure spinelle. Les cristallites externes sont riches en fer tandis que l'oxyde interne est riche en chrome, fer et nickel. La comparaison des echantillons sur zones irradiees et non irradiees a permis de montrer que la nature et la densite de defauts proches de l'interface metal/oxyde jouent un role sur la morphologie, l'epaisseur et la composition des oxydes. Les oxydes sont similaires a ceux formes en pointe de fissure d'IASCC prelevee sur le composant extrait. Ces travaux demontrent que l'orientation cristallographique du metal de base influence la cinetique d'oxydation et qu'une relation d'epitaxie s'etablit entre les oxydes et le substrat. Par ailleurs, il a ete constate que l'ecrouissage et la presence d'inclusion affectent les oxydes formes. L'ensemble de ces resultats a permis d'apporter de nouveaux elements de comprehension relatifs a la formation et croissance des oxydes formes sur les aciers inoxydables austenitiques en milieu primaire. Ces travaux mettent de plus en avant l'effet des defauts d'irradiation sur les oxydes formes et l'alternative que representent les pre-irradiations synthetiques pour emuler les microstructures neutroniques. Un mecanisme de corrosion prenant en compte l'orientation cristallographique, l'etat de surface du materiau et les defauts d'irradiation a ete propose. (auteur)Original Title
Etude des effets d'irradation sur les premiers stades d'oxydation d'un acier austenitique inoxydable 316L
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13 Dec 2018; 297 p; 209 refs.; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses; These de Doctorat de l'Universite de Toulouse, specialite: Science et Genie des Materiaux
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Miscellaneous
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CHEMICAL REACTION KINETICS, COLD WORKING, CRACK PROPAGATION, CRYSTAL STRUCTURE, EPITAXY, FRACTURE PROPERTIES, GRAIN BOUNDARIES, GRAIN ORIENTATION, INCLUSIONS, INTERFACES, OXIDATION, POST-IRRADIATION EXAMINATION, RAMAN SPECTROSCOPY, SCANNING ELECTRON MICROSCOPY, SEGREGATION, STAINLESS STEEL-316L, STRESS CORROSION, TRANSMISSION ELECTRON MICROSCOPY, X-RAY DIFFRACTION
ALLOYS, AUSTENITIC STEELS, CARBON ADDITIONS, CHEMICAL REACTIONS, CHROMIUM ALLOYS, CHROMIUM STEELS, CHROMIUM-MOLYBDENUM STEELS, CHROMIUM-NICKEL STEELS, CHROMIUM-NICKEL-MOLYBDENUM STEELS, COHERENT SCATTERING, CORROSION, CORROSION RESISTANT ALLOYS, CRYSTAL GROWTH METHODS, DIFFRACTION, ELECTRON MICROSCOPY, FABRICATION, HEAT RESISTANT MATERIALS, HEAT RESISTING ALLOYS, HIGH ALLOY STEELS, IRON ALLOYS, IRON BASE ALLOYS, KINETICS, LASER SPECTROSCOPY, LOW CARBON-HIGH ALLOY STEELS, MATERIALS, MATERIALS WORKING, MECHANICAL PROPERTIES, MICROSCOPY, MICROSTRUCTURE, MOLYBDENUM ALLOYS, NICKEL ALLOYS, ORIENTATION, REACTION KINETICS, SCATTERING, SPECTROSCOPY, STAINLESS STEELS, STEEL-CR17NI12MO3-L, STEELS, TRANSITION ELEMENT ALLOYS
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