Jonathan Perret
Several metallic components of pressurized water reactors (PWR) used in nuclear power plants are exposed to the combined degradation by friction and corrosion (tribocorrosion). In PWR, corrosion arises from the water pressurized at 150 bars and maintained at 300°C and results in the build up of a micrometer thick surface oxide film. Tribocorrosion is of complex nature as it involves multi-scale interactions between mechanical, chemical and material factors. Nevertheless, PWR component manufacturers are interested in understanding the deterioration mechanisms in order to select appropriate materials as well as predicting the component lifetime. This thesis is a contribution towards the elucidation of the tribocorrosion mechanisms of a specific PWR component (austenitic stainless steel control rods). The research is focused on two inter-related aspects related to the subsurface deformation induced by friction and to the high temperature and high-pressure oxidation kinetics of austenitic stainless steel under tribocorrosion conditions. The subsurface deformation is investigated by using a model tribocorrosion system consisting in an alumina ball sliding against a 304L austenitic stainless steel in sulphuric acid at ambient temperature under electrochemical control. This model system allows studying subsurface deformation in absence of a thick high temperature oxide films that can complicate the interpretation of the results. Subsurface deformation was characterized using SEM, EBDS and FIB cross-sections. Good correlation was found with the deformation found in pressurized water. Subsurface deformation was found to result in the formation of a recrystallised layer of nano-grains close to the surface and an underlying layer exhibiting a deformation gradient. The thickness of the recrystallized zone is highly affected by the presence or the absence of a few nm thick oxide in the contact. However, no obvious correlation between the thickness of the recrystallized zone, or any other measured deformation appearance, and wear could be found. The effect of oxidation was studied using a simulator (Aurore), reproducing the chemical and mechanical PWR conditions of control rods. It includes an electrochemical set-up allowing measuring in-situ and in real time the oxidation kinetic. The oxidation kinetic was found to follow a parabolic law (diffusion controlled oxide growth). Rubbing resulted in repeated scratching of the surface leading to a thinning of the oxide film and thus to an enhanced anodic oxidation. A quantitative model of the electrochemical response of stainless steel in PWR conditions was developed. Based on these results and on the third body theory of wear, a mechanistic model was proposed for describing the material behaviour in contacts operating in pressurized water. This model explains a certain number of practical observations obtained in nuclear plants or in simulators concerning chemical and materials effects on component degradation.
EPFL2010
