Modeling the effects of nuclear environments on crevice corrosion of pure nickel by coupling of phase and polarization behavior

Abstract

As from long-term operating experience the high purity primary water cycle of light water nuclear reactors may exhibit excursions from the recommended water chemistry leading to potentially favorite conditions for stress corrosion cracking (SCC) which may be initiated and its propagation controlled by local pitting and crevice corrosion. Deterministic modeling of local corrosion including incubation times for crevice corrosion should therefore provide a basis for lifetime predictions of components, which have been subjected to sporadic intermediate water chemistry fluctuations. Based on previous work for room temperature (RT), the chloride-induced crevice corrosion at 288 °C of pure nickel as an important base element in respective high alloyed nuclear materials is modeled by coupling anodic polarization with the precipitation of nickel oxide and nickel chloride calculated from the water–hydrogen–nickel chloride heterogeneous phase equilibrium diagram. The surface corrosion potentials are fixed by bulk levels of hydrogen and oxygen contents as well as pH simulating hydrogen treatment of irradiation subjected cooling water for the reduction of corrosion potentials and mitigation of SCC at operating temperature 288 °C in Boiling Water Reactors (BWRs). Assuming chemical equilibrium conditions during the selected time steps in a relevant component crevice the calculated change of the crevice solution composition is quantitatively shown to initiate crevice corrosion by the breakdown of the passive nickel oxide layer followed by the formation of non-passive nickel chloride and the subsequent acidification of the crevice solution. The effects of corrosion potentials, bulk levels of pH and chlorides, are investigated. As a result, the reduction of corrosion potentials and increase in bulk pH provide significant increases in the passive layer breakdown times and acidification times inside the crevice. Depending on bulk pH and corrosion potentials the reduction of bulk chlorides down to recommended levels in BWRs retards crevice corrosion significantly. For a standard 100,000 h time for crevice acidification to locally less than pH = 0 the respective chloride–pH domain is evaluated. Such diagrams may be related to respective effects on stress corrosion cracking and its mitigation by hydrogen water chemistry (HWC).