Kinetics of passivation of a nickel-base alloy in high temperature water

The kinetics of passivation and the composition of the surface oxide layer, in high temperature and high pressure water, of a nickel-chromium-iron alloy (Alloy 600) have been investigated by X-ray Photoelectron Spectroscopy (XPS). The samples have been exposed for short (0.4 - 8.2 min) and longer (0 - 400 hours) time periods to high temperature (325 deg. C) and high pressure water (containing boron and lithium) under controlled hydrogen pressure. The experiments were performed in two types of autoclaves: a novel autoclave dedicated to short time periods and a classic static autoclave for the longer exposures. In the initial stage of passivation, a continuous ultra-thin layer of chromium oxide (Cr2O3) is rapidly formed on the surface with an external layer of chromium hydroxide. For longer times of passivation, the oxide layer is in a duplex form with an internal chromium oxide layer and an external layer of nickel hydroxide. The growth of the internal Cr2O3 oxide layer has been fitted by three classical models (parabolic, logarithmic and inverse logarithmic laws) for the short passivation times, and the growth curves have been extrapolated to longer passivation periods. The comparison with the experimental results reveals that the kinetics of passivation of Alloy 600 in high temperature and high pressure water, for passivation times up to 400 hours, is well fitted by a logarithmic growth law. (authors)