Electrical characterization of waterside corrosion films formed on ZrNb(1%)O(0.13%) impedance spectroscopy, zirconium alloys, oxidation, frequency-temperature equivalence, dielectric dispersion

摘要

Oxide films formed by water oxidation at 360℃ on ZrNb(1%)O(0.13%) for several durations (50-300 days) were studied by impedance spectroscopy (IS) in gaseous atmosphere. The electrical behavior of oxide layers was investigated as a function of the temperature (25-300℃) at constant oxygen partial pressure (0.3 Pa). Cole-Cole diagrams suggest a frequency-temperature equivalence. A simple electrical model has been derived from the as-deduced 14 decade master curve. Equivalent circuit includes a series association of two layers exhibiting different dielectric properties: a dense layer near the oxide-metal interface and a porous layer at the waterside. Electronic conductivity is predominant within the whole temperature range, but ionic contribution was proposed to increase for temperature higher than 170℃. During the parabolic oxidation step, the oxide thickness of the barrier layer increases but oxide growth would not be only a geometrical one. The kinetic modification to a constant oxidation rate was observed to be correlated to the increase of the dense layer thickness. Such a behavior suggests that the mechanism controlling oxidation rate is not a pure mechanism of oxygen diffusion through this layer. Finally, a qualitative model of activated electrons transport based on an hopping mechanism was proposed in order to take into account that the Arrhenius diagrams of both total conductivity and dispersion factor are characterized by a break point with two activation energy values.