Oxidation of Zircaloy Fuel Cladding in Water-Cooled Nuclear Reactors

Our work involved the continued development of the theory of passivity and passivity breakdown, in the form of the Point Defect Model, with emphasis on zirconium and zirconium alloys in reactor coolant environments, the measurement of critically-important parameters, and the development of a code that can be used by reactor operators to actively manage the accumulation of corrosion damage to the fuel cladding and other components in the heat transport circuits in both BWRs and PWRs. In addition, the modified boiling crevice model has been further developed to describe the accumulation of solutes in porous deposits (CRUD) on fuel under boiling (BWRs) and nucleate boiling (PWRs) conditions, in order to accurately describe the environment that is contact with the Zircaloy cladding. In the current report, we have derived expressions for the total steady-state current density and the partial anodic and cathodic current densities to establish a deterministic basis for describing Zircaloy oxidation. The models are “deterministic” because the relevant natural laws are satisfied explicitly, most importantly the conversation of mass and charge and the equivalence of mass and charge (Faraday’s law). Cathodic reactions (oxygen reduction and hydrogen evolution) are also included in the models, because there is evidence that they control the rate of the overall passive film formation process. Under open circuit conditions, the cathodic reactions, which must occur at the same rate as the zirconium oxidation reaction, are instrumental in determining the corrosion potential and hence the thickness of the barrier and outer layers of the passive film. Controlled hydrodynamic methods have been used to measure important parameters in the modified Point Defect Model (PDM), which is now being used to describe the growth and breakdown of the passive film on zirconium and on Zircaloy fuel sheathing in BWRs and PWRs coolant environments. The modified PDMs recognize the existence of a thick oxide outer layer over a thin barrier layer. From thermodynamic analysis, it is postulated that a hydride barrier layer forms under PWR coolant conditions whereas an oxide barrier layer forms under BWR primary coolant conditions. Thus, the introduction of hydrogen into the solution lowers the corrosion potential of zirconium to the extent that the formation of ZrH2 is predicted to be spontaneous rather than the ZrO2. Mott-Schottky analysis shows that the passive film formed on zirconium is n-type, which is consistent with the PDM, corresponding to a preponderance of oxygen/hydrogen vacancies and/or zirconium interstitials in the barrier layer. The model parameter values were extracted from electrochemical impedance spectroscopic data for zirconium in high temperature, de-aerated and hydrogenated environments by optimization. The results indicate that the corrosion resistance of zirconium is dominated by the porosity and thickness of the outer layer for both cases. The impedance model based on the PDM provides a good account of the growth of the bi-layer passive films described above, and the extracted model parameter values might be used, for example, for predicting the accumulation of general corrosion damage to Zircaloy fuel sheath in BWR and PWR operating environments. Transients in current density and film thickness for passive film formation on zirconium in dearated and hydrogenated coolant conditions have confirmed that the rate law afforded by the Point Defect Model (PDM) adequately describes the growth and thinning of the passive film. The experimental results demonstrate that the kinetics of oxygen or hydrogen vacancy generation at the metal/film interface control the rate of film growth, when the potential is displaced in the positive direction, whereas the kinetics of dissolution of the barrier layer at the barrier layer/solution interface control the rate of passive film thinning when the potential is stepped in the negative direction. In addition, the effects of second phase particles (SPPs) on the electrochemistry of passive zirconium in the hydrogenated, high temperature aqueous solutions were examined by using different heat-treated Zircaloy-4 samples; i.e., as-received, -quenched, and -annealed. The average size of the second phase particles in the Zircaloy-4 samples was in the sequence of -quenched < -annealed < as-received, with the reverse sequence being observed in the areal density. Electrochemical studies show that the size and density of the second phase particles are the determining factors of the electrochemical properties of the passive films. The second phase particles may cause short circuits in the electrical path across the passive film, which would explain the effect of the size and the density of the SPPs, and hence heat treatment, on the corrosion properties of passive Zircaloy-4.