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 ...

Corrosion and hydrogen pickup of zirconium alloy fuel cladding in water cooled nuclear reactors are life-limiting phenomena for fuel. This thesis studies the fate of hydrogen liberated by waterside corrosion of Zircaloy-4 fuel cladding in Pressurized Water Reactors (PWRs): are the adsorbed protons incorporated into the oxide and eventually the metal, or are they evolved into molecular hydrogen and released into the coolant? Water chemistry modeling was used to understand effects of radiolysis and CRUD. Density functional theory (DFT) was used to investigate the role of oxidized Zr(Fe,Cr)2 second phase particles. Chemical potentials and the electron chemical potential were used to connect these two modeling efforts. A radiolysis model was developed for the primary loop of a PWR. Dose profiles accounting for fuel burnup, boron addition, axial power profiles, and a CRUD layer were produced. Dose rates to the bulk coolant increased by 21-22% with 12.5-75 pim thick CRUD layers. Radially-averaged core chemistry was compared to single-channel chemistry at individual fuel rods. Calculations showed that local chemistry was more oxidizing at high-power fuel and fuel with CRUD. Local hydrogen peroxide concentrations were up to 2.5 ppb higher than average levels of 5-8 ppb. Radiolysis results were used to compute chemical potentials and the corrosion potential. Marcus theory was applied to compare the band energies of oxides associated with Zircaloy-4 and the energy levels for proton reduction in PWR conditions. Hydrogen interactions with Cr203 and Fe203, both found in oxidized precipitates, were studied with DFT. Atomic adsorption of hydrogen was modeled on the Cr and Feterminated (0001) surfaces. Climbing Image-Nudged Elastic Band calculations were used to model the competing pathways of hydrogen migration into the subsurface and molecular hydrogen formation. A two-step mechanism for hydrogen recombination was identified consisting of: reduction of an adsorbed proton (H+) to a hydride ion (H-) and H2 formation from an adjacent adsorbed proton and hydride ion. Overall, results suggest that neither surface will be an easy entrance point for hydrogen ingress and that Cr203 is more likely to be involved in hydrogen evolution than the Fe203.

The oxidation rate was found to be relatively insensitive to various types of surface preparations in the temperature range 400 to 700 deg C. No dependence of reaction rate on oxygen pressure was observed. The cubic rate law also was obeyed by foil specimens at 700 deg C; however, the rate constants were slightly larger than values obtained from parallelepiped samples.

The behavior of Zircaloy-clad fuel rods for light water reactors under off-normal operating conditions is being studied in the Power Burst Facility. Fuel rods from three irradiation experiments conducted under power-cooling-mismatch conditions have been examined destructively in remote handling facilities. The postirradiation examinations of these pressurized water reactor-type rods have included visual and photographic examination, physical dimensioning, and metallography.