Hydrogen entry in Zircaloy-4 fuel cladding : an electrochemical study

Abstract

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.