The Development of an In-situ TEM Technique for Studying Corrosion Behavior as Applied to Zirconium-based Alloys

Zirconium-based alloys are a commonly used material for nuclear fuel rod cladding, due to its low neutron cross section and good corrosion properties. However, corrosion is still a limiting factor in fuel rod lifespan, which restricts burn up levels, and thus efficiency, that can be achieved. While long-term corrosion behavior has been studied through both reactor and autoclave samples, the oxide nucleation and growth behavior has not been extensively studied. This work develops a new technique to study the initial stages of corrosion in zirconium-based alloys and the microstructural effects on this process by developing an environmental cell system for the TEM. Nanoscale oxidation parameters are developed, as is a new FIB technique to support this method. Precession diffraction is used in conjunction with in-situ TEM to observe the initial stages of corrosion in these alloys, and oxide thickness is estimated using low-loss EELS. In addition, the stress stabilization of tetragonal ZrO2 is explored in the context of sample preparation for TEM. It was found that in-situ environmental TEM using an environmental cell replicates the oxidation behavior observed in autoclaved samples in both oxide structure and phases. Utilizing this technique, it was shown that cracking of the oxide layer in zirconium-based alloys is related to oxide relaxation, and not thermal changes. The effect of secondary phase particles on oxidation behavior did not present significant results, however a new method for studying initial oxidation rates using low-loss EELS was developed.Ph.D., Materials Science and Engineering -- Drexel University, 201