Characterization of zirconium oxides part I: Raman mapping and spectral feature analysis

Raman mapping of sectioned zirconium cladding oxides was performed to analyze different spectral features before and after breakaway, as well as between zirconium and its alloys Zr-2.65Nb, Zry-3, and Zry-4. Oxide phase composition, or percent tetragonality, was defined to compare tetragonal to monoclinic zirconia. Percent tetragonality was spatially mapped to support distinction of zirconia phase distribution. A tetragonal-rich layer was seen at the metal/oxide interface, while post-breakaway samples exhibited increased amount of tetragonal phase in the bulk of their oxides. Spatial mapping of spectral peak location and half-width at half-maximum was accomplished to distinguish differences in stability mechanisms of tetragonal-rich zirconia phase. Shifts in monoclinic peak positions provided mapping of relative stress state, supporting the differences in stabilization of tetragonal phase near the metal/oxide interface and tetragonal phase in the bulk of the oxide. Tetragonal phase near the metal/oxide interface is stabilized through support of oxygen sub-stoichiometry and compressive stress. Tetragonal phase observed in the bulk of the oxide is stabilized through oxygen sub-stoichiometry, void of compressive stress. A linear trend between percent tetragonality and stress state was determined. This resulted in a connection between mechanism of tetragonal to monoclinic phase transformation and a cladding's ability to resist oxidation and breakaway. Poor performing samples displayed greater stress gradients, driven by lattice mismatch at the metal/oxide interface, as well as between tetragonal and monoclinic phase boundaries. Tetragonal phase at the metal/oxide interface for superior performing samples have reduced epitaxial growth of tetragonal grains, lowering compressive stress gradients and provided more resistant inner-oxide layers. With increased utility of Raman spectroscopy for characterizing zirconium cladding materials, different degradation mechanisms can be further understood.