Assessing Li accommodation at amorphous ZrO2 grain boundaries

Lithium Stabilization of Amorphous Zro2

“…Raman spectroscopy showed limited results due to small crystal size that was later confirmed through STEM which showed crystal sizes to be between 10 and 20 nm. In addition to this, no evidence could be gained to indicate that Li formed solid solution in bulk ZrO 2 which confirmed previous simulation work that showed limited solubility (Stephens et al, 2023). Samples that were placed in deionised water resulted in the suspension of ZrO 2 and the dissolution of Li from the samples.…”

“…It was found that the segregated Li after crystallisation was highly soluble in water. When combined with simulation work indicating that lithium can increase vacant oxygen concentrations and increase oxygen diffusion (Owen et al, 2021;Stephens et al, 2023), this experimental work provides additional potential to understand the accelerated corrosion of zirconium alloys in the presence of Li and opens a range of investigative avenues that may be explored. In-situ XPS may be used to identify the form lithium takes once segregated from grain boundaries during crystallisation.…”

“…Simulation work indicated that Li doped amorphous ZrO 2 may increase the vacant oxygen defects found within the grain boundaries (Stephens et al, 2023). When coupled with Li stabilization of the grain boundaries, this may provide a route to increase oxygen flux through the oxide and increase corrosion of the metal surface.…”

“…Amorphous structures can be expected to form more readily at lower temperatures due to limited kinetic energy availability for crystalline atomic orientations (below 450 • C (Lebeau et al, 2020)). Further atomic scale simulation work has been undertaken to assess transport mechanisms of lanthanide dopants through the disordered oxide grain boundary (Owen et al, 2021) Recent atomistic modelling has identified an indication of Li solution in the amorphous structures coupled with an associated increase of vacant oxygen defects as a result (Stephens et al, 2023).…”

“…This investigation prepared and characterised amorphous oxides with different Li levels to support the simulations and provide extra insight into the behaviour of the surrogate grain boundary material. It also looked at the impact of Li stabilizing an amorphous structure, analogous to a highly complex grain boundary, which have been found through simulation to potentially modify grain boundary mobility of corrosive species (Owen et al, 2021;Stephens et al, 2023).…”