Thermal transport is a key performance metric for thorium dioxide in many applications where defect-generating radiation fields are present. An understanding of the effect of nanoscale lattice defects on thermal transport in this material is currently unavailable due to the lack of a single crystal material from which unit processes may be investigated. In this work, a series of high-quality thorium dioxide single crystals are exposed to 2 MeV proton irradiation at room temperature and 600 °C to create microscale regions with varying densities and types of point and extended defects. Defected regions are investigated using spatial domain thermoreflectance to quantify the change in thermal conductivity as a function of ion fluence as well as transmission electron microscopy and Raman spectroscopy to interrogate the structure of the generated defects. Together, this combination of methods provides important initial insight into defect formation, recombination, and clustering in thorium dioxide and the effect of those defects on thermal transport. These methods also provide a promising pathway for the quantification of the smallest-scale defects that cannot be captured using traditional microscopy techniques and play an outsized role in degrading thermal performance.
Abstract Crystallite orientation identification is invaluable, but is often limited to small area identification or requires a large area sample. Nondestructive optical methods such as polarized Raman spectroscopy, in contrast, can be used to completely map a variety of sample sizes, but their potential is not yet fully realized. Here, we report a systematic study of polarized Raman scattering of high‐quality, hydrothermally grown, single crystals of urania and thoria. The peak intensity variations for as‐grown major crystal planes, post‐growth polished crystal planes, and a post‐growth polished non‐crystallographic plane are directly linked to crystallographic orientation and crystal rotation, and agree with computed models. In particular, the parallel polarized peak intensity results are directly correlated with metal–oxygen–metal chains in the fluorite structure and can be used to determine both orientation and rotational alignment of a given crystal face if sufficiently small rotational steps are applied. These results are structure based, being applicable to the larger fluorite phase space, which is useful for optical, semiconductor, nuclear, and solid oxide fuel cell industries. Further, these results suggest that Raman spectroscopy can identify non‐crystallographic orientations that are not discernable by traditional means.
