High-temperature and melting behaviour of nanocrystalline refractory compounds: an experimental approach applied to thorium dioxide

The behaviour from 1500 K up to melting of nanocrystalline (nc) thorium dioxide, the refractory binary oxide with the highest melting point (3651 K), was explored here for the first time using fast laser heating, multi-wavelength pyrometry and Raman spectroscopy for the analysis of samples quenched to room temperature. Nc-ThO2 was melted at temperatures hundreds of K below the melting temperature assessed for bulk thorium dioxide. A particular behaviour has been observed in the formed liquid and its co-existence with a partially restructured solid, possibly due to the metastable nature of the liquid itself. Raman spectroscopy was used to characterize the thermal-induced structural evolution of nc-ThO2. Assessment of a semi-empirical relation between the Raman active T2g mode peak characteristics (peak width and frequency) and crystallites size provided a powerful, fast and non-destructive tool to determine local crystallites growth within the nc-ThO2 samples before and after melting. This semi-quantitative analysis, partly based on a phonon-confinement model, constitutes an advantageous, more flexible, complementary approach to electron microscopy and powder x-ray diffraction (PXRD) for the crystallite size determination. The adopted experimental approach (laser heating coupled with Materials Research Express 1 (2014) 025034 2053-1591/14/025034+12$33.00 © 2014 IOP Publishing Ltd Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI. Raman spectroscopy) is therefore proven to be a promising methodology for the high temperature investigation of nanostructured refractory oxides. S Online supplementary data available from stacks.iop.org/MRX/1/025034/ mmedia