Thermal annealing of natural, radiation-damaged pyrochlore

Abstract

Abstract Radiation damage in minerals is caused by the α-decay of incorporated radionuclides, such as U and Th and their decay products. The effect of thermal annealing (400–1000 K) on radiation-damaged pyrochlores has been investigated by Raman scattering, X-ray powder diffraction (XRD), and combined differential scanning calorimetry/thermogravimetry (DSC/TG). The analysis of three natural radiation-damaged pyrochlore samples from Miass/Russia [6.4 wt% Th, 23.1·1018 α-decay events per gram (dpg)], Panda Hill/Tanzania (1.6 wt% Th, 1.6·1018 dpg), and Blue River/Canada (10.5 wt% U, 115.4·1018 dpg), are compared with a crystalline reference pyrochlore from Schelingen (Germany). The type of structural recovery depends on the initial degree of radiation damage (Panda Hill 28%, Blue River 85% and Miass 100% according to XRD), as the recrystallization temperature increases with increasing degree of amorphization. Raman spectra indicate reordering on the local scale during annealing-induced recrystallization. As Raman modes around 800 cm−1 are sensitive to radiation damage (M. T. Vandenborre, E. Husson, Comparison of the force field in various pyrochlore families. I. The A2B2O7 oxides. J. Solid State Chem. 1983, 50, 362, S. Moll, G. Sattonnay, L. Thomé, J. Jagielski, C. Decorse, P. Simon, I. Monnet, W. J. Weber, Irradiation damage in Gd2Ti2O7 single crystals: Ballistic versus ionization processes. Phys. Rev. 2011, 84, 64115.), the degree of local order was deduced from the ratio of the integrated intensities of the sum of the Raman bands between 605 and 680 cm−1 divided by the sum of the integrated intensities of the bands between 810 and 860 cm−1. The most radiation damaged pyrochlore (Miass) shows an abrupt recovery of both, its short- (Raman) and long-range order (X-ray) between 800 and 850 K, while the weakly damaged pyrochlore (Panda Hill) begins to recover at considerably lower temperatures (near 500 K), extending over a temperature range of ca. 300 K, up to 800 K (Raman). The pyrochlore from Blue River shows in its initial state an amorphous X-ray diffraction pattern superimposed by weak Bragg-maxima that indicates the existence of ordered regions in a damaged matrix. In contrast to the other studied pyrochlores, Raman spectra of the Blue River sample show the appearance of local modes above 560 K between 700 and 800 cm−1 resulting from its high content of U and Ta impurities. DSC measurements confirmed the observed structural recovery upon annealing. While the annealing-induced ordering of Panda Hill begins at a lower temperature (ca. 500 K) the recovery of the highly-damaged pyrochlore from Miass occurs at 800 K. The Blue-River pyrochlore shows a multi-step recovery which is similarly seen by XRD. Thermogravimetry showed a continuous mass loss on heating for all radiation-damaged pyrochlores (Panda Hill ca. 1%, Blue River ca. 1.5%, Miass ca. 2.9%).