Hosted by: Ian Robinson

In situ characterization of the phase behavior of materials in the lab is complicated by the difficulty of designing compatible sample environments as well as the long time scales required to acquire diffraction data with sufficient counting statistics for crystallographic analyses. The high energy x-rays available at synchrotron sources allow for penetration of most sample environments, while high flux allows for rapid acquisition of diffraction patterns, thereby allowing construction of detailed phase diagrams. Low and negative thermal expansion (NTE) materials have been studied extensively, as they can potentially be used to create composites with finely controlled thermal expansion characteristics, improved resistance to thermal shock, and a broader range of operating temperatures.1-4 While the thermal expansion behavior of the NTE materials ZrW2O8 and HfW2O8 was well-described at ambient pressures,4-6 knowledge of the effects of stress on their thermal expansion was limited.7 In situ synchrotron powder diffraction was utilized to explore the role of orientational disorder in determining both the phase behavior and the thermoelastic properties of these materials. An especially designed pressure cell allowed for simultaneous sampling of temperatures up to 513 K and pressures up to 414 MPa.8 Reversible compression-induced orientational disordering of MO4 tetrahedra occurred concomitantly with elastic softening on heating and enhanced negative thermal expansion upon compression in ZrW2O8 and HfW2O8, but only in the ordered phase.9, 10 In light of the comparatively recent nuclear disaster in Fukushima, understanding interactions and phase behavior in nuclear fuels under severe accident conditions is of paramount interest. While diffraction measurements have been performed on materials recovered from melts of corium (UO2-ZrO2), there is a lack of in situ characterization of this material at elevated temperatures. Achieving the extreme temperatures required