Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at ∼14.5 GPa.

IR pyrometry in diamond anvil cell above 400 K.

Temperature measurements in a laser heated diamond anvil cell (DAC) are currently limited to temperatures above 1000 K using optics and detectors in the visible range. We have built a pyrometer in the IR range and expanded the lower limit of temperature detection to 400 K. The pyrometer is designed for very low thermal radiation intensities, measured sequentially through a set of bandpass filters in the range of 1.2-3.4 microm using very efficient IR photodetectors. The thermal radiation from the center of the cw Nd:YAG laser heated spot is least square fitted to a Planck curve, using a gray body approximation. Melting is detected by changes in the light scattering picture of an auxiliary He-Ne laser from the surface of the hot spot, and by a change in slope in the plot of hot spot temperature versus laser power. In this work we demonstrate measurement of the melting curve of zinc up to 25 GPa. The melting curve is in very good agreement with previous results which were taken up to 6 GPa in a large volume press.