文摘
We present the results of cerium LIII X-ray absorption near edge structure (XANES) studies of two series (-I and -II) of alkali boro-aluminosilicate based glasses prepared from compositions containing different amounts of CeO2 and P2O5, and melted at a variety of temperatures and redox conditions. Model XANES spectra for Ce3+ in the glass, Ce4+ in the glass, and crystalline CeO2, were used to fit the Ce LIII XANES spectra obtained from the glasses. This analysis allowed both the [Ce4+]/[Cetotal] ratio and the distribution of Ce environments to be determined for each glass. The [Ce4+]/[Cetotal] ratios, which varied from 0.00 to 0.58, determined independently by XANES spectroscopy were found to have a correlation, r>0.9, with those previously obtained using wet chemical methods. Furthermore, using this method, these two series of glasses, which differed in the amounts of BaO, Bi2O3, SnO2, and ZrO2, had different distributions in their cerium environments. The Ce LIII XANES spectra obtained from series II glasses (1.0 wt % BaO, 1.0 wt % Bi2O3, no SnO2, and 1.0 wt % ZrO2) melted at 1350°C were able to be fit using only Ceglass3+ and Ceglass4+ environments; whereas, those from series I glasses (2.7 wt % SnO2, no BaO or Bi2O3, and 5.1 wt % ZrO2) melted at 1120°C could only be fit when an additional component was included, confirming the previous assessment that the series I glasses exhibited CeO2 related heterogeneities.