Atomistic origin of germanate anomaly in GeO2 and Na-germanate glasses: insights from two-dimensional 17O NMR and quantum chemical calculations.
The prominent problem in archetypal germanate glasses is the germanate anomaly where the density exhibits maxima at 15-20 mol % of the alkali oxide content. Here we report (17)O two-dimensional NMR spectra for GeO(2) and Na-germanate glasses where the presence of both bridging oxygen linking ([4])Ge and highly coordinated Ge (([5,6])Ge-O-([4])Ge) and nonbridging oxygen, and an increase in topological disorder are demonstrated at the density maximum, manifesting atomic origins of the anomaly. These densification mechanisms in germanate glasses with Na content are remarkably similar to densification in v-B(2)O(3) with pressure.
Lee
Sung Keun
SK
Laboratory of Physics and Chemistry of Earth Materials, School of Earth and Environmental Sciences, Seoul National University, Seoul 151-742, Korea. sungklee@snu.ac.kr
Lee
Bum Han
BH