Oxygen sites and network coordination in sodium germanate glasses and crystals: high-resolution oxygen-17 and sodium-23 NMR.
Sodium germanate glasses are well-studied materials in which, unlike silicates but analogous to borates, the major structural consequence of alkali addition is generally thought to involve a coordination number increase of the network-forming Ge cations. However, the nature of this change, in particular quantifying fractions of nonbridging oxygens and of five- and/or six-coordinated Ge, has remained unresolved. We present here high-resolution 17O results, including triple-quantum MAS NMR (3QMAS), on a series of crystalline model compounds that allow the definition of ranges of chemical shifts corresponding to oxygens bonded to various coordinations of Ge. These include quartz- and rutile-structured GeO2, Na4Ge9O20, Na2Ge4O9, and Na2GeO3 (germanium dioxide, sodium enneagermanate, sodium tetragermanate, and sodium metagermanate). 3QMAS spectra of Na-germanate glasses ranging from 0% to 27% Na2O clearly show the development of partially resolved peaks as alkali is added, corresponding to signals from nonbridging oxygens (in the highest Na glasses) and to oxygen bridging between one four-coordinated and one higher coordinated Ge. As in conventional models of this system, nonbridging oxygen contents are much lower than in corresponding silicates. Although we do not directly distinguish between five- and six-coordinated Ge, modeling of bridging oxygen populations and comparison with measured speciation suggest that substantial proportions of both species are likely to be present. High-field 23Na MAS NMR shows systematic decreases in mean Na-O bond distance and/or coordination number with increasing alkali content that can be compared with published results for high-temperature liquids. These results, as well as comparison of molar volumes of glasses and high-temperature liquids, suggest the possibility of significant temperature effects on liquid structure.