Application of infrared spectroscopy to studies of silicate glass structure: Examples from the melilite glasses and the systems Na2O-SiO2 and Na2O-Al2O3-SiO2

Infrared (IR) and Raman spectroscopic methods are important complementary techniques in structural studies of aluminosilicate glasses. Both techniques are sensitive to small-scale (<15 Å) structural features that amount to units of several SiO4 tetrahedra. Application of IR spectroscopy has, however, been limited by the more complex nature of the IR spectrum compared with the Raman spectrum, particularly at higher frequencies (1200–800 cm−1) where strong antisymmetric Si-O and Si-O-Si absorptions predominate in the former. At lower frequencies, IR spectra contain bands that have substantial contributions from ‘cage-like’ motions of cations in their oxygen co-ordination polyhedra. In aluminosilicates these bands can provide information on the structural environment of Al that is not obtainable directly from Raman studies. A middle frequency envelope centred near 700 cm−1 is indicative of network-substituted AlO4 polyhedra in glasses with Al/(Al+Si)>0·25 and a band at 520–620cm−1 is shown to be associated with AlO6 polyhedra in both crystals and glasses. The IR spectra of melilite and melilite-analogue glasses and crystals show various degrees of band localization that correlate with the extent of Al, Si tetrahedral site ordering. An important conclusion is that differences in Al, Si ordering may lead to very different vibrational spectra in crystals and glasses of otherwise gross chemical similarity.