PNNL

Abstract

Four compositions of high density (~8 g/cm3) heavy metal oxide glasses composed of PbO, Bi2O3, and Ga2O3 were produced and refractivity parameters (refractive index and density) were computed and measured. Optical basicity was computed using three different models – average electronegativity, ionic-covalent parameter, and energy gap – and the basicity results were used to compute oxygen polarizability and subsequently refractive index. Refractive indices were measured in the visible and infrared at 0.633 µm, 1.55 µm, 3.39 µm, 5.35 µm, 9.29 µm, and 10.59 µm using a unique prism coupler setup, and data were fitted to the Sellmeier expression to obtain an equation of the dispersion of refractive index with wavelength. Using this dispersion relation, single oscillator energy, dispersion energy, and lattice energy were determined. Oscillator parameters were also calculated for the various glasses from their oxide values as an additional means of predicting index. Calculated dispersion parameters from oxides underestimate the index by 3 to 4%. Predicted glass index from optical basicity, based on component oxide energy gaps, underpredicts the index at 0.633 µm by only 2%, while other basicity scales are less accurate. The predicted energy gap of the glasses based on this optical basicity overpredicts the Tauc optical gap as determined by transmission measurements by 6 to 10%. These results show that for this system, density, refractive index in the visible, and energy gap can be reasonably predicted using only composition, optical basicity values for the constituent oxides, and partial molar volume coefficients. Calculations such as these are useful for a priori prediction of optical properties of glasses.