Glasses with composition xBi2O3–24Na2O–(75 − x)B2O3–1Er2O3 (where x = 0, 5, 10, 15, 25, 33, 40 mol%), were
prepared by the melt quenching technique. The effect of Bi2O3 content on thermal stability, optical properties and
structures of these glasses is systematically investigated by X-ray diffraction, infrared spectroscopy and DTA
techniques. The variations in the optical band gap energies, with Bi2O3 content have been discussed in terms of
changes in the glass structure. Urbach energy increases with increasing Bi2O3 content in the present glass system.
It is found that the density, molar volume and optical basicity increase with increasing Bi2O3. The glass transition
temperature (Tg) of the samples was found to decrease with the Bi2O3 content. IR measurements revealed an
existence of trigonal BO3 pyramid, tetrahedron BO4, pyramidal BiO3 and octahedron BiO6 structural units in the
network of the investigated glass. Furthermore, a decrease in BO4 and an increase in BO3 take place against the
increase of x which means that, Bi2O3 plays the role of network modifier in the structural network.