Alteration of amorphous Bi4Ge3O12 by Tl2O and Na2O

Ternary thallium and sodium bismuth germanate glasses were prepared and their densities refractive indices, and infra-red spectra obtained. The effect of univalent cations on the stability of the arrangement of decoupled GeO₄ tetrahedra in amorphous Bi₄Ge₃O₁₂ was compared with the effect of divalent cations. The molar volumes of glasses with the nominal mol% composition 20 M₂O(MO).20 Bi₂O₃.60 GeO₂ are directly related to the size and charge type of M^z+. However, the molar volumes of such glasses are inversely related to the ionic potential (z/r) of M^z+. The infra-red spectra of these ternary glasses exhibitv _Ge?O shifts that reflect the presence of both isolated and small clusters of GeO₄ tetrahedra compared to amorphous Bi₄Ge₃O₁₂. This slight increase in the degree of polymerization appears to be directly related to the ionic potential of M^z+.