Structural origin of the weak germanate anomaly in lead germanate glass properties

Abstract Binary PbO–GeO 2 glasses have been studied in detail from 5 to 75 mol% PbO using high‐resolution neutron diffraction, high‐energy X‐ray diffraction, 207‐Pb NMR, pycnometry, and thermal analysis. The Ge–O coordination number displays a broad maximum n GeO = 4.14(3) close to 27 mol% PbO. This is smaller than the maximum n GeO = 4.3 reported in CaO–GeO 2 glasses but occurs at a similar composition. This structural behavior appears to explain the relatively weak germanate anomaly manifest in lead germanate glasses, for example as a maximum in the measured atom number density and a plateau in the glass transition temperatures. The structural role of Pb(II) is complex. On the one hand, short covalent Pb–O bonds and small Pb–O coordination numbers of ∼3 to 4 indicate glass network former character for Pb(II), associated with a stereochemically active electron lone pair. On the other hand, the presence of some GeO 5 or GeO 6 units, in addition to the majority GeO 4 tetrahedral species, indicates some modifier character of Pb(II) at low PbO contents, giving rise to the observed weak germanate anomaly, as well as elongation and enhanced ionicity of the Pb–O bonds. Overall, the observed structural behavior of Pb(II) in lead germanate glasses appears as intermediate between that observed in lead silicate and lead borate glasses. Despite rapid quenching, at low PbO contents, the glasses studied exhibited nanoscale heterogeneity, evidenced by small‐angle X‐ray scattering consistent with the early stages of spinodal decomposition.