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

• Published in: Journal of the American Ceramic Society 2022-02, Vol.105 (2), p.1010-1030
• Main Authors: Alderman, Oliver L. G., Hannon, Alex C., Holland, Diane, Dupree, Ray, Feller, Steve
• Format: Article
• Language: English
• Subjects: Coordination numbers; Elongation; Germanium oxides; Glass transition temperature; Heterogeneity; Lead oxides; Lead silicate; Neutron diffraction; NMR; Nuclear magnetic resonance; Rapid quenching (metallurgy); Spinodal decomposition; Thermal analysis
• ISSN: 0002-7820; 1551-2916
• DOI: 10.1111/jace.18166

Binary PbO–GeO2 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 nGeO = 4.14(3) close to 27 mol% PbO. This is smaller than the maximum nGeO = 4.3 reported in CaO–GeO2 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 GeO5 or GeO6 units, in addition to the majority GeO4 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. Atom number densities of PbO–GeO2 and analogous alkaline earth germanate glasses. The lead germanates clearly show a different behavior to the strontium germanate glasses, despite similar ionic size as a function of metal–oxygen coordination (inset). This, combined with the weak “germanate anomaly” maximum for the lead germanates belies the amphoteric role of lead as a network former with partial modifier character.