The structure of sodium silicate glass from neutron diffraction and modeling of oxygen‐oxygen correlations

• Published in: Journal of the American Ceramic Society Vol. 104; no. 12; pp. 6155 - 6171
• Main Authors: Hannon, Alex C., Vaishnav, Shuchi, Alderman, Oliver L. G., Bingham, Paul A.
• Format: Journal Article
• Language: English
• Published: Columbus Wiley Subscription Services, Inc 01.12.2021
• Subjects: bond length; Coordination numbers; Correlation; Crystal structure; Crystals; glass; Modelling; Neutron diffraction; Oxygen; silicates; Silicon; Sodium; Sodium silicates; structure; Tetrahedra
• ISSN: 0002-7820; 1551-2916
• DOI: 10.1111/jace.17993

It is shown that modeling the first oxygen‐oxygen peak in the neutron correlation function of a glass enables structural information about other correlations to be obtained, and the method is illustrated by application to a sodium silicate glass. The first O–O coordination number can be calculated from network theory, and sodium silicate crystal structures show that the mean O–O distance can be calculated from the Si–O distance, despite the distortion of the SiO4 tetrahedra. Modeling the O–O peak for a sodium silicate glass allows the Na‐O bond length distribution to be determined. For a binary glass with 42.5 mol% Na2O, it is found that the Na–O coordination number is 4.8(2) with an average bond length of 2.45 Å, and the Na–O bond lengths are more widely distributed than in sodium silicate crystal structures. Sodium ions are bonded mostly to non‐bridging oxygens (NBOs), and the Na–NBO coordination number may be four as in crystals. Sodium ions are also bonded to a smaller number of bridging oxygens (BOs). Contrary to previous reports, it is not concluded that Na–NBO bonds are shorter than Na–BO bonds, but instead that the Na–BO distribution is relatively narrow, whilst the Na–NBO distribution extends to both shorter and longer distance. The broad distribution of Na–O bond lengths arises from a relatively broad distribution of Na–NBO bond valences, subject to the overall requirement of charge balance. Sodium ions in sodium silicate glasses have a strong preference to bond to four non‐bridging oxygens, and they also bond to a smaller number of bridging oxygens. Na‐NBO bonds are more widely distributed than Na–BO bonds, extending to shorter and longer distances.