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Structure and disorder in Pb‐Na metasilicate (PbO:Na 2 O:2SiO 2 ) glasses: A view from high‐resolution 17 O solid‐state NMR
Author(s) -
Kim HyoIm,
Lee Seoyoung,
Kim Eun Jeong,
Lee Sung Keun
Publication year - 2021
Publication title -
journal of the american ceramic society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.9
H-Index - 196
eISSN - 1551-2916
pISSN - 0002-7820
DOI - 10.1111/jace.17536
Subject(s) - silicate , alkali metal , natural bond orbital , chemistry , silicate glass , solid state nuclear magnetic resonance , mineralogy , nmr spectra database , materials science , analytical chemistry (journal) , crystallography , spectral line , density functional theory , nuclear magnetic resonance , physics , organic chemistry , astronomy , computational chemistry , chromatography
Knowledge of the structure of lead (Pb)‐bearing silicate glasses, such as degree of polymerization and arrangement among cations, provides improved prospects for understanding their macroscopic properties. Despite the importance, the detailed disorder in Pb‐bearing silicate glasses with varying composition (i.e., Pb/alkali content) has not been systematically explored. Here, we reveal the first unambiguous structural information of PbO‐Na 2 O‐SiO 2 glasses with varying PbO content [i.e., X PbO = PbO/(Na 2 O + PbO)], which are the fundamental model system for multicomponent Pb‐bearing glasses, using high‐resolution 17 O solid‐state NMR. 17 O NMR spectra clearly show the resolved multiple oxygen sites, such as Na‐O‐Si, Si‐O‐Si, and [Na,Pb]‐O‐Si. As X PbO increases, the fraction of [Na,Pb]‐O‐Si peak increases markedly at the expanse of substantial reduction in the fraction of Na‐O‐Si/total NBO. This trend indicates the relative predominance of the dissimilar pairs around non‐bridging oxygen (NBO) and, therefore, can be explained well with the pronounced chemical ordering among Na + and Pb 2+ . These results confirm that Pb is primarily a network‐modifier in the glasses studied here. Atomic environments around both NBO and BO are affected by the change in Na/Pb ratio, while topological disorder due to cation mixing around NBO is much more prominent in Pb endmember. The structural details of short‐range configurations around oxygen in alkali Pb‐silicate glasses provide atomistic insights for understanding the properties of Pb‐bearing multicomponent silicate glasses.