Nuclear magnetic resonance studies of 7Li ionic motion in alkali silicate and borate glasses

Abstract

Nuclear magnetic resonance (NMR) studies of 7Li ionic motion in four lithium and lithium-potassium silicate glasses of the R2O·4SiO2 and R2O·2SiO2 composition were made before and after heat treatment, and a newly developed equation was used for the analysis of the data. Other data from alkali borate glasses of the 3R2O·7B2O3 composition were reanalyzed using the equation, which eliminates the problem of a distribution of ionic relaxation times. It is shown how heterogeneities in the form of barriers to alkali ion motion in the glasses can be detected and studied by NMR. Although all glasses with higher alkali contents appear to be homogeneous, both the borates and silicates with lower alkali contents appear to be heterogeneous. These heterogeneities appear to be on a smaller scale in the borates than in the silicates. In addition to long-range 7Li ionic motion observed in homogeneous glasses (and intermediate-range motion in heterogeneous glasses), there is evidence of short-range motion within severely restricted regions in nearly all glasses studied. The data show that the long-range 7Li ionic motion in glasses proceeds by an interstitial process. The 7Li NMR data of several crystallized lithium silicate glasses in which polycrystalline lithium disilicate was formed reveal that the local atomic structure in the crystal differs from that of the glasses. A large difference found between the activation energies for 7Li long-range motion in glassy (0.648 eV) and crystalline (2.19 eV) lithium disilicate supports this conclusion. Changes of the 7Li activation energy in lithium borate glasses upon partial substitution of lithium-7 by other alkali species follow a trend in accord with an explanation of the mixed-alkali effect in glass previously proposed by the authors.

Solid-state Li NMR with applications to the translational dynamics in ion conductors

“…Subsequent temperature studies of the 7 Li and 11 B NMR in both crystalline and glassy lithium borates demonstrated that in the glass motional narrowing occurs at surprisingly low temperatures. Since these early results there have been numerous observations of motional narrowing of 7 Li spectra in ion conducting glasses, for example [342,86,359,79,353,377,347,[360][361][362]. In [347] the motional narrowing of both the central and satellite transitions are reported.…”

NMR Spectroscopy in Glass Science: A Review of the Elements

“…Lithium NMR, using 7 Li (spin-3/2; 92.58%), was demonstrated in glass science again by Bray, showing in the early 1970s the ability to study ionic motion in glasses [45]. Müller-Warmuth also demonstrated early the importance of 7 Li NMR in glasses [46].…”

Study of alkaline metal ions and glass-formers in glasses with advanced NMR methods and quantum mechanic calculations

“…There is plenty of experimental evidences [1][2][3][4][5][6] on the MAE and also several attempts for explanation [7][8][9][10][11][12][13][14][15][16][17][18][19] of this anomaly. In general, some of the proposed theories [7][8][9][10][11][12][13][14][15][16], consider the type of the interaction between dissimilar alkali ions and the relation of this interaction with the glassy structure.…”