Solid-state NMR study of metastable immiscibility in alkali borosilicate glasses

In several series of lithium, sodium, and potassium borosilicate glasses whose compositions traverse known regions of liquid–liquid phase separation, we have applied triple-quantum magic-angle spinning (3QMAS) 11B and 17O NMR to obtain high-resolution information about short-range structure and connections among various network structural units, and their variation with composition and thermal history. Oxygen-17 3QMAS spectra reveal changes in connectivities between silicate and BO3 ([3]B) and BO4 ([4]B) units, by quantifying populations of bridging oxygens such as B–O–B, Si–O–B and Si–O–Si, and of non-bridging oxygens. [3]B–O–Si and [4]B–O–Si as well as [3]B–O–[3]B and [4]B–O–[3]B linkages can be distinguished. 11B MAS and 3QMAS at a magnetic field of 14.1 T allow proportions of several borate units to be determined, including [3]B in boroxol ring and non-ring sites and [4]B with 3 versus 4 Si neighbors. By combining the 11B and 17O NMR results, detailed information on Si/B mixing in sodium borosilicates can be derived, showing, for example, that [4]B and non-ring [3]B tend to mix with silicate units, while ring [3]B is mainly connected to borate groups. In a preliminary study of the effects of varying alkali cation, potassium-containing glasses are similar to those in the sodium borosilicate system, but a lithium borosilicate seems to exhibit considerably greater chemical heterogeneity. In annealing experiments that converted an optically clear to obviously phase-separated glasses, the ratio of [3]B to [4]B does not change significantly, but part of the non-ring [3]B converts to ring [3]B as the degree of unmixing increases.