Probing alkali coordination environments in alkali borate glasses by multinuclear magnetic resonance

Five series of binary alkali borate glasses were prepared to compare the alkali dependence of network and modifier short-range order. ¹¹B magic-angle spinning (MAS) NMR reveals that the fraction of four-coordinate boron depends strongly upon alkali type at high-alkali concentrations: heavier alkalis favour the formation of non-bridging oxygens, whereas lithium borates contain a much higher concentration of tetrahedral boron units. The alkali modifiers were observed directly by MAS NMR to measure the change in chemical shift with composition. All alkali peaks shift to higher frequency with increasing loading, indicative of decreasing average coordination numbers. Relative to their known chemical shift ranges, the heavier alkalis exhibit the greatest shifts, whereas the lithium shifts are subtle. This is interpreted in terms of the availability of charged and partially charged coordinating oxygens in the network. Moreover, the ¹³³Cs chemical shifts plateau at 40 mol%, implying that the Cs⁺ coordination number reaches a lower limit at this composition. This work demonstrates that NMR instrumentation and methodology have reached a level where even challenging nuclei like ³⁹K and ⁸⁷Rb can be probed to yield structural information in glasses.