Site connectivities in silver borophosphate glasses: new results from 11B{ 31P} and 31P{ 11B} rotational echo double resonance NMR spectroscopy

Abstract

Local and medium range order in the glass system 50Ag 2O–50[(B 2O 3) x –(P 2O 5) 1− x ] ( x=0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6) have been investigated by high-resolution solid state nuclear magnetic resonance (NMR) techniques. The detailed local site distribution has been derived from deconvolution analysis of the 11B and 31P magic-angle spinning (MAS) NMR signals. Quantitative information regarding the extent of boron–oxygen–phosphorus connectivity has been obtained on the basis of 11B[ 31P} and 31P{ 11B} rotational echo double resonance experiments. Incorporation of borate into silver metaphosphate glasses produces four-coordinate BO 4/2 − sites, which crosslink the metaphosphate chains, resulting in a significant increase in the glass transition temperature. Furthermore, the presence of borate favors the disproportionation of P (2) chain-like units into P (1) and P (3) sites, an effect not observed in binary alkali phosphate glasses. Finally, borate incorporation beyond x=0.3 results in the formation of neutral BO 3/2 units, indicating some net charge transfer from the borate to the phosphate network former species. This latter result corresponds to the general metal ion scavenging effect observed for phosphate species in other mixed network former glass systems. In the present system, the effect is relatively moderate, however, suggesting that anionic BO 4/2 − groups are stabilized by the interaction with the phosphate groups.