Characterization of the disordered phosphate network in CaO–P2O5 glasses by 31P solid-state NMR and Raman spectroscopies

In this study, the disordered network of calcium phosphate glasses is investigated by Raman scattering and 31P magic angle spinning (MAS) solid-state NMR spectroscopies. The use of both spectroscopies in a combined approach allows drawing a detailed understanding of the structure of these glasses. The P―O―P connectivity between successive PO4 tetrahedra is probed using through-bond double quantum–single quantum (DQ–SQ) and triple quantum–single quantum (TQ–SQ) MAS NMR correlation experiments. Over the broad range of glass compositions studied here, two very different phosphate network topologies are encountered. The results obtained for the polyphosphate compositional range (above 50 mol% Ca) allow determining the phosphate chain-length distribution in the glass as a function of the modifier cation content. For the ultraphosphate region (below 50 mol% Ca), the network topology undergoes a sudden change close to 39 mol% Ca which can be interpreted in terms of a rigidity transition.