An x-ray diffraction and 31P MAS NMR study of rare-earth phosphate glasses, (R2O3)x(P2O5)1-x, x = 0.175-0.263, R = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er

An X-ray diffraction and P-31 MAS NMR study of rare-earth phosphate glasses of composition, (R2O3)(x)P2O5)(1-x), where x = 0.175-0.263 and R = La-Er (except for Pm), is presented. The structures of these materials were investigated as a function of (a) rare-earth atomic number and (b) glass composition, The results show an increase in rare-earth coordination number from six to seven as the rare-earth ion increases in size. This effect is most evident for the rare earths, Ce, Pr and Nd, and appears to be independent of composition variation. The implications of sevenfold coordination in these glasses with respect to the possibilities of rare-earth clustering are discussed, as is the role of the incorporation of aluminium impurities in this regard. The increase in levels of cross-linking within the phosphate network, as a consequence of these small amounts of aluminium, is illustrated, as is the changing nature of the phosphate groups as a function of composition. The first reliable and quantitative parametrization of the second and third neighbour R-(O)-P and R-(OP)-O correlations is also given and the stability of the structures to strain when the glasses are drawn as fibres or exposed to different thermal conditions is described.