Structure of rare-earth phosphate glasses by X-ray and neutron diffraction

Abstract Previous diffraction studies of the structures of rare-earth phosphate glasses (R2O3)x(P2O5)1−x are extended to glasses with smaller R3+ ions with R = Sm, Gd, Dy, Er, Yb, Y for x = ∼0.25 and with R = Nd, Sm, Gd for x = ∼0.15. Parameters for the P–O, R–O and O–O first-neighbor peaks were obtained by Gaussian fitting. P–P and R–P distances were estimated from the positions of peak maxima. Effects of residual silica or alumina contents present as a result of glass processing were taken into account for selected samples. The P–O coordination number, NPO, and the P–O, O–O, P–P distances are consistent with the presence of phosphate tetrahedra and are insensitive to the R species and the R2O3 content. Rare-earth coordination numbers, NRO, decrease from ∼8 to ∼6.5 when x is increased from ∼0.15 to ∼0.25. NOO and NPP decrease with increasing R2O3 content indicating the network disintegration. The numbers NRO of the metaphosphate glasses (x = ∼0.25) decreases from ∼7 to ∼6 when R is changed from La to Yb. This change is also indicated by the behavior of the R–O distances and by constant number densities of atoms. The decrease in NRO with increasing R2O3 content is due to the reduction in the number of terminal O (OT) available for coordination of the R3+ ions (six at metaphosphate composition). Especially for smaller R3+ ions sharing OT between two R sites is not favored. The decrease by ∼0.04 nm of the prominent R–R first-neighbor distance with a change of R from La to Yb at the metaphosphate composition is indicated by a shift to higher magnitude of scattering vector of the shoulder occurring in front of the first main diffraction peak.