Structure of GeO(2)-P(2)O(5) glasses studied by x-ray and neutron diffraction.

The structures of three xGeO(2)-(1- x)P(2)O(5) glasses, where x = 0.98,0.88, and 0.81, have been studied by neutron and x-ray diffraction experiments that yield well resolved P-O and Ge-O bond distances. The Ge-O coordination number (N(GeO)) increased from 4.0 ± 0.2 to 4.5 ± 0.2 with the decrease in x from 0.98 to 0.81. The increase in N(GeO) is consistent with a structural model that assumes that all oxygen form Ge-O-Ge and P-O-Ge linkages between Ge polyhedra and P tetrahedra and that new GeO(5) or GeO(6) polyhedra are formed with isolated PO(4) units when P(2)O(5) is added to GeO(2). The bond valencies in the P-O bonds of the PO(4) tetrahedra are greater than unity and are balanced in P-O-Ge bridges with underbonded Ge-O links in the GeO(5) or GeO(6) polyhedra. Mixed site connections are expected for the GeO(5) (or GeO(6)) and PO(4) units in glasses with relatively low (<20 mol%) P(2)O(5) content due to the overwhelming fraction of GeO(4) tetrahedra. The structural changes are compared with those reported for alkali germanate glasses. Several features indicate different characteristics for the compositional dependence of N(GeO) for the GeO(2)-P(2)O(5) and alkali germanate glasses. However, the distributions of the first-neighbour Ge-O distances are found to be nearly identical for the GeO(2)-P(2)O(5) and K(2)O-GeO(2) glasses of equimolar K(2)O and P(2)O(5) content.