Anisotropic structure of alkali metaphosphate glasses

Orientation anisotropy, which is well known in organic polymers with appropriate network structures, is less common in oxide glasses. We present the intermediate-range order in anisotropic alkali metaphosphate glass which consists of oriented PO₄ tetrahedral chains and intervening alkali cations along the elongation direction. The X-ray total structure factor S(Q) indicates that the inter-chain spacing depends on the size of alkali cations and varies from 5.03 to 6.28 Å. The mixed alkali effect is primarily related to an increase of the separation. The total correlation function T(r) provides the first definite evidence that the anisotropic structure is composed of phosphorus-bridging oxygen bonds (P–O_B) lying along the elongation direction and phosphorus-non-bridging oxygen bonds (P–O_T) oriented perpendicular to the elongation direction. The present result unveils fundamental aspects of the anisotropic structure of an oxide glass and provides essential information for the development of oxide glasses to control structural anisotropy.