X-ray diffraction experiments are used to obtain short-range order information of gallium phosphate glasses of meta-and pyrophosphate compositions. Parameters of the first-neighbor peaks, such as coordination numbers and distances, are obtained. A strong decrease of the Ga-O coordination number from 6.0 0.2 to 4.6 0.2 upon Ga 2 O 3 addition is found, which is accompanied by a shortening of the Ga-O distances. Only GaO 6 octahedra exist at the metaphosphate composition. Close to the pyrophosphate composition, the majority of Ga atoms occupies already tetrahedral sites. The Ga-O coordination number behaves equivalent with the ratio TO = (O T )/ (Ga), thus, with the number (O T ) of terminal oxygen atoms (O T ) in phosphorus-O T bonds which are available for the coordination of each Ga atom. Thus, P-O T -Ga bridges are formed for all O T atoms. The GaO polyhedra neither share O T atoms nor form Ga-O-Ga bridges. With increasing fraction of GaO 4 tetrahedra and decreasing lengths of the phosphate chains the network expands.
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