Ternary phosphates are found to vitrify within large domains of compositions inside the phase diagrams P 2 O 5 -WO 3 -A 2 O (A ‫؍‬ Li, Na). Structural approach of the highly modified glasses P 2 O 5 -A 2 MoO 4 -A 2 O (M ‫؍‬ Mo,W) was investigated using various spectroscopic techniques such as infrared, Raman, and electron spin resonance (ESR). These glasses were found to contain MO 6 octahedra, MO 4 tetrahedra, M 2 O 7 dimers, PO 4 tetrahedra, and also P 2 O 7 or metaphosphate chains, depending on the composition considered. As shown in earlier studies, the glass network is progressively depolymerized as the content of A 2 O increases. ESR experiments were conducted on both X-ray irradiated and unirradiated samples. Unirradiated glasses exhibit two ESR signals attributed to W 5؉ and Mo 5؉ centers that are octahedrally coordinated. Irradiation of these glasses induces new paramagnetic centers ascribed to the phosphorus-oxygen-hole-center and peroxy radicals. The M 5؉ concentration depends strongly on the sample composition and temperature. ESR parameters are determined using a computer simulation approach adapted for vitreous materials.

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