Structural effect of cobalt ions added to a borophosphate-based glass system

A new melt derived glass system consisting of Co2O3 added to 40P(2)O(5)center dot 25B(2)O(3)center dot 25CaO center dot 10Na(2)O matrix was investigated in order to evaluate the influence of cobalt ions on the network structure. Multiple techniques, i.e. Xray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy and X-ray Photoelectron Spectroscopy (XPS) were used to characterize the local structure, the nature of the chemical bonding and the surface composition of these samples. The XRD measurements proved the vitreous character of samples with 0 and 3 mol% Co2O3. At higher cobalt oxide content (5, 7 and 10 mol%) the occurrence of a crystalline phase characteristic to Co2P4O12 has been observed. The complementary spectroscopic studies (FTIR and Raman) revealed that the incorporation of Co2O3 enhances the network connectivity and thereby the short range order in samples. Depending on their amount, the cobalt ions differently influence the borophosphate network via the tetraborate/triborate and metaphosphate/pyrophosphate ratios. For the sample containing 10 mol% Co2O3 the FTIR analysis indicates absorptions assigned to vibrations in CoO6 tetrahedra and suggests the presence of six-coordinated cobalt ions in Co3+ valence state. This study has proven that borophosphate based glasses are able to entrap cobalt ions, are sensitive from structural point of view to the amount of Co2O3 and possess interesting structural peculiarities.