Optical and structural investigations on iron-containing phosphate glasses

Abstract

The article reports the preparation and complex characterization of iron-containing phosphate glasses considered to be ecological materials, as they contain non-toxic compounds related to environment. The oxide system Li2O–MgO–(CaO)–Al2O3–P2O5–(FeO/Fe2O3) was investigated in respect to its structural changes caused by MgO replacement with CaO and by the iron addition. UV–vis–NIR (ultraviolet–visible–near infrared) spectroscopy as well as thermo-gravimetric (TG) measurements, differential thermo-analysis (DTA), X-ray diffraction (XRD) analysis, electronic paramagnetic resonance (EPR), and Mossbauer (nuclear gamma resonance) spectroscopy have been used to investigate redox states and coordination symmetry of iron, together with vitreous network changes during the heat treatment up to 1000 °C. UV–vis–NIR transmission spectroscopy revealed no structural modifications when MgO was substituted by CaO, but noteworthy absorption bands attributed to Fe2+/Fe3+ species. TG analysis made in the 20–1000 °C range shows low weight loss accompanied by several thermal effects, as evidenced by DTA. XRD patterns for the glass samples heat treated at about 700 °C revealed the presence of different phosphate crystalline phases containing Mg, Al, and Fe ions. EPR spectroscopy revealed the presence of paramagnetic Fe3+ ions and the change of the first coordination symmetry, when the samples are heated below the vitreous transition temperature. Mossbauer spectroscopy has evidenced two paramagnetic species, Fe2+ and Fe3+, both in octahedral coordination symmetry and a clustering process supported by only Fe3+ ions.