Relationship between Chemical Durability, Structure and the Ionic-Covalent Character of Me-O-P Bond (Me = Cr, Fe), in the Vitreous Part of the System 60P 2 O 5 -2Cr 2 O 3 -(38 - x) Na 2 O-xFe 2 O 3 (with 3 ≤ x ≤ 33 mol%)

Abstract

The structure and chemical durability in the vitreous part of the system 60P2O5-2Cr2O3-xFe2O3-(38 - x)Na2O phosphate glasses (with 3 ≤ x ≤ 33 mol%) were investigated using various techniques such as IR spectroscopy, X-ray diffraction and M?ssbauer spectroscopy. The presence of Cr2O3 and the increase of Fe2O3 at the expense of Na2O in the glass network lead to a large number of covalent and rigid Fe-O-P and Cr-O-P bonds. The infrared and XRD spectra indicate a radical change of structure and show that the increase of the Fe2O3 content favors the depolymerization of the vitreous network towards pyrophosphate chains. The presence of Cr2O3 in the glass seems to favor the covalent Cr-O-P bonds linked to the most probable cyclic metaphosphate chains. However, when the Fe2O3 content increases (≥23 mol%), its impact on the glass network is stronger than that of Cr2O3. The infrared and XRD spectra indicate a radical change of structure and show that the increase in Fe2O3 content favors the depolymerization of the vitreous network to short pyrophosphate chains. The results of M?ssbauer spectroscopy indicate the presence of both Fe (III) and Fe (II) ions which occupied more or less deformed octahedral sites. The growth of the glass transition temperature (Tg) with the increase of the iron oxide in the vitreous network, leads to an improvement of the glass rigidity. This explains the decrease of the ionic radius of the iron and the reinforcement of the interconnection of the chains of vitreous networks. The structure of sodium-chromium-iron phosphate glasses can be considered largely as pyrophosphate units linked to ferric and ferrous ions in octahedral or deformed octahedral coordination. The dissolution rate is 200 times lower than that of the silicate glasses.