Correlation between Chemical Durability Behaviour and Structural Approach of the Vitreous Part of the System 55P2O5-2Cr2O3-(43-x) Na2O-xPbO

Various characterisation techniques were used to study the composition of the glass series 55-P2O5-2Cr2O3-(43-x) Na2O-xPbO (with 8 ≤ x ≤ 38;mole %) in terms of chemical durability, IR spectroscopy and scanning electron microscopy (SEM). The change in the dissolution rate as a function of time when the studied glasses were kept submerged in distilled water at 90°C for 20 days showed an improvement in the chemical durability when Na2O content was substituted to PbO content. IR spectroscopy revealed a structural change from ultraphosphate groups to pyrophosphate, orthophosphate and probably ring metaphosphate groups. SEM revealed the existence of two phases: a vitreous phase and a crystalline phase. The presence of Cr2O3, even in small amounts, seems to play an important role in the formation of crystallites in the glass network. The improved chemical durability is attributed to the replacement of the easily hydrated Na-O-P and P-O-P bonds by covalent and resistant Pb-O-P bands. Both the increase in PbO content and in the Pb + Cr/P ratio causes an increase in the number of covalent Pb-O-P and Cr-O-P bonds, making the glass structure more rigid. The increase of the covalent Pb-O-P bands leads to a clear evolution of the structure and chemical resistance, caused by grain-boundary resistance as a result of glass crystallisation. The IR spectra indicate that the increase in PbO content favours the formation of isolated PO3-4 orthophosphate groups at the expense of pyrophosphate groups. The radical change in the structure from ultraphosphate groups to pyrophosphate and orthophosphate groups seems to be the cause of the formation of crystallites. The existence of crystallites in these glasses results in a marked improvement in their chemical durability. However, when the crystallites exceed a certain limit, the equilibrium between the glass bath and these crystallites is no longer maintained;we notice, once, a decrease in the chemical durability.

Study of Chromium-Lead-Phosphate Glasses by XRD, IR, Density and Chemical Durability

Glasses in the ternary system Cr2O3-PbO-P2O5 were prepared by direct melting of the mixture with stoichiometric proportions of the reagents Cr2O3, PbO and (NH4)2HPO4 at 1080℃. The glasses obtained are transparent in colour and have a non-hygroscopic appearance. The study of the dissolution rate was carried out on ternary glasses xCr2O3-(45-x)PbO-55P2O5 with (1 ≤ x ≤ 4;mol%), immersed in distilled water at 90℃ for 24 days, indicating a maximum of chemical durability when the level of chromium oxide passed through 2 mol%. Both, IR spectra and X-ray diffraction have indicated the predominance of metaphosphate or cyclic metaphosphate groups with some traces of isolated orthophosphate groups when the Cr2O3 content is equal to x = 2. Analysis of the density values also, has showed a maximum density for x = 2 mol%. The covalent radius values of oxygen have indicated that the minimum value rcal (O2–) is observed for x = 2 mol% and therefore a relatively high reinforcement of the metal-oxygen-phosphorus (Cr-O-P) bonds. SEM Micrographs have exhibited two phases, a vitreous phase and a crystalline phase. The radical change in the structure from ultraphosphate Q3 groups to ring metaphosphate Q2 and orthophosphate groups Q0 seems to be the cause of the formation of crystallites. Beyond 2 mol% of Cr2O3, the structure of the glass changed relatively and the orthophosphate phases increased to the detriment of the metaphosphate phases. We observed a decrease in chemical durability. However, it was confirmed that the dissolution rate (DR) of the S2 analysed compound is comparable to the values of borosilicate glasses which are used as alternative materials for the immobilisation of nuclear waste substances.

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 60P₂O₅-2Cr₂O₃-(38 - x) Na₂O-xFe₂O₃(with 3 ≤ x ≤ 33 mol%)

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.