Chemical Durability, Properties and Structural Approach of the Glass Series xFe2O3-(45-x) PbO-55P2O5 (with 0 ≤ x ≤ 20;mol%)

The synthesis for glasses series xFe2O3-(45-x)PbO-55P2O5, (with 0 ≤ x ≤ 20;mol%) carried out in a temperature (1050 ± 10)°C, leads to obtaining transparent glasses, brown in color and with a non-hygroscopic appearance. The study of glasses dissolution rate, immersed in distilled water at 90°C for 24 days, indicates a considerable chemical durability. The increase in the Fe2O3 content in the vitreous network to the detriment of PbO is a favorable factor for the chemical durability improvement. Different techniques have been used such as X-ray diffraction, infrared spectroscopy, DSC, SEM and density for the study of these glasses. These techniques have led to establish correlations between chemical and structural properties. Thus the results obtained confirmed the creation of P-O-M bonds (M = Pb, Fe) with a strongly covalent nature to the detriment of the hydrated P-O-P bonds and led to the formation, mainly, of pyrophosphate groups. The low melting point of Pb-O makes it possible to play an important role, at the same time, on the viscosity, on the equilibrium between the vitreous bath and the crystallites formed. The dissolution rate obtained is 100 times smaller than that of silicate glasses used as an alternative form for the vitrification of radioactive waste.

Chemical Durability, Structure Properties and Bioactivity of Glasses 48P<SUB>2</SUB>O<SUB>5</SUB>-30CaO-(22−x)Na<SUB>2</SUB>O-xTiO<SUB>2</SUB>(With 0 <x ≤ 3;mol%)

Phosphate glasses of composition 48P2O5-30CaO-(22−x)Na2O-xTiO2 (with 0 < x ≤ 3, mol%) were prepared by direct melting at 1080°C ± 20°C. The chemical durability of these glasses shows an improvement when the TiO2 content varies from 0 to 2 mol%. The measurements of differential thermal analysis and density, both, indicate the increase of the glass transition temperature and the density. The increase of Tg leads to an improvement of glass rigidity. X-ray diffraction analysis of the glasses annealed at 650°C for 48 h, indicates the appearance of a mixture of metaphosphate and pyrophosphate phases when the TiO2 content varies from 0 to 2 mol%, the last become majority when the TiO2 content rich 2 mol%. Nevertheless, when the TiO2 content exceeds 2 mol%, the analysis, both, by infrared spectroscopy and X-ray diffraction, reveals a radical change of structure with the formation of majorities isolated orthophosphate groups. SEM micrographs illustrated that the number of crystallites increased in the glass network when the TiO2 content increased at the expense of the Na2O content. An increase in the TiO2 content beyond 2 mol% led to the formation of a larger number of crystallites of different sizes, dominated by small crystallite sizes assigned to majority isolated short orthophosphate groups. This phenomenon led to a decrease in chemical durability and seems to be the main cause promoting the bioactivity of glasses. The results of the bioactivity, after a test in an SBF physiological solution within 15 days, shows, both, the formation of hydroxyapatite and tricalcium phosphate layers, in addition to the layer Ca2P2O7, known by its bioactivity, in some samples. The results obtained on the glasses studied make them potential candidates for an application in tissue engineering.

Structural Features and Properties of the Vitreous Part of the System 50P₂O₅-25CaO-(25-x)Na₂O-xCoO (with 0 ≤ x ≤ 25;mol%)

The glass series 50P2O5-25CaO-(25-x)Na2O-xCoO (with (0 ≤ x ≤ 25;mol%), has been prepared by direct melting at 1080°C ± 20°C. The introduction of cobalt in calcium phosphate glasses is used to compare its effect with calcium in inhibition corrosion. The dissolution rate has been investigated. It indicated an improvement of chemical durability when the cobalt oxide increases in the network glass at the expense of Na2O content. Both, IR spectroscopy and X-ray diffraction have confirmed the structure changes when the CoO content increases in the glass. This change results in the disappearance of isolated orthophosphate groups followed of a polymerizing of the structure from isolated orthophosphate towards pyrophosphate chains (Q1) by promoting the formation of olygophosphates (mixed Q1-Q2) rich in pyrophosphates. Analysis of the density values, showed an increase of density with the increase CoO content. The covalent radius values of oxygen rcal (O2-) indicate a significant decrease and therefore a relatively high reinforcement of the metal-oxygen-phosphorus (Co-O-P) bonds. SEM micrograph confirms the evolution of the glass structural morphology. The sample having a maximum CoO content confirms a homogeneous glass phase with quite crystalline particles. This property is prerequisite for many interesting industrial applications.

Elaboration and Characterization of Glasses and Ceramic-Glasses within Theternary Diagram Li₂O-Cr₂O₃-P₂O₅

Use of the regular melting-quench method allowed the isolation of a small glass domain within the ternary system Li2O-P2O5-Cr2O3 at 1000°C. Electrical conductivity and dielectric permittivity measures on sample glasses and ceramic glasses of this domain were performed at a frequency of 10 kHz and at temperatures between 25°C and 300°C. The values of dielectric permittivity and electrical conductivity increase with increasing Li2O content. However, increases of Cr2O3 content, even at low concentrations, induce a change in electrical conductivity behaviour from that of a glass to that of a ceramic glass. The introduction of an increasing amount of Li2O content in vitreous phosphorus pentoxide changes its three-dimensional network;rupture of the P-O-P bond then occurs and there is formation of easily polarisable entities with quite high values of . The vibrational spectroscopy technique I.R has allowed an efficient investigation of the structural change versus composition within the above indicated ternary diagram. The maximal dielectric permittivity obtained at 300°C, both for the glasses and for the ceramic glasses varied in the order 104 to 3 × 105, while the maximum electrical conductivity obtained at 300°C for the ceramic glasses was in the order of 10-3 Ωcm-1.

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.