Preparation and characterization of sol–gel derived glasses in the ternary Na₂O–Al₂O₃–P₂O₅ system

Abstract

A new sol–gel synthesis route to organic free Na₂O–Al₂O₃–P₂O₅ xerogels was developed. These xerogels contain P₂O₅ up to 67.5 mole % and Al₂O₃ up to 20 mole % and could be melted to homogeneous glasses in air at significantly lower temperatures than those applied using the conventionally melting method. Aluminum isopropoxide dissolved in isopropanol, orthophosphoric acid dissolved in isopropanol and sodium nitrate were used as precursors for Al₂O₃, P₂O₅ and Na₂O respectively. Clear stable alcoholic solutions were prepared in the presence of HNO₃. Addition of HNO₃ in the concentration used, enabled homogeneous mixing of the precursors, controlled over the gelation step and prevented the fast precipitation of the AlPO₄ crystalline phase which breaks down the glass formation ability. The sol–gel route developed was investigated using different analytical tools. Differential thermal analysis (DTA) coupled with thermo-gravimetric (TG) analysis indicated that neither organic residues nor sodium nitrate residues were present in the dried gels after gelation. Fourier transform infrared spectroscopy (FTIR) showed the presence of all characteristic phosphate groups and bonds in the dried gels, especially the P=O and the P–O–P bonds. Solid state ³¹P Magic angle spinning nuclear magnetic resonance (MAS NMR) revealed the formation of Q² chain-like polyphosphates of variable polymerization degrees in the dried gels. Solid state ²⁷Al MAS NMR revealed that octahedrally coordinated Al is the preferred moiety in the dried gels. However, powder X-ray diffraction (XRD) investigation indicated the presence of crystalline Q¹ oligomeric pyrophosphate species in the dried gels. Isotropic chemical shifts belonging to these pyrophosphate species were also recorded in the ³¹P MAS NMR spectra. Characterization of the prepared glasses showed that their properties are in very good agreement with those glasses prepared by the conventionally melting method.