Glasses and glass-ceramics in the oxyfluoride ternary system Pb(PO3)2-WO3-PbF2

Abstract Glasses were prepared by the melt-quenching method in the ternary system Pb(PO 3 ) 2 -WO 3 -PbF 2 and doped with Er 3+ in order to prepare luminescent transparent glass-ceramics. This work focused on thermal and structural characterization of tungsten lead-phosphate glasses and crystallization study for preparing transparent glass-ceramics. Thermal properties such as thermal stability and crystallization behavior upon heating were investigated by DSC in function of PbF 2 content. For low PbF 2 concentrations, only one crystallization peak due to Pb 3 (PO 4 ) 2 is observed whereas samples containing more than 15% of PbF 2 present another exothermic event at lower temperatures related with precipitation of PbF 2 , Pb 2 P 2 O 7 and Pb 2 OF 2 . Structural investigations by Raman spectroscopy suggest that PbF 2 modifies the tungsten-phosphate network through the formation of P―F and P―O―Pb bonds but the average network connectivity remains almost constant. A crystallization study has been performed by DSC to investigate the dominant crystallization mechanisms in these glasses and it has been established that Pb 3 (PO 4 ) 2 is nucleated on the surface whereas PbF 2 , Pb 2 P 2 O 7 and Pb 2 OF 2 crystallize dominantly from the glassy bulk. Transparent glass-ceramics containing nanosized PbF 2 crystallites were also prepared by suitable heat-treatment on the glass sample containing 20% of PbF 2 and Raman microscopy of these glass-ceramics supports the crystallization mechanisms determined by DSC.