Influence of synthesis conditions on glass formation, structure and thermal properties in the Na2O-CaO-P2O5 system doped with Si3N4 and Mg

Abstract

Oxynitride phosphate glasses and glass-ceramics were prepared using new synthesis routes for phosphate glasses. Materials were melted from pre-prepared glass samples in the system Na-Ca-P-O with addition of Mg and/or Si3N4 powders under different preparation conditions. The melting process was conducted at 1000–1500 °C either under air or nitrogen atmosphere to obtain materials with different nitrogen content. Their topography and structure were characterized by Confocal Microscopy, Scanning Electron Microscopy, X-ray powder diffraction and Raman and infrared spectroscopy techniques, while their chemical compositions were examined by Energy Dispersive X-ray spectroscopy (EDS). All materials prepared under nitrogen atmosphere were found to contain a relative low quantity of nitrogen and high amount of Nb leached from the crucible. The reaction with the Nb crucible was not previously observed for silicon-based oxynitride glasses. The synthesized materials form two groups: glasses and glass-ceramics. The first ones, were prepared under air and nitrogen atmospheres at temperatures up to 1400 °C, and were found to be amorphous and homogeneous. Raman and infrared spectroscopy measurements confirm the presence of amorphous phosphates in the synthesized materials. The samples of the second group were prepared at temperatures above 1400 °C and were found to be translucent and partially crystallized. They contain nanocrystallites of calcium and sodium phosphates including hydroxyapatite (HAp). The thermal properties of samples were studied by Differential Scanning Calorimetry (DSC). The obtained glass transition temperatures range from about 360 °C to 640 °C and exhibit high values for glass-ceramic materials. Stability is improved in the studied glass-ceramics because of the increased degree of network polymerization of the remaining glassy matrix. The approximate fragility index decreases two times for oxynitride materials compared to the primary glass. The synthesized new materials may be competitive to well-known bioactive phosphate glasses thanks to their improved stability by Mg, Si, N and Nb doping.