Papers by Author: Adam Calver

Abstract: Apatite-mullite glass-ceramics have been developed based on SiO2-Al2O3-P2O5-CaOCaF2 glasses. The glasses crystallise to form fluorapatite (FAP) and mullite with an appropriate heat treatment. The crystallisation mechanism has been thought to occur via a prior amorphous phase separation. The aim of this study was to carry out real time neutron diffraction of apatite-mullite glass-ceramics in order to develop an understanding of the crystal growth and crystal dissolution phenomena in the temperature regime between 550 and 1200oC. The results show that during the initial stages of fluorapatite crystallisation pronounced line broadening was observed indicating crystallisation on a nanoscale. Mullite starts to crystallise once there is insufficient charge balancing cations in the glass to maintain aluminium in a four fold coordination state. As a result of this work it is suggested that the mechanism of crystal growth of FAP is thought to involve the dissolution of smaller FAP crystals during the crystal growth temperature followed by re-crystallisation of FAP on the remaining larger crystallites during cooling.

Abstract: Strontium is one of the most common substituents in apatite crystals. The presence and behavior of Sr in apatite-group phases are of considerable significance in biology. The present paper investigates the substitution of strontium for calcium in a glass-ceramic of the following composition 4.5SiO23Al2O31.5P2O54CaO1CaF2. The glasses were characterized using Differential Thermal Analysis (DTA), X-ray powder diffraction (XRD), neutron diffraction (ND) and 19F Resonance Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR). The all calcium glass crystallized to calcium fluorapatite (Ca5(PO4)3F). Substituting strontium partially for calcium resulted in the formation of a mixed strontium/calcium fluorapatites. In contrast complete substitution resulted in the formation of strontium fluorapatite. MAS-NMR showed the the F to be present as F-Ca(3) representing a fluoride ion surrounded by three Ca2+ ions in the all calcium glass and was present as F-Sr(3) in the all strontium glass. In the mixed glasses fluorine was present as FCa( 3), F-Ca(2)Sr, F-CaSr(2) and F-Sr(3). Ca had a higher tendency to occupy the F-M(3) sites than Sr which may reflect the higher charge to size ratio of Ca2+ relative to Sr2+ and its greater affinity for F- ions.