Glasses and glass-ceramics have had a tremendous impact upon society and continue to have profound industrial, commercial and domestic importance. A remarkable number of materials, with exceptional optical and mechanical properties, have been developed and enhanced using the glass-ceramic method over many years. In order to develop glass-ceramics, glass is initially prepared via high temperature synthesis and subsequently heat treated, following a carefully designed and controlled process. A glass-ceramic system comprises crystalline and non-crystalline phases; in multicomponent systems these phases are significantly different from the initial glass composition. The properties of glass-ceramics are defined by microstructure, crystal morphology as well as the final chemical composition and physical properties of the residual glass. Knowing the mechanism of glass crystallisation, it is possible to predict and design a glass-ceramic system with near-ideal properties that exactly fulfil the requirements for a particular application. This tutorial review is a basic introduction to the crystallisation in glasses and mainly focuses on silicate and closely related oxide glasses. The review describes and discusses key learning points in five different sections, which facilitate the understanding of glass crystallisation and development of glass-ceramics.

The changes in the structure of 45S5 Bioglass® and its heat-treated versions upon SrO substitution were investigated by solid-state multinuclear magic angle spinning nuclear magnetic resonance (MAS-NMR), X-ray diffraction and differential scanning calorimetry. A series of the melt-derived glasses with SrO gradually substituted for calcium (0, 25, 50, 75 and 100%) on a molar basis was synthesised. The glass transition temperature, T_g, and crystallisation temperature decreased upon SrO substitution. Glasses with 75 and 100% of SrO substitution showed a minor crystalline phase. ³¹P MAS-NMR showed that phosphorus is present as orthophosphate in the entire glass series; ²⁹Si MAS-NMR data showed a predominantly Q² silicate network. A small step change in the position of the ³¹P and ²⁹Si MAS-NMR signals found between the glasses with 25 and 50% of SrO substitution is attributed due to an increase in the ring-type fraction of the Q² silicate glass over the mainly chain topology in the original 45S5 glass. On heat treatment combeite (Na₂Ca₂Si₃O₉) and combeite-type (Na₂CaSi₂O₆) silicate phases were identified. For glasses with increasing SrO contents the equivalent Sr²⁺ substituted phases were formed (viz. Na₂Sr₂Si₃O₉ and Na₂SrSi₂O₆) above 600 °C. The polymerisation degree of phosphorus increased and in addition to orthophosphate amorphous pyro- and meta-phosphate species were observed on heat treatment between 600 and 650 °C, the amount of which reduced with SrO substitution. Above 800 °C, changes in ³¹P MAS-NMR spectra suggested that several phosphate containing phases crystallised and the fraction of the remaining glass was below the detection limit. In contrast to the SrO containing glasses, in the original 45S5 composition a significant fraction of phosphorus remained amorphous even after heat treatment at temperatures above 800 °C.

The bioactivity of a series of fluoride-containing sodium-free calcium and strontium phosphosilicate glasses has been tested in vitro. Glasses with high fluoride content were partially crystallised to apatite and other fluoride-containing phases. The bioactivity study was carried out in Tris and SBF buffers, and apatite formation was monitored by XRD, FTIR and solid state NMR. Ion release in solutions has been measured using ICP-OES and fluoride-ion selective electrode. The results show that glasses with low amounts of fluoride that were initially amorphous degraded rapidly in Tris buffer and formed apatite as early as 3 h after immersion. The apatite was identified as fluorapatite by ¹⁹F MAS-NMR after 6 h of immersion. Glass degradation and apatite formation was significantly slower in SBF solution compared to Tris. On immersion of the partially crystallised glasses, the fraction of apatite increased at 3 h compared to the amount of apatite prior to the treatment. Thus, partial crystallisation of the glasses has not affected bioactivity significantly. Fast dissolution of the amorphous phase was also indicated. There was no difference in kinetics between Tris and SBF studies when the glass was partially crystallised to apatite before immersion. Two different mechanisms of apatite formation for amorphous or partially crystallised glasses are discussed.

With an increasingly elderly population, there is a proportionate increase in bone injuries requiring hospitalization. Clinicians are increasingly adopting tissue-engineering methods for treatment due to limitations in the use of autogenous and autologous grafts. The aim of this study was to synthesize a novel, bioactive, porous, mechanically stable bone graft substitute/scaffold. Strontium- and zinc-containing bioactive glasses were synthesized and used with varying amounts of alginate to form scaffolds. Differential scanning calorimetric analysis (DSC), FTIR, XRD, and NMR techniques were used for the characterization of scaffolds. SEM confirmed the adequate porous structure of the scaffolds required for osteoconductivity. The incorporation of the bioactive glass with alginate has improved the compressive strength of the scaffolds. The bioactivity of the scaffolds was demonstrated by an increase in the pH of the medium after the immersion of the scaffolds in a Tris/HCl buffer and by the formation of orthophosphate precipitate on scaffolds. The scaffolds were able to release calcium, strontium and zinc ions in the Tris/HCl buffer, which would have a positive impact on osteogenesis if tested in vivo.

Chloride is known to volatilize from silicate glass melts and until now, only limited studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amount of CaCl₂.