Thermal and Chemical Properties of a Glass in the SiO2-CaO-F System for Dental Applications

The crystallization behaviour of a glass in the SiO₂-CaO-F system was analyzed using differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Three crystalline phases were detected according to ICDD patterns. The first phase formed at 583°C was identified as CaF₂. The morphology was spherulitic with a diameter of approximately 100 nm. The second phase was formed at 664°C. It was identified as calcium fluoride silicate ‘Ca₂SiO₂F₂’ (ICDD 35-0002). SEM investigation showed that the crystals were spherulitic with a diameter smaller than 100 nm. The crystals were precipitated in the volume of the glass and homogeneously distributed. As a third phase, cristobalite crystallized at 895°C. The simultaneous release of calcium and fluorine ions from the vitreous glass in lactate buffer solution at pH 4.0, simulating an acidic oral environment, was investigated using X-ray photoelectron spectroscopy (XPS). The release of calcium and fluorine ions is of special interest for dental applications. The atomic ratios of the components Si, Ca and F at the glass surface after different leaching periods were determined. In order to investigate the leaching process, concentration profiles were measured using ion beam sputtering with Ar⁺ -ions. The dependence of the atomic ratios of Si, Ca and F on the sputter time was determined in order to measure the depth of the leaching layers. Most probably, the release of calcium and fluoride was controlled by a surface layer rich in calcium and flourine ions which dissolved with increasing leaching time. After 2 min leaching, a fluoride-rich surface layer measuring approximately 10 nm was detected. The atomic ratios of Si, Ca and F were different from the bulk composition ratios in a surface reaction layer of 800 nm thickness. After 30 min leaching time, a calcium- and fluoride-rich surface layer approximately 50 nm thick was formed. The bulk composition was reached at a depth of approximately 500 nm. The main component in the surface layer, after 12 days leaching in acidic environment, was silicon. This revised version was published online in August 2006 with corrections to the Cover Date.