Microstructure, mechanical, and in vitro properties of mica glass-ceramics with varying fluorine content

The design and development of glass ceramic materials provide us the unique opportunity to study the microstructure development with changes in either base glass composition or heat treatment conditions as well as to understand processing-microstructure-property (mechanical/biological) relationship. In the present work, it is demonstrated how various crystal morphology can develop when F(-) content in base glass (K(2)O-B(2)O(3)-Al(2)O(3)-SiO(2)-MgO-F) is varied in the range of 1.08-3.85% and when all are heat treated at varying temperatures of 1000-1120 degrees C. For some selected heat treatment temperature, the heat treatment time is also varied over 4-24 h. It was established that with increase in fluoride content in the glass composition, the crystal volume fraction of the glass-ceramic decreases. Using 1.08% fluoride, more than 80% crystal volume fraction could be achieved in the K(2)O-B(2)O(3)-Al(2)O(3)-SiO(2)-MgO-F system. It was observed that with lower fluoride content glass-ceramic, if heated at 1040 degrees C for 12 h, an oriented microstructure with 'envelop like' crystals can develop. For glass ceramics with higher fluorine content (2.83% or 3.85%), hexagonal-shaped crystals are formed. Importantly, high hardness of around 8 GPa has been measured in glass ceramics with maximum amount of crystals. The three-point flexural strength and elastic modulus of the glass-ceramic (heat treated at 1040 degrees C for 24 h) was 80 MPa and 69 GPa of the sample containing 3.85% fluorine, whereas, similar properties obtained for the sample containing 1.08% F(-) was 94 MPa and 57 GPa, respectively. Further, in vitro dissolution study of the all three glass-ceramic composition in artificial saliva (AS) revealed that leached fluoride ion concentration was 0.44 ppm, when the samples were immersed in AS for 8 weeks. This was much lower than the WHO recommended safety limits of 1.5 ppm. Among all the investigated glass-ceramic samples, the glass ceramic with 3.85% F(-) content in base glass (heat treated at 1040 degrees C for 12 h), exhibits the adherence of Ca-P layer, which consists of spherical particles of 2-3 mum. Other ions, such as Mg(+2) and K(+1) ion concentrations in the solution were found to be 8 and 315 ppm after 8 weeks of leaching, respectively. The leaching of all metal ions is recorded to decrease with time, probably due to time-dependent kinetic modification of sample surface. Summarizing, the present study illustrates that it is possible to obtain a good combination of crystallization, mechanical and in vitro dissolution properties with the careful selection of base glass composition and heat treatment conditions.