Compositional dependence of calcium phosphate layer formation in fluoride Bioglasses

Bioglasses form a double layer composed of apatite and a silica-rich layer when placed in a simulated physiological solution as well as in living tissue [A.E. Clark, C.G. Pantano, and L. L. Hench, "Auger spectroscopic analysis of bioglass corrosion films," J. Am. Ceram. Soc., 59(1-2), 37-39 (1976).]. In the present work, the mechanisms of the calcium phosphate layer and the silica-rich layer formation of fluoride Bioglasses in Tris-buffer solution are studied as a function of the SiO2 content. Fourier Transform Infrared Reflection Spectroscopy (FTIRS) is used to investigate the mechanism of formation of calcium phosphate and silica-rich layers on the glass surface. Ion concentration in reacted solution and elemental depth profiles are obtained by Induced Coupled Plasma Atomic Emission Spectrometry (ICP) and Auger Electron Spectroscopy (AES), respectively. Si--O bonds with one nonbridging oxygen and Si--O--Si bonds form at the early stage of reaction. Strong phosphorus ion uptake occurs when an amorphous calcium phosphate layer crystallizes. Glasses with high silica content (conventional glass) form the silica-rich layer first followed by a calcium phosphate layer on top. However, glasses with low silica content (invert glass) form both layers simultaneously. The rate of apatite formation decreases with increasing SiO2 content, especially in the region of conventional glass compositions. Ion release rates decreases as SiO2 content increases, with a significant change occurring at the compositional boundary between invert and conventional glasses.