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Hollow HAP microspheres in sub-millimeter size were prepared and investigated as a drug delivery vehicle. The LCB (lithium-calcium borate) glass microspheres, which were made through flame spray process, were chosen as precursor for hollow HAP microspheres. The LCB glass microspheres reacted with phosphate buffer (K2HPO4) solution for 5 days at 37 ℃. During the reaction the Ca-P-OH compound precipitated on the surface of LCB glass microspheres and formed porous shells. Then the microspheres ted to be hollow ones with the same diameter as the glass microspheres after LCB glass run out in the chemical reaction. After heat-treated at 600 ℃ for 4 h, the Ca-P-OH compound became HAP, thus the hollow HAP microspheres were produced. The mechanism of forming hollow HAP microspheres through the chemical reaction between phosphate buffer and LCB glass was confirmed by the XRD analysis. The microstructure characteristics of the hollow, porous microspheres were observed by SEM.