This work studied transmission electron microscopy on the setting mechanism of tetracalcium phosphate/dicalcium phosphate anhydrous (TTCP/DCPA)-based calcium phosphate cement. The results suggest the process for early-stage apatite formation as the follows: when TTCP and DCPA powders are mixed in the phosphate-containing solution, the TTCP powder is quickly dissolved because of its higher solubility in the acidic solution. The dissolved calcium and phosphate ions, along with those ions readily in the solution, are then precipitated predominantly on the surface of DCPA particles. Few apatite crystals were observed on the surface of TTCP powder. During the later stages of reaction, the extensive growth of apatite crystals/whiskers, with a calcium/phosphorous ratio very close to that of hydroxyapatite, effectively linked DCPA particles together and also bridged the larger TTCP particles. It is suggested that, when the large TTCP particles are locked in place by the bridging apatite crystals/whiskers, the CPC is set and would not dissolve when immersed in Hanks' solution after 20-40 min of reaction.
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