TenHuisen K S, Brown P W
The Pennsylvania State University, Materials Research Laboratory, University Park 16802, USA.
Biomaterials. 1998 Dec;19(23):2209-17. doi: 10.1016/s0142-9612(98)00131-8.
This study investigated the factors influencing the kinetics of Ca9HPO4(PO4)5OH (calcium deficient hydroxyapatite or CDHAp) formation from alpha-Ca3(PO4)2 (alpha-TCP). The kinetics of CDHAp formation were investigated by isothermal calorimetry at constant temperatures ranging between 30 and 75 degrees C and by changes in pH at 37.4 and 70 degrees C. The calorimetric curves were characterized by two reaction peaks. Activation energies were calculated for the events resulting in these peaks. Values obtained were 48.4 and 67.7 kJ mol(-1), respectively, indicating nucleation and growth mechanisms for both events. Temperature had a significant effect on the growth rate as indicated by a decrease in surface area (26.5-15.0 m2 g(-1)) of the CDHAp with increasing temperature (30-75 degrees C). A linear relationship between hydrolysis temperature and CDHAp surface area was observed. The morphology of the CDHAp was plate-like and the crystallites became more regular as the reaction temperature was increased. A rapid elevation in pH upon mixing with water indicated the synthesis method initially used did not entirely eliminate slight compositional variations within the alpha-Ca3(PO4)2. Rapid elevation in pH retarded subsequent reaction. This effect was eliminated by increasing the duration of high-temperature firing during alpha-TCP synthesizing.
本研究调查了影响由α-Ca3(PO4)2(α-磷酸三钙或α-TCP)形成Ca9HPO4(PO4)5OH(缺钙羟基磷灰石或CDHAp)动力学的因素。通过在30至75摄氏度的恒定温度下进行等温量热法以及在37.4和70摄氏度下测量pH值变化来研究CDHAp的形成动力学。量热曲线具有两个反应峰。计算了导致这些峰的事件的活化能。得到的值分别为48.4和67.7 kJ mol(-1),表明这两个事件分别为成核和生长机制。温度对生长速率有显著影响,随着温度升高(30至75摄氏度),CDHAp的表面积减小(从26.5至15.0 m2 g(-1))。观察到水解温度与CDHAp表面积之间存在线性关系。CDHAp的形态为板状,随着反应温度升高,微晶变得更加规则。与水混合后pH值迅速升高表明最初使用的合成方法并未完全消除α-Ca3(PO4)2内的轻微成分变化。pH值的迅速升高阻碍了后续反应。通过增加α-TCP合成过程中高温烧制的持续时间,这种影响得以消除。
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