纳米晶TiO₂涂层上磷灰石形成的机制与动力学:石英晶体微天平研究

Mechanism and kinetics of apatite formation on nanocrystalline TiO2 coatings: a quartz crystal microbalance study.

作者信息

Yang Zhengpeng, Si Shihui, Zeng Xiaoming, Zhang Chunjing, Dai Hongjuan

机构信息

College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China.

出版信息

Acta Biomater. 2008 May;4(3):560-8. doi: 10.1016/j.actbio.2007.10.003. Epub 2007 Oct 22.

Abstract

Apatite (Ca5(PO4)3OH) has long been considered as an excellent biomaterial to promote bone repairs and implant. Apatite formation induced by negatively charged nanocrystalline TiO2 coatings soaked in simulated body fluid (SBF) was investigated using in situ quartz crystal microbalance (QCM), scanning electron microscopy (SEM), Fourier-transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) techniques, and factors affecting its formation such as pH, size of TiO2 particles and thickness of TiO2 coatings, were discussed in detail. Two different stages were clearly observed in the process of apatite precipitation, indicating two different kinetic processes. At the first stage, the calcium ions in SBF were initially attracted to the negatively charged TiO2 surface, and then the calcium titanate formed at the interface combined with phosphate ions, consequently forming apatite nuclei. After the nucleation, the calcium ions, phosphate ions and other minor ions (i.e. CO3(2-) and Mg2+) in supersaturated SBF deposited spontaneously on the original apatite coatings to form apatite precipitates. In terms of the in situ frequency shifts, the growth-rate constants of apatite (K1 and K2) were estimated, respectively, at two different stages, and the results were (1.96+/-0.14)x10(-3)s(-1) and (1.28+/-0.10)x10(-4)s(-1), respectively, in 1.5 SBF solution. It was found that the reaction rate at the first stage is obviously higher than that at the second stage.

摘要

长期以来,磷灰石(Ca5(PO4)3OH)一直被认为是促进骨修复和植入的优良生物材料。利用原位石英晶体微天平(QCM)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和能量色散X射线光谱(EDX)技术,研究了浸泡在模拟体液(SBF)中的带负电荷的纳米晶TiO2涂层诱导的磷灰石形成,并详细讨论了影响其形成的因素,如pH值、TiO2颗粒尺寸和TiO2涂层厚度。在磷灰石沉淀过程中清晰地观察到两个不同阶段,表明存在两种不同的动力学过程。在第一阶段,SBF中的钙离子首先被吸引到带负电荷的TiO2表面,然后在界面处形成的钛酸钙与磷酸根离子结合,从而形成磷灰石核。成核后,过饱和SBF中的钙离子、磷酸根离子和其他微量离子(即CO3(2-)和Mg2+)自发沉积在原始磷灰石涂层上形成磷灰石沉淀。根据原位频率变化,分别估算了两个不同阶段磷灰石的生长速率常数(K1和K2),在1.5 SBF溶液中的结果分别为(1.96±0.14)x10(-3)s(-1)和(1.28±0.10)x10(-4)s(-1)。发现第一阶段的反应速率明显高于第二阶段。

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