锰和氟共修饰羟基磷灰石陶瓷涂层的制备与表征

由于钛及钛合金具有优越的理化性能，其已被广泛应用于各种植入体，例如骨科、牙科及心血管支架等。然而，钛基材表面具有生物惰性，其与周边骨组织形成骨整合的能力较弱，延缓了组织愈合的时间。因此，改善钛植入体表面生物性能具有重要的临床意义。钛基材表面羟基磷灰石(HAP)复合涂层的制备已成为一种重要的表面生物活性改良手段。在含有F-，Mn2+，Ca2+和PO3-₄的电解液中，用单电流阶跃沉积法，在钛金属(Ti)表面上涂覆锰和氟共修饰羟基磷灰石(FMnHAP)复合薄膜。采用扫描电子显微镜(SEM)、能量弥散X射线谱(EDS)、X-射线衍射(XRD)对涂层进行初步表征，用傅里叶变换红外光谱(FTIR)技术验证了氟离子和锰离子的共修饰对HAP分子构象和生物活性的影响。结果表明：锰部分取代磷灰石中的钙，氟部分取代磷灰石中的羟基，FMnHAP晶格常数变小，薄膜表面形貌由微米级的针状变为纳米级的绒毛状。FTIR技术验证显示，由于磷灰石晶体结构中F取代部分OH，致使改变了结构中OH的弯曲振动模式的对称性;模拟体液体外矿化表明，涂层表面有含碳酸根的类骨磷灰石形成，则涂层的体外生物活性较好。极化曲线测试表明，涂层提高了Ti在生理环境中的耐腐蚀性。

Preparation and Characterization of Manganese and Fluorine Co-Modified Hydroxyapatite Composite Coating

Titanium and titanium alloys have been widely used as orthopedic, dental implants and cardiovascular stents owing to their superior physical properties. However, titanium surface is inherently bio-inert, thus could not form efficient osseointegration with surrounding bone tissue. Therefore, to improve the surface property of titanium implant is significantly important in clinical application. Manganese and fluorine co-doped hydroxyapatite (FMnHAP) coatings were prepared on titanium substrate by electrochemical deposition technique. The as-prepared coatings were examined by scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) tests. The results indicated that the FMnHAP coatings take the morphology of nanoscale-villous-like，the composite coating becomes more compact. The FTIR test indicated that the symmetry of bending vibration modes of hydroxyl changed，simulated body fluid immersion test proved that the FMnHAP coatings had induce carbonate-apatite formation, indicating that the composite coating possess excellent biocompatibility. In the electrochemical corrosion testing, the FMnHAP coatings showed stronger corrosion resistance than pure Ti.