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Ti基大块金属玻璃表面制备生物活性涂层的研究
Study of the Preparation of Bioactive Layer on the Ti-based Bulk Metallic Glasses
【作者】 胡浩;
【导师】 崔振铎;
【作者基本信息】 天津大学 , 材料学, 2012, 博士
【摘要】 Ti40Zr10Cu36Pd14大块金属玻璃不含Ni、Al、Be等有害元素,具有较高的玻璃形成能力(临界直径达到6mm)和热稳定性、良好的综合力学性能、理化性能和较低的弹性模量,因此在生物材料领域具有良好的应用前景。但作为一种非晶合金,其表面惰性极大地限制了它的应用范围。本文采用表面改性的方法改善非晶合金的生物活性和生物相容性。采用酸碱处理法在Ti基金属玻璃表面构建多孔结构,改善其表面活性,并通过模拟人体溶液(SBF-simulated body fluid)中的仿生矿化生长的方法在此多孔粗糙表面上制备类骨磷灰石层。利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、X射线光电子能谱(XPS)和激光显微Raman光谱仪等分析手段对表面涂层的形貌、物相组成、成分价态等进行表征。结果表明:当经过HN03浸泡和NaOH热碱处理后,Ti40Zr10Cu36Pd14大块金属玻璃表面形成均匀表面多孔结构。经过酸碱处理,Ti基金属玻璃可以在SBF中快速沉积类骨磷灰石层;分析表明类骨磷灰石的主要组成是羟基磷灰石(HA),并初步探讨了酸碱处理工艺对非晶基体的影响。涂层钙磷比(Ca/P)随反应时间增加,至14 d后达到1.62,同时观察到仿生生长可分两个阶段:(1)首先形成一层厚度均匀致密的涂层;(2)涂层表面形成较大的球状沉积颗粒。除此之外,本文还采用溶胶凝胶法在Ti基金属玻璃试样表面制得Ti02层,经170。C水热处理后形成锐钛矿结构;SBF浸泡实验证实该复合涂层结构具有诱导磷灰石形核的能力。
【Abstract】 Ti-based bulk metallic glasses (BMGs) have been studied extensively as a new type of biomaterials owing to their excellent mechanical properties, low Young’s modulus and high elastic limit. Ti4oZr10Cu34Pd16alloys system, without any toxic elements, exhibits good glass-forming ability. However, the biocompatibility of Ti-based bulk glassy alloy is essential when it is used as the candidate for implant.In this work, a Surface modification method is developed to improve the biocompatibility of Ti-based bulk glassy. A bioavtive surface was formed by Acid-alkali pretreatment and a layer of calcium phosphate was prepared n the surface of Ti40Zr10Cu36Pd14BMG samples. The scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron (XPS) and Micro-Raman Spectroscopy were employed to investigate the morphology, component and microstructure of the composite coatings.The result shows that:a bioactive layer was formed on the surface ofthe sample dipped in HNO3 aqueous solution and boiled in 1 M NaOH aqueous solution. After immersion in 1.5×simulated body fluid (SBF) for 14 d, a coating mainly consist of hydroxyapatite (HA) was deposited on the surface pre-treated samples. The Ca/P of the apatite coating was 1.62, and increased by immersion time. The formation of the apatite coating can be divided in two subsequent steps:(1) uniform thin layer first generated and (2) rough layer composed of bigger globules.In addition, a TiO2 coating in anatase type was prepared by sol-gel technique, and in SBF immersion, the TiO2 coatings can induce deposition of calcium phosphate coating composed of hydroxyapatite.
【Key words】 Ti-based bulk metallic glasses; acid and alkali pretreatment; hydroxyapatite coatings; TiO2 coatings; biomimetic growth; sol-gel;