【作者】 白玲；

【导师】 崔春翔；

【作者基本信息】 河北工业大学 ， 材料学， 2009， 博士

【摘要】 本文根据Ti-Si二元合金相图和3d电子理论,设计并制备了可用于生物医学领域的、不含有毒元素的Ti-Zr-Si系非晶合金T17、TF14、TFM23和TFMN31。通过X射线衍射仪和透射电镜研究了Ti-Zr-Si系非晶合金的组织和形貌。利用Inoue经验理论和非晶钛合金的特征温度研究了合金的玻璃形成能力。此外,分别通过模拟体液法检测了材料的生物活性,运用电化学法测试了材料在不同介质中的耐蚀性,通过常温下合金的拉伸实验检测了合金的弹性模量和抗拉强度。四种非晶合金的X-射线衍射谱表明,合金元素含量变化为14%～31%的Ti-Zr-Si系非晶合金具有较好的玻璃形成能力,其基体组织均为非晶态结构。Inoue经验理论和各合金的特征温度表明,四种非晶合金的玻璃形成能力由强到弱依次为TFM23>T17>TF14>TFMN31。首先,按各组元之间的混合焓的负值大小将四种合金排序如下:TFM23 > T17 > TF14 > TFMN31。其次,各合金的过冷液相区(△Tx)、约化温度Trg和γ判据由大到小依次为TFM23 > T17 > TF14 > TFMN31,此结果与通过Inoue经验理论得到的结论相吻合。模拟体液法实验发现:在模拟体液中培养15天后,四种非晶合金表面均可以看到致密的网状涂层,这种多孔的球形网状结构可以促进骨细胞的粘附和增殖。涂层能谱分析结果表明,涂层主要由Ca、P、O和C等元素组成,且Ca与P的原子百分比n (C a)n(P)大约为1.6,此值接近羟基磷灰石中Ca与P的原子百分含量比值1.66;涂层的红外吸收光谱表明,涂层中含有OH-,PO43-等原子团,证实了涂层的主要成分为HA。非晶钛合金分别在NaCl和PBS溶液中的阳极极化曲线结果表明,与具有优异的耐蚀性能的非晶合金Ti60Zr10Ta15Si15相比,Ti-Zr-Si系非晶合金在3%的NaCl和PBS溶液均具有优异的耐蚀性能。其中,合金TFMN31在NaCl溶液中发生孔蚀行为,其孔蚀电位为1750mV。合金TF14在PBS溶液中发生孔蚀行为,其孔蚀电位为-699.17mV。Ti-Zr-Si系非晶合金的应力-应变曲线的研究表明,Ti-Zr-Si系非晶合金的弹性模量比同种成分的晶态合金低14～59%。其拉伸过程中变形特征为:弹性-塑性变形,材料的失效方式为典型的韧性断裂。更多还原

【Abstract】 Based on the phase diagrams of Ti alloys and 3d electron theory, this dissertation deals with design and preparation of Ti-Zr-Si amorphous alloys system such as T17, TF14, TFM23 and TFMN31 without toxic elements by especially taking the applications of Ti alloys as biomaterials into account. The phase compositions were determined by X-ray diffraction patterns. The surface topography was observed using TEM. The glass forming ability （GFA） of Ti-Zr-Si amorphous alloys was evaluated by Inoue’s experimental rules and characteristic temperatures, respectively. The bioactivity of Ti-Zr-Si amorphous alloys was tested in simulated body fluid （SBF）. The corrosion resisting properties of Ti-Zr-Si amorphous alloys were explained by polarization curves in NaCl and PBS solutions. And Young’s modulus and fracture strength were investigated by stress-strain curves of Ti-Zr-Si amorphous alloys.The X-ray diffraction patterns results showed that the T17, TF14, TFM23 and TFMN31 own amorphous structure.The GFA of the alloys changed more continuously in the order of TFM23 > T17 > TF14 > TFMN31. Firstly, the values of mixing enthalpy of the four alloys were all less than zero and the order from the greatest negative value to the smallest was indicated as follows: TFM23 > T17 > TF14 > TFMN31. Secondly, the region of supercooled liquid （△Tx）, the reduced temperature （Trg） and theγcriterion varied in order of TFM23 > T17 > TF14 > TFMN31, which was consistent with the results of Inoue’s experiential rules.The bioactivity of the four amorphous alloys was tested in SBF. It was found that a compact and netlike and porous layer had been deposited on the surface of alloys after 15 days, which were helpful for the bone cell to conglutinate and proliferate. The element analysis result of the deposition tested by EDS showed that the depositions were composed of Ca, P, O and C etc., and n （C a）n（P） ratio for the deposition is about 1.6 which approached to that of Human bone of 1.66. In addition, the results of IR absorption spectra of deposition showed that the deposition contain OH- and PO₄^3– etc., which confirmed that the deposition consisted of HA.The polarization curves of T17, TF14, TFM23 and TFMN31 in NaCl and PBS solutions showed that T17, TF14, TFM23 and TFMN31 owned excellent corrosion resisting property, compared with amorphous Ti60Zr10Ta15Si15 with excellent corrosion resisting property. In 3% mass NaCl solution at 298K, pitting corrosion generated in TFMN31, whose potential of pitting corrosion was 1750 mV. And, in PBS solution at 310K, pitting corrosion generate in TF14, whose potential of pitting corrosion was -699.17 mV.The stress-strain curves indicated that the values of Young’s modulus of the four amorphous alloys were lower than that of crystals with identical component. Elastic-plastic deformations occurred in the four alloys when the test samples bore stress. The fracture strength and elongation ratio of the TFMN31 were the highest in the four amorphous alloys. In addition, a lot of slipping band could be seen on amorphous surface. At the same time, great deals of dimples appeared on the surface of the fracture which was typical fractography of ductile rupture.更多还原