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微弧氧化法在Ti2448合金表面制备生物活性氧化膜的研究
其他题名Synthesis of a bioactive oxide layer on a Ti2448 alloy by micro-arc oxidation
陶晓杰
学位类型博士
导师郭正晓
2008-03-04
学位授予单位中国科学院金属研究所
学位授予地点金属研究所
学位专业材料学
关键词Ti2448合金 表面改性 微弧氧化 生物活性 抗腐蚀 细胞增殖 蛋白质吸附
摘要Ti2448合金是一种新型的高强度多功能型钛合金,具有很多优异的特点,如较低的杨氏模量、较好的可恢复弹性应变和能量吸收率;较高的强度、不含有毒元素等。但这种合金仍属于生物惰性材料,其表面自发形成的钝化膜在生理条件下不能诱导生物活性物质形成,需经表面改性处理以赋予其生物活性才能满足临床要求。本文采用微弧氧化和热处理相结合的方法在Ti2448合金表面生成一层具有多孔形貌的含钙氧化膜,并对该氧化膜的生物活性、抗腐蚀性能和细胞黏附、增殖、蛋白质吸附等组织相容性进行评价。 本研究确定了一种微弧氧化和热处理相结合的表面处理方法,简称为MH处理。微弧氧化工艺为醋酸钙水溶液作为电解质,直流稳压电源作为工作电源,最终工作电压为250伏。热处理工艺为600oC热处理1小时,炉冷至室温。氧化膜由薄而致密的内层和多孔的外层组成,总厚度可达4µm;氧化膜的粗糙度有显著增加;氧化膜的化学成分主要包括TiO2、CaO、Nb2O5和SnO2,其中TiO2有锐钛矿和金红石两种结构;氧化膜与基体的结合力较好;经模拟生理溶液浸泡实验,七天内氧化膜表面生成完整的磷灰石层。上述研究表明,这一表面处理工艺获得的氧化层有利于提高Ti2448合金的生物活性。 初步探索了微弧氧化,碱处理和热处理的三步处理方法,简称MAH处理。微弧氧化和热处理方法同上,碱处理工艺是60oC,5 M NaOH溶液处理24小时。应用此方法在Ti2448合金表面生成一层具有网格状精细结构的多孔层,其化学组成为Na2TiOx、CaTiO3 和 Nb2O5,此方法进一步提高了合金的表面生物活性。 研究了Ti2448合金在模拟生理环境中的抗腐蚀性能及上述两种表面处理方法对其抗腐蚀性能的影响。Ti2448合金在偏酸性介质中及含有 H2O2或蛋白质的介质中,抗腐蚀性能优于c.p.Ti和 Ti-6Al-4V合金;在近中性和碱性环境中时基本与c.p.Ti和 Ti-6Al-4V合金相当。MH处理后的样品,其抗腐蚀性能比未经处理的合金有明显的提高。氧化层的成分主要包括TiO2和 Nb2O5,它们均为惰性氧化物,在腐蚀体系中的溶解度很低,对合金的抗腐蚀性能有良好作用。MH处理后的样品表面存在大量小孔,但不降低其抗腐蚀性能。MAH处理后的合金抗腐蚀性能也高于未经处理的样品,但低于经MH处理后的样品。 最后研究了MH处理工艺对Ti2448合金表面的细胞黏附、增殖和蛋白质吸附等组织相容性的影响。处理后,样品表面层上的细胞数量明显增加;细胞出现大量伪足,抓附在小孔和台阶处,相互联通,表明细胞活性更好。样品更易吸附蛋白质,蛋白质的吸附量增加。对于不同蛋白质(牛血清蛋白和牛血红蛋白),样品吸附牛血清蛋白质的量要比牛血红蛋白质多,有利于新骨形成。
其他摘要Ti2448 alloy is a new kind of high strength and multi-functional -titanium alloy. This alloy has some desirable properties suitable for biomedical applications, e. g., low elastic modulus, good recoverable elastic strain and energy adsorptivity, high strength and biosaft. However, this alloy is bioinert like other titanium alloys. The naturally formed oxide layer of the alloy can not induce bioactive compound to form on itself. Therefore, in order to meet all the clinical requirements, surface modification should be performed to improve its biological properties. In this work, a micro arc oxidation (MAO) plus heat treatment process is applied to the Ti2448 alloy to form a porous and Ca-contained oxide layer on the surface of the alloy, and then the effects of this process on bioconductiviy, corrosion resistance and histocompatibility, such as ostealblast adhesion, propagation, protein adsorption, are evaluated. In this research, a micro arc oxidation plus heat treatment process, defined as the MH treatment, is developed. In MAO treatment, acetate calcium aqueous solution is used as the electrolyte; the MAO treatment is performed on a DC power supply with a final working voltage of 250V. And heat treatment is performed at 600 °C for 1 h and then cooled in furnace to room temperature. It shows that the oxide layer is porous and two-layered, which is composed of TiO2, Nb2O5, CaO, SnO2 and TiO2 including rutile and anatase crystal structure. The bonding strength between the oxide layer and substrate is strong. After soaked in simulated body fluid, the oxide layer is covered by apatite on its surface in 7 days. The results indicate that the MH treatment improves bioconductivity of the oxide layer. A MAO plus alkaline treatment plus heat treatment process, defined as MAH three-step treatment, is developed too. MAO and heat treatment are the same as that mentioned above, while the process of alkaline treatment is that the specimens are soaked in 5M NaOH solution at 60 °C for 24 hours. After this three-step treatment, a networked, porous layer is formed on the surface of the alloy. This layer is composed of Na2TiOx, CaTiO3 and Nb2O5. The MAH treatment further improves the bioconductivity of this alloy. The corrosion resistance of Ti2448alloy in simulated body environment and the effects of two processes above on this alloy are studied. The corrosion resistance of Ti2448 is better than that of c. p. Ti and Ti-6Al-4V in acid mediums and a medium that contained H2O2 or bovine serum albumin, while is the same as the latter two in neutral and basic mediums. After the MH treatment, the corrosion resistance of Ti2448alloy is significantly improved. The oxide layer mainly consisted of TiO2 and Nb2O5. These two oxides are inert and hardly soluble in corrosive medium, which is beneficial for the corrosion resistance of Ti2448 alloy. The pores structure do not impair the corrosion resistance of the alloy. After the MAH treatment, the corrosion resistance of Ti2448 alloy is also improved, but is not as good as those after the MH treatment. Finally, the effects of the MH treatment on the histocompatibility such as osteolblast adhesion, propagation, protein adsorption of Ti2448 alloy are analyzed. The number of osteolblast cells propagated on the surface after the MH treatment is larger than that of the untreated one. The pseudopods on the osteolblast cells fasten in the pores and stages It shows that these osteolblast cells are bioactive. The specimens after the MH treatment absorb proteins much easier and much more than the untreated ones. The number of bovine serums albumin adsorbed on the specimens after MH treatment is larger than that of bovine hemoglobins that is beneficial for the bone healing.
页数137
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/17045
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
陶晓杰. 微弧氧化法在Ti2448合金表面制备生物活性氧化膜的研究[D]. 金属研究所. 中国科学院金属研究所,2008.
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