为了改善植入钛合金材料在人体环境中耐蚀性能,采用双阴极等离子反应溅射沉积方法,在医用Ti-6Al-4V钛合金表面制备了厚度为40 μm、平均晶粒尺寸为12.8 nm的Ta₂N纳米晶涂层。采用纳米压入仪、Vikers压痕仪和划痕仪考察了Ta₂N纳米晶涂层的硬度、弹性模量、韧性以及涂层与基体间的结合力。结果表明,Ta₂N涂层的硬度和弹性模量分别为(32.1±1.6) GPa和(294.8±4.2) GPa,涂层与基体的结合力为56 N;在压入载荷为0.49~9.8 N下,Vikers压痕表面以及横断面均未观察到微裂纹,反映其具有较高的压痕韧性。采用动电位极化、电化学阻抗谱、恒电位极化和电容测量(Mott-Schottky)等多种电化学表征技术,对Ta₂N涂层在Ringer's生理溶液中的电化学腐蚀行为进行了深入研究,并从钝化膜组成、致密性和半导体特性3个方面探讨了涂层的腐蚀防护机理。结果表明,在Ringer's生理溶液中,Ta₂N涂层表面形成的钝化膜更加致密,其腐蚀抗力明显优于Ti-6Al-4V合金。XPS分析结果表明,在较低的极化电位下,Ta₂N涂层的钝化膜主要由TaO_xN_y构成,随着外加极化电位的升高,其进一步氧化形成Ta₂O₅;电容测试结果表明,Ta₂N涂层表面所生成的钝化膜具有n型半导体特征,其施主浓度和载流子扩散系数明显低于Ti-6Al-4V 合金表面生成的钝化膜。

Due to its combination of outstanding characteristics, such as superior biocompatibility, excellent mechanical properties as well as good corrosion resistance, Ti-6Al-4V alloy has gained much attention as one of the most popular load-bearing biomedical metals in the area of orthopedic and dental. Unfortunately, Ti-6Al-4V alloy suffers from the localized corrosion damage in human body ?uids containing high chloride ion concentrations, which leads to the release of metal ions into the human body. The released ions (e.g., Al and V) are found to not only cause allergic and toxic reactions but also exhibit potential negative effects on osteoblast behavior. To improve the corrosion resistance of Ti-6Al-4V alloy in simulated body ?uids, a 40 μm thick Ta₂N nanocrystalline coating with an average grain size of 12.8 nm was engineered onto a Ti-6Al-4V substrate using a double cathode glow discharge technique. The hardness and elastic modulus of the Ta₂N coating were determined to be (32.1±1.6) GPa and (294.8±4.2) GPa, respectively, and the adhesion strength of the coating deposited on Ti-6Al-4V substrate was found to be 56 N. There is no evidence of crack formation within the coating under loads ranging from 0.49 N to 9.8 N, implying that the Ta₂N nanocrystalline coating has a high contact damage resistance. Moreover, the corrosion resistance of the Ta₂N nanocrystalline coating is significantly greater than that of Ti-6Al-4V alloy when tested in naturally aerated Ringer's solution at 37 ℃. This is due to that the passive film developed on the coating has superior compactness compared with that formed on the uncoated Ti-6Al-4V alloy. XPS analysis indicated that at a low polarized potential, the passive film consisted of TaO_xN_y, which would be converted to Ta₂O₅ at a higher polarized potential. The analysis of Mott-Schottky curves suggested that the passive film formed on the coating exhibits n-type semiconductor properties and, as such, the density and diffusivity of carrier for the coating was considerably lower than that for the uncoated Ti-6Al-4V alloy.