TC4表面沉积Nb涂层在模拟体液环境下的电化学性能研究

doi:10.11902/1005.4537.2019.270

中国腐蚀与防护学报

2021, Vol. 41

Issue (1): 71-79 DOI: 10.11902/1005.4537.2019.270

研究报告

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TC4表面沉积Nb涂层在模拟体液环境下的电化学性能研究

史昆玉, 吴伟进, 张毅, 万毅, 于传浩(

)

武汉工程大学机电工程学院武汉 430205

Electrochemical Properties of Nb Coating on TC4 Substrate in Simulated Body Solution

SHI Kunyu, WU Weijin, ZHANG Yi, WAN Yi, YU Chuanhao(

)

School of Mechanical & Electrical Engineering, Wuhan Institute of Technology, Wuhan 430205, China

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摘要:

利用双阴极等离子溅射技术在Ti-6Al-4V (TC4) 合金表面沉积Nb涂层，采用XRD、XPS和SEM研究涂层的组成及横截面形貌，并采用电化学工作站对涂层与基体的电化学性能及其钝化膜半导体特性进行研究。电化学测试均在模拟人体体液环境的Ringer's溶液中37 ℃下进行。结果表明，Nb涂层厚度约为18 μm，无孔洞、裂纹等缺陷，在 (200) 晶面呈现择优取向。涂层表面钝化膜成分主要为Nb₂O₅。相比TC4基体，涂层具有更高的开路电位E_OCP、腐蚀电位E_corr和更低的腐蚀电流密度I_corr；涂层与基体合金试样均表现出单一容抗弧，但涂层具有更高的阻抗和较低的有效电容值；两种试样的钝化膜均表现出n型半导体特性，在不同的成膜电位E_f下，Nb涂层的钝化膜具有更低的平带电位E_fb，施主密度N_d和扩散系数D₀。

关键词 ： Ti-6Al-4V合金, Nb涂层, 耐腐蚀性能, 钝化膜, 半导体特性

Abstract：

To improve the corrosion resistance of Ti-alloy applied to human implants, Nb coating was deposited on the surface of Ti-6Al-4V (TC4) alloy by double cathode plasma sputtering technique. The composition and the cross-sectional morphology of the coating were characterized by XRD, XPS and SEM. The electrochemical properties of the coating and the semiconductor properties of the passivation film for the coating and the substrate were studied in Ringer's simulated body solution at 37 ℃ by electrochemical workstation. The results show that the Nb coating exhibits a preferred orientation on the (200) crystal plane, and the coating thickness is about 18 μm without defects such as holes and cracks. The passive film on the Nb coating is mainly Nb₂O₅. Comparing with the TC4 substrate, the coating has higher open circuit potential (E_OCP), corrosion potential (E_corr) and lower corrosion current density (I_corr). Both of the TC4 alloys with and without Nb coating exhibit a single capacitance loop, however, the coated alloy exhibits higher impedance and lower effective capacitance rather than the substrate. The passivation films of two samples exhibit n-type semiconductor characteristics. By different formation potential (E_f), the flat band potential (E_fb), the donor density (N_d) and diffusion coefficient (D₀) of the passivation film on the coating are always lower than that on the bare TC4 alloy.

Key words： Ti-6Al-4V alloy Nb coating corrosion resistance passive film semiconductor property

收稿日期: 2019-12-19

ZTFLH:

TG174.445

基金资助:武汉工程大学研究生教育创新基金项目(CX2019242)

通讯作者: 于传浩 E-mail: yuchuanhaowh@126.com

Corresponding author: YU Chuanhao E-mail: yuchuanhaowh@126.com

作者简介: 史昆玉，女，1972年生，博士

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引用本文:

史昆玉, 吴伟进, 张毅, 万毅, 于传浩. TC4表面沉积Nb涂层在模拟体液环境下的电化学性能研究[J]. 中国腐蚀与防护学报, 2021, 41(1): 71-79.
Kunyu SHI, Weijin WU, Yi ZHANG, Yi WAN, Chuanhao YU. Electrochemical Properties of Nb Coating on TC4 Substrate in Simulated Body Solution. Journal of Chinese Society for Corrosion and protection, 2021, 41(1): 71-79.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2019.270 或 https://www.jcscp.org/CN/Y2021/V41/I1/71

图1 Nb涂层的X射线衍射图谱

图2 不同分辨率下Nb涂层的横截面形貌像

图3 Nb涂层与TC4基体在37 ℃的Ringer's溶液中的开路电位-时间曲线

图4 Nb涂层与TC4基体在37 ℃的Ringer's溶液中的动电位极化曲线

表1 Nb涂层与TC4基体在37 ℃的Ringer's溶液中的极化参数

图5 Nb涂层与TC4基体在Ringer's溶液中的阻抗谱

图6 阻抗谱拟合电路图Rs(Q1(R1(Q2R2)))

表2 Nb涂层与TC4基体在Ringer's溶液中的阻抗谱拟合数据

图7 Nb涂层在37 ℃的Ringer's溶液中以1.0 V恒电位极化1 h所形成钝化膜的XPS测量谱

图8 Nb涂层与TC4基体在37 ℃的Ringer's溶液中的Mott-Schottky测试结果

表3 Nb涂层与TC4基体的钝化膜在37 ℃ Ringer's溶液中的电容测量和计算结果

图9 涂层与基体的施主密度与成膜电位的关系曲线

图10 Nb涂层与TC4的稳态钝化膜厚度和电容与成膜电位的关系曲线

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