Electrochemical corrosion behaviors of commercially pure titanium fabricated by equal channel double angular pressing
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摘要: 采用BC路径等通道双转角挤压（ECDAP）方法成功制备出2道次工业纯钛。以3.5%NaCl腐蚀溶液为介质，对大塑性变形前后工业纯钛的电化学腐蚀行为进行了研究，获得了开路电位、动电位极化曲线、电化学阻抗的变化规律。同时，测试分析了显微硬度变化情况。结果表明，相比原始材料，ECDAP工艺制备的超细晶纯钛兼具更高的显微硬度与更优异的耐腐蚀性能。2道次变形试样显微硬度(HV)达157.4，相比原始材料增幅为20.6%。单道次变形试样的开路电位值高于原始材料，低于2道次变形试样。在阳极氧化过程中，变形试样的电流更加稳定，钝化状态更加不易被破坏。极化电阻结果表明，2道次变形试样极化电阻最高，腐蚀过程中试样越不容易出现点蚀。相比变形试样，原始材料腐蚀表面点蚀坑数量更多，蚀孔又大又深。ECDAP变形处理试样耐腐蚀性能优于原始材料，并且2道次ECDAP试样耐腐蚀性能最佳。Abstract: Commercially pure titanium (CP-Ti) was successfully fabricated by 2 passes of equal channel double angular pressing (ECDAP) process under BC route. The electrochemical corrosion behaviors of CP-Ti before and after ECDAP were also tested and analyzed in a 3.5%NaCl solution. The variation laws of circuit potential, dynamic potential polarization curve, and electrochemical impedance were obtained. The microhardness of the deformed specimens was tested and analyzed. The result shows, compared to the original material, the ultra-fine crystalline pure titanium fabricated by ECDAP process has higher microhardness and better corrosion resistance. The microhardness (HV) of the 2-pass deformed sample reaches 157.4 with an increase of 20.6% compared to the original material. The open circuit potential value of the 1-pass deformed sample is higher than that of the original material and lower than that of the 2-pass deformed sample. During the anodizing process, the current of the deformed sample is more stable, and the passivation state is less likely to be destroyed. The polarization resistance results show that the 2-pass deformed sample has the highest polarization resistance, and the sample is less prone to pitting corrosion during the corrosion process. Compared to the deformed samples, the original material has more corrosion pits with larger and deeper sizes on the corrosion surface. The corrosion performance of ECDAP deformed specimens is better than the original annealed sample, and the 2-pass deformed sample shows the best corrosion resistance.
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图 2 （a）电化学测试固封样品；（b）电化学工作站
Figure 2. (a)Encapsulated sample; (b) electrochemical workstation
图 3 工业纯钛挤压变形试样宏观形貌
Figure 3. Macroscopic morphology of the deformed billets of commercially pure titanium
图 6 不同条件下工业纯钛的开路电压
Figure 6. Open circuit potential curves of CP-Ti under different conditions
图 7 不同条件下工业纯钛的动电位极化曲线
Figure 7. Dynamic potential polarization curves of CP-Ti under different conditions
图 10 不同条件下工业纯钛的Nyquist图
Figure 10. Nyquist spectra of CP-Ti under different conditions
图 11 不同条件下工业纯钛的腐蚀形貌
（a）原始退火态；（b）1道次ECDAP挤压态；（c）2道次ECDAP挤压态
Figure 11. Corrosion morphology of CP-Ti under different conditions
表 1 不同条件下工业纯钛的动电位极化曲线特征参数
Table 1. Characteristic parameters of dynamic potential polarization curve of CP-Ti under different conditions
挤压道次 Ecorr/V ba bc Icorr/(A·cm−2) Rp/(Ω·cm−2) 0 − 1.2658 0.133 −0.017 1.38931 E-066099.78654 1 − 1.2342 0.140 −0.068 1.31311 E-0643780.07482 2 − 1.2027 0.077 −0.053 9.62 E-07 76882.50184 
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表 2 不同条件下工业纯钛在3.5%NaCl溶液中等效电路拟合结果
Table 2. Values of equivalent circuit elements of CP-Ti under different conditions
道次 Rs/(Ω·cm−2) Rp/(Ω·cm−2) C/(F·cm−2) n 0 20.15 141 000 0.00002826 0.8343 1 26.23 162 700 0.00004146 0.8531 2 11.56 835 500 0.00008785 0.8784
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