不同离子对<strong>TC4</strong>钛合金电化学腐蚀行为的协同作用机制

doi:10.11900/0412.1961.2021.00266

金属学报

2023, Vol. 59

Issue (7): 939-946 DOI: 10.11900/0412.1961.2021.00266

研究论文

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不同离子对TC4钛合金电化学腐蚀行为的协同作用机制

赵平平¹, 宋影伟¹^,²(

), 董凯辉¹^,², 韩恩厚¹^,²

¹中国科学院金属研究所中国科学院核用材料与安全评价重点实验室沈阳 110016
²南方海洋科学与工程广东省实验室(珠海) 珠海 519000

Synergistic Effect Mechanism of Different Ions on the Electrochemical Corrosion Behavior of TC4 Titanium Alloy

ZHAO Pingping¹, SONG Yingwei¹^,²(

), DONG Kaihui¹^,², HAN En-Hou¹^,²

¹CAS Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
²Southern Marine Science and Engineering Guangdong Laboratory (Zhuhai), Zhuhai 519000, China

引用本文:

赵平平, 宋影伟, 董凯辉, 韩恩厚. 不同离子对TC4钛合金电化学腐蚀行为的协同作用机制[J]. 金属学报, 2023, 59(7): 939-946.
Pingping ZHAO, Yingwei SONG, Kaihui DONG, En-Hou HAN. Synergistic Effect Mechanism of Different Ions on the Electrochemical Corrosion Behavior of TC4 Titanium Alloy[J]. Acta Metall Sin, 2023, 59(7): 939-946.

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摘要:

采用电化学方法研究了H⁺、F^-及其2者协同作用加速TC4钛合金腐蚀的机制，以及添加Fe³⁺后TC4钛合金腐蚀的缓蚀机理。结果表明，H⁺对TC4钛合金表面钝化膜的破坏作用较小，而F^-对钝化膜破坏作用极大，尤其当F^-和H⁺共存时协同加速TC4钛合金的腐蚀，但加入一定浓度的Fe³⁺后，对TC4钛合金的腐蚀起到抑制作用，原因是Fe³⁺加速阴极还原反应，使阳极从活化-钝化区转移到钝化区，同时溶液中Fe³⁺通过络合作用消耗F^-，减弱了F^-对钝化膜的破坏作用。

关键词 ：钛合金, 电化学腐蚀, 协同作用, 钝化膜, 离子

Abstract：

Due to the compact passive film, titanium alloys exhibit excellent corrosion resistance. However, during practical applications, the passive film is inevitably damaged by aggressive ions. Among the common ions, F^- is the most harmful to the passive film because of its high complexation with Ti. However, the destructiveness of F^- varies with pH. Moreover, there are inhibitory ions that reduce the aggressiveness of F^-. The acceleration effects of H⁺ and F^- as well as the inhibition effect of Fe³⁺ on the corrosion behavior of TC4 alloy were examined in this work using electrochemical polarization curves measurements and electrochemical impedance spectroscopy (EIS). The results reveal that whereas H⁺ has slight destructive effect on the passive film, F^- has a considerable aggressive effect. In particular, F^- and H⁺ work synergistically to accelerate the corrosion of the TC4 alloy. The addition of Fe³⁺ can somewhat reduce corrosion of the TC4 alloy. This can be attributable to the fact that the faster cathodic reduction caused by Fe³⁺ moves the anodic curves from active-passive region to passive region. Meanwhile, F^- is consumed by forming a compound with Fe³⁺, which mitigates the corrosive effect of F^- on passive film.

Key words： titanium alloy electrochemical corrosion synergistic effect passive film ion

收稿日期: 2021-06-29

ZTFLH:

TG178

基金资助:南方海洋科学与工程广东省实验室(珠海)创新团队建设项目(311021013)

通讯作者: 宋影伟，ywsong@imr.ac.cn，主要从事轻合金的腐蚀与防护

Corresponding author: SONG Yingwei, professor, Tel: (024)23893115, E-mail: ywsong@imr.ac.cn

作者简介: 赵平平，女，1994年生，博士生

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图1 TC4钛合金显微组织的OM像

图2 TC4钛合金在含不同浓度H+的3.5%NaCl中的极化曲线和EIS结果

表1 TC4钛合金在含不同浓度H+的3.5%NaCl中极化曲线的拟合结果

图3 TC4钛合金在含不同浓度F-的3.5%NaCl中的极化曲线和EIS结果

表2 TC4钛合金在含不同浓度F-的3.5%NaCl中极化曲线的拟合结果

图4 TC4钛合金在含不同浓度F-的酸性3.5%NaCl + 50 mmol/L H+中的极化曲线和EIS结果

表3 TC4钛合金在含不同浓度F-的酸性3.5%NaCl + 50 mmol/L H+中极化曲线的拟合结果

图5 TC4钛合金在含不同浓度H+的3.5%NaCl + 3 mmol/L F-溶液中的极化曲线

图6 TC4钛合金在含不同浓度Fe3+的酸性含氟溶液3.5%NaCl + 50 mmol/L H+ + 3 mmol/L F-中的极化曲线和EIS结果

表4 TC4钛合金在含不同浓度Fe3+的酸性含氟溶液3.5%NaCl + 50 mmol/L H+ + 3 mmol/L F-中极化曲线的拟合结果

图7 Fe3+对TC4钛合金在3.5%NaCl中阴极和阳极极化曲线的影响

图8 不同离子对钛合金极化曲线影响示意图

1	Yan M Q, Chen L Q, Yang P, et al. Effect of hot deformation parameters on the evolution of microstructure and texture of β phase in TC18 titanium alloy [J]. Acta Metall. Sin., 2021, 57: 880
1	颜孟奇, 陈立全, 杨平等. 热变形参数对TC18钛合金β相组织及织构演变规律的影响 [J]. 金属学报, 2021, 57: 880 doi: 10.11900/0412.1961.2020.00352
2	Xu X, Liang W P, Miao Q, et al. Effect of ZrN modified layer on friction and wear properties of TA18 titanium alloy [J]. Surf. Technol., 2021, 50(5): 133
2	许肖, 梁文萍, 缪强等. ZrN改性层对TA18钛合金摩擦磨损性能的影响 [J]. 表面技术, 2021, 50(5): 133
3	Dong J J, Fan J, Zhang H B, et al. Electrochemical performance of passive film pormed on Ti-Al-Nb-Zr alloy in simulated deep sea environments [J]. Acta Metall. Sin. (Engl. Lett.), 2020, 33: 595 doi: 10.1007/s40195-019-00958-4
4	Wang Y H, Li X, Alexandrov I V, et al. Impact of equal channel angular pressing on mechanical behavior and corrosion resistance of hot-rolled Ti-2Fe-0.1B alloy [J]. Materials (Basel), 2020, 13: 5117 doi: 10.3390/ma13225117
5	Zhao P P, Song Y W, Dong K H, et al. Effect of passive film on the galvanic corrosion of titanium alloy Ti60 coupled to copper alloy H62 [J]. Mater. Corros., 2019, 70: 1745
6	Hu C Y, Lo S L, Kuan W H, et al. Treatment of high fluoride-content wastewater by continuous electrocoagulation-flotation system with bipolar aluminum electrodes [J]. Sep. Purif. Technol., 2008, 60: 1 doi: 10.1016/j.seppur.2007.07.040
7	Zhang C W, Fu T L, Chen H Y, et al. Research progress on crevice corrosion, plasma nitriding and surface nanocrystallization of titanium alloys [J]. Surf. Technol., 2019, 48(11): 114
7	张乘玮, 付天琳, 陈涵悦等. 钛合金缝隙腐蚀、离子渗氮与表面纳米化的研究进展 [J]. 表面技术, 2019, 48(11): 114
8	Pang J J, Blackwood D J. Corrosion of titanium alloys in high temperature near anaerobic seawater [J]. Corros. Sci., 2016, 105: 17 doi: 10.1016/j.corsci.2015.12.011
9	Amrutha M S, Fasmin F, Ramanathan S. Effect of HF concentration on anodic dissolution of titanium [J]. J. Electrochem. Soc., 2017, 164: H188 doi: 10.1149/2.0501704jes
10	Wang Z B, Hu H X, Liu C B, et al. The effect of fluoride ions on the corrosion behavior of pure titanium in 0.05 M sulfuric acid [J]. Electrochim. Acta, 2014, 135: 526 doi: 10.1016/j.electacta.2014.05.055
11	Robin A, Meirelis J P. Influence of fluoride concentration and pH on corrosion behavior of titanium in artificial saliva [J]. J. Appl. Electrochem., 2007, 37: 511 doi: 10.1007/s10800-006-9283-z
12	Noel J J. The electrochemistry of titanium corrosion [D]. Winnipeg: University of Manitoba, 2000
13	Levy M. Anodic behavior of titanium and commercial alloys in sulfuric acid [J]. Corrosion, 1967, 23: 236 doi: 10.5006/0010-9312-23.8.236
14	Cobb J R, Uhlig H H. Resistance of titanium to sulfuric and hydrochloric acids inhibited by ferric and cupric ions [J]. J. Electrochem. Soc., 1952, 99: 13 doi: 10.1149/1.2779651
15	Stern M. The mechanism of passivating-type inhibitors [J]. J. Electrochem. Soc., 1958, 105: 638 doi: 10.1149/1.2428683
16	Liu Y, Schaller R F, Asselin E. Effect of Fe(III) and Cu(II) on the passivation of Ti-2 in acidic chloride solutions [J]. J. Electrochem. Soc., 2019, 166: C76 doi: 10.1149/2.1021902jes
17	Zhao P P, Song Y W, Shi L J, et al. Destruction of few fluorides to passive film of Ti-6Al-4V alloy under oxygen deficiency crevice conditions [J]. J. Mater. Sci., 2021, 56: 3510 doi: 10.1007/s10853-020-05456-y
18	Zhao P P, Song Y W, Dong K H, et al. Corrosion behavior of dual-phase Ti-6Al-4V alloys: A discussion on the impact of element Fe [J]. J. Alloys Compd., 2021, 858: 157708 doi: 10.1016/j.jallcom.2020.157708
19	Geng L, Qiao G Y, Gu K K. The effect of fluoride on electrochemical corrosion of the dental pure titanium before and after adhesion of Streptococcus mutans [J]. Shanghai J. Stomatol., 2016, 25: 150 pmid: 27329875
19	耿黎, 乔广艳, 顾凯凯. 氟对变形链球菌黏附前后纯钛表面腐蚀性能的影响 [J]. 上海口腔医学, 2016, 25: 150
20	Wang Z B. Study of the critical fluoride concentration for the corrosion of pure titanium and its protective measurements in desulfurized wet flue gas environment [D]. Shenyang: University of Chinese Academy of Sciences, 2017
20	王政彬. 脱硫湿烟气环境下纯钛腐蚀的临界氟离子浓度现象及防护措施研究 [D]. 沈阳: 中国科学院大学, 2017
21	Barão V, Mathew M T, Assunção W, et al. Stability of cp-Ti and Ti-6Al-4V alloy for dental implants as a function of saliva pH—An electrochemical study [J]. Clin. Oral Implants Res., 2012, 23: 1055 doi: 10.1111/clr.2012.23.issue-9
22	Li X F, Wu X F, Liu S W, et al. Effects of fluorine on photocatalysis [J]. Chin. J Catal., 2020, 41: 1451 doi: 10.1016/S1872-2067(20)63594-X
23	Huang H H. Effects of fluoride concentration and elastic tensile strain on the corrosion resistance of commercially pure titanium [J]. Biomaterials, 2002, 23: 59 doi: 10.1016/S0142-9612(01)00079-5
24	Yue G K, Zhao L M, Olvera O G, et al. Speciation of the H₂SO₄-Fe₂(SO₄)₃-FeSO₄-H₂O system and development of an expression to predict the redox potential of the Fe³⁺/Fe²⁺ couple up to 150^oC [J]. Hydrometallurgy, 2014, 147-148: 196 doi: 10.1016/j.hydromet.2014.05.008
25	Liang Y J, Che Y C. Handbook of Thermodynamics of Inogranic Substances [M]. Shenyang: Northeastern University Press, 1993: 616
25	梁英教, 车荫昌. 无机物热力学数据手册 [M]. 沈阳: 东北大学出版社, 1993: 616

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