钛合金表面铱 −钽涂层的耐强酸腐蚀性能

Strong acid corrosion resistance of iridium−tantalum coating on titanium alloy

摘要

[目的]探究铱−钽涂层的长效防护性能及其腐蚀产物层的形成机制，为苛刻环境下涂层钛合金的工程选材与寿命评估提供理论与实验依据。[方法]利用腐蚀仿真分析技术并结合真实的腐蚀实验验证，研究了不带涂层和带有铱−钽涂层的 TA2 钛合金在 4.5 mol/L 硫酸溶液中的腐蚀机制及腐蚀损伤演化规律。通过极化曲线测量，建立腐蚀数值模型的边界条件，模拟强酸环境下的电解液电流密度、电位分布及腐蚀厚度变化。采用扫描电镜(SEM)、能谱(EDS)等手段对不同腐蚀时间后的涂层表面进行表征，对比仿真及实验后的质量损失。[结果]铱−钽涂层显著提升了 TA2 钛合金的耐蚀性，使其腐蚀电位正移，腐蚀电流密度降低。TA2 在浸泡 1 d 后发生严重腐蚀穿孔，而涂层试件在相同条件下仅发生微米级腐蚀。涂层表面随浸泡时间延长而形成致密且稳定的腐蚀产物层，腐蚀速率趋缓并稳定在 0.341 g/(m ²·d)。[结论]铱−钽涂层不仅依靠高的电化学稳定性，更得益于长期腐蚀中形成的保护性产物层，从而具备优异的长效防护能力。本研究为苛刻环境下涂层钛合金的选材与寿命评估提供了实验与理论依据。

Abstract

[Objective] To investigate the long-term protective performance of iridium−tantalum coatings and the formation mechanism of their corrosion product layer, providing theoretical and experimental basis for material selection and life assessment of coated titanium alloys in harsh environments. [Method] Combining the corrosion simulation analysis with experimental verification, the corrosion mechanism and damage evolution of titanium-based alloy TA2 with and without iridium−tantalum coating in 4.5 mol/L sulfuric acid solution were studied. The electrolyte current density, potential distribution, and corrosion thickness variation in the strong acid environment were simulated based on the boundary conditions of the corrosion numerical model established by polarization curve measurement. The coating surface was characterized by scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) after different corrosion durations, and the mass loss data from simulation and experiment were compared. [Result] The iridium−tantalum coating significantly improved the corrosion resistance of TA2 titanium alloy, shifting its corrosion potential positively and reducing the corrosion current density. The uncoated TA2 underwent severe corrosion perforation after 1 day of immersion, while the coated specimen only experienced micron-scale corrosion under the same conditions. With the increasing of immersion time, a compact and stable corrosion product layer formed on the coating surface, and the corrosion rate gradually decreased and stabilized at 0.341 g/(m ²·d). [Conclusion] The iridium−tantalum coating exhibited excellent long-term protective performance, attributed not only to its high electrochemical stability but also to the protective product layer formed during long-term corrosion. This research provides experimental and theoretical support for material selection and life assessment of coated titanium alloys in harsh environments.

关键词

钛合金 / 铱−钽涂层 / 强酸腐蚀 / 仿真

Key words

titanium alloy / iridium–tantalum coating / strong acid corrosion / simulation

参考文献

[1] 李全龙, 陶媛媛, 王梦迪, 等. 全钒液流电池用关键材料技术指标特性需求分析和产业发展状况[J]. 储能科学与技术, 2025, 14(11): 4170-4183.

[2] LI Q L, TAO Y Y, WANG M D, et al. Technical indicator requirement analysis and industrial development status of key materials for vanadium flow battery[J]. Energy Storage Science and Technology, 2025, 14(11): 4170-4183.

[3] 胡飞飞, 王程, 王宝华, 等. 氨气气相还原法短程制备 3.5 价钒电解液[J]. 化工学报, 2025, 76(12): 6633-6643.

[4] HU F F, WANG C, WANG B H, et al. Preparation of 3.5-valent vanadium electrolyte via ammonia gas-phase reduction[J]. CIESC Journal, 2025, 76(12): 6633-6643.

[5] 胡超, 董玉明, 张伟, 等. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(增刊 1): 338-345.

[6] HU C, DONG Y M, ZHANG W, et al. Preparation of high-concentration positive electrolyte of vanadium redox flow battery by activating vanadium pentoxide with highly concentrated sulfuric acid[J]. CIESC Journal, 2023, 74(S1): 338-345.

[7] 毕俊, 柳小祥, 杨金梦, 等. SPE 电解水用钛双极板表面氮化物涂层的制备与评价[J]. 电镀与涂饰, 2020, 39(23): 1632-1637.

[8] BI J, LIU X X, YANG J M, et al. Preparation and evaluation of nitride coating on the surface of titanium bipolar plate for SPE water electrolysis[J]. Electroplating & Finishing, 2020, 39(23): 1632-1637.

[9] 单东方, 申桂鑫, 彭善龙, 等. 电泳沉积制备质子交换膜水电解用钛双极板氮化钛涂层[J]. 电镀与涂饰, 2022, 41(7): 497-501.

[10] SHAN D F, SHEN G X, PENG S L, et al. Electrophoretic deposition of TiN coating on titanium bipolar plate used for PEM water electrolysis[J]. Electroplating & Finishing, 2022, 41(7): 497-501.

[11] 高尚奇, 丁明玥, 梁潇, 等. 不同制备工艺对铂/钛双极板性能的影响[J]. 电镀与涂饰, 2025, 44(8): 102-106.

[12] GAO S Q, DING M Y, LIANG X, et al. Effect of different preparation method on properties of platinum/titanium bipolar plates[J]. Electroplating & Finishing, 2025, 44(8): 102-106.

[13] 范晨尧, 冯奇, 范洪强. 镀金双极板应用于质子交换膜燃料电池中的腐蚀失效分析[J]. 电镀与涂饰, 2020, 39(13): 850-854.

[14] FAN C Y, FENG Q, FAN H Q. Analysis on failure caused by corrosion of gold-coated bipolar plates applied to proton exchange membrane fuel cell[J]. Electroplating & Finishing, 2020, 39(13): 850-854.

[15] 冯芷晴, 罗凤盈, 罗浩秋, 等. PEMFC 耐蚀导电金属双极板涂层的研究进展[J/OL]. 中国表面工程, 2025−09−05. https://link.cnki.net/urlid/11.3905.TG.20250905.1523.004.

[16] FENG Z Q, LUO F Y, LUO H Q, et al. Research advances in corrosion-resistant and highly conductive coatings for metal bipolar plates in PEMFCs[J/OL]. China Surface Engineering, 2025−09−05. https://link.cnki.net/urlid/11.3905.TG.20250905.1523.004.

[17] 李涛, 张涵怡, 严义刚. PEMFC 钛双极板表面 TiCr/TiCrN 涂层性能的研究[J]. 表面技术, 2025, 54(16): 111-120.

[18] LI T, ZHANG H Y, YAN Y G. Performance of TiCr/TiCrN coatings on titanium bipolar plates for PEMFC[J]. Surface Technology, 2025, 54(16): 111-120.

[19] 卞贵学, 黄海亮, 魏梓林, 等. 酸性 NaCl 溶液下钛合金和钢镀镉−钛层的电偶腐蚀仿真与验证[J/OL]. 中国表面工程, 2025−06−04. https://link.cnki.net/urlid/11.3905.TG.20250603.1622.002.

[20] BIAN G X, HUANG H L, WEI Zi L, et al. Galvanic corrosion simulation and verification of cadmium-titanium coating plated on titanium alloy and steel in acidic NaCl solution[J/OL]. China Surface Engineering, 2025−06−04. https://link.cnki.net/urlid/11.3905.TG.20250603.1622.002.

[21] WERNER J M, ZENG W, FREE M L, et al. Modeling and validation of local electrowinning electrode current density using two phase flow and Nernst-Planck equations[J]. Journal of the Electrochemical Society, 2018, 165(5): 190-207.

[22] 陈嘉冀, 刘月晨, 崔嘉豪, 等. 阴离子交换膜电解水制氢双极板表面TiC_xN_1−x 导电涂层性能研究 [J]. 电镀与涂饰, 2026, 45(1): 108-114.

[23] CHEN J J, LIU Y C, CUI J H, et al. Properties of TiC_xN_1−x conductive coating on bipolar plate for anion exchange membrane water electrolysis [J]. Electroplating & Finishing, 2026, 45(1): 108-114.

[24] 裴锋, 贾蕗路, 田旭, 等. 镍含量对铜铝镍合金接地材料显微组织及耐腐蚀性能的影响[J]. 电镀与涂饰, 2026, 45(1): 129-138.

[25] PEI F, JIA L L, TIAN X, et al. Effect of nickel content on microstructure and corrosion resistance of Cu−Al−Ni alloy grounding material[J]. Electroplating & Finishing, 2026, 45(1): 129-138.

基金资助

中国电气装备集团科学技术项目──钒电解液电解技术提升实验平台和 500 kW 液流储能实证平台建设(5191BG25009)