钛合金钝化膜结构及钝化动力学机理研究进展

王泽政; 查小琴; 房坤; 孙晓栋; 徐阳; 罗先甫; 王佳; 孙绪鲁; 张欣耀

doi:10.16490/j.cnki.issn.1001-3660.2026.01.014

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表面技术 ›› 2026, Vol. 55 ›› Issue (1) : 157-176. DOI: 10.16490/j.cnki.issn.1001-3660.2026.01.014

装备表面工程

钛合金钝化膜结构及钝化动力学机理研究进展

王泽政¹, 查小琴^1,2,*, 房坤¹, 孙晓栋¹, 徐阳¹, 罗先甫¹, 王佳¹, 孙绪鲁¹, 张欣耀^1,2

作者信息 +

Research Progress on the Structure and Passivation Kinetic Mechanism of Titanium Alloy Passivation Films

WANG Zezheng¹, ZHA Xiaoqin^1,2,*, FANG Kun¹, SUN Xiaodong¹, XU Yang¹, LUO Xianfu¹, WANG Jia¹, SUN Xulu¹, ZHANG Xinyao^1,2

Author information +

文章历史 +

摘要

钛合金的优异耐蚀性得益于其良好的钝化及再钝化能力。在自然环境中,钛合金表面会自发形成一层纳米级钝化膜,其在遭受破坏后会快速修复,有效隔离基体与腐蚀介质的接触,显著提升材料耐蚀性;但在海洋工程等复杂的服役工况下,钝化膜的“溶解-成膜”动态过程对稳态膜结构有较大影响,从而决定其耐蚀性,为此,表征钛合金钝化膜结构并探究其在环境中的钝化动力学行为对于分析钛合金服役安全性、可靠性及优化钛合金耐蚀性具有重要意义。针对这一需求,本文首先综述了钛合金钝化膜结构表征技术研究现状,并在此基础上详述了钝化膜的厚度、组分、形貌表征及结构模型构建的最新研究成果;其次探讨了典型的金属动力学模型特点,包括高场模型、原子位置交换模型和点缺陷模型,总结出点缺陷模型是融合了微观粒子迁移机制和长程缺陷运动的物理模型,其理论框架更为完善;最后结合钛合金未来在海洋环境中推广应用需要,基于点缺陷模型分析了海洋环境用钛合金成分、组织以及氯离子、pH值、溶解氧含量、静水压力和温度等海洋环境主要因素对膜结构及耐蚀性影响规律,为分析钛合金在海洋环境中的钝化动力学行为及研究其耐蚀性提供理论支撑。

Abstract

Titanium alloy has become a critical material for upgrading engineering equipment due to its excellent corrosion resistance, high specific strength, superior fatigue performance and strong impact resistance, and its core corrosion resistance advantage is derived from the dynamic self-healing mechanism of the surface passivation film, namely good passivation and re-passivation capabilities. In natural environment, the surface atoms of titanium alloy will rapidly combine with oxygen and form a nanoscale passivation film through spontaneous passivation reactions to maintain a more stable thermodynamic state, which is mainly composed of densely arranged TiO₂. The film will quickly self-heal through a re-passivation process when it is damaged, and isolate the substrate from corrosive medium effectively, thereby significantly improving the corrosion resistance of the material. However, under complex service conditions such as those in marine engineering, aviation and aerospace, the "dissolution-formation" dynamic process of passivation film has significant effect on its steady-state film structure. That is, the dissolution and passivation processes occur simultaneously, and both of the two reaction rates jointly determine the actual state of the passivation film, thus determining the corrosion resistance. Therefore, characterizing the structure of titanium alloy passivation film and exploring the passivation kinetics behavior in the environment is of great significance for analyzing the safety and reliability of titanium alloys in service and optimizing the corrosion resistance of titanium alloys. The core support of materials research is characterization techniques, and its development level directly determines the depth of understanding of the essential laws of materials. In view of this, the current research status of the characterization techniques for the passivation film structure of titanium alloys is reviewed, the latest research results regarding the thickness, composition, morphology characterization, and physical structural model establishment of the passivation film is expounded, and the atomic/nanoscale analysis of the dynamic growth process and interface characteristics of passivation films is further conducted. Furthermore, based on the in-depth development of metal passivation theory, various kinetics models have become important tools for revealing the dynamic behavior of passivation films, systematically describing the dynamic laws during film formation, growth and destruction process. In recent years, the combination of passivation kinetics models with other theories has emerged as a prominent research hotspot. Researchers have attempted to integrate new elements on the basis of classical models, such as combining density functional theory (DFT), to reveal the microscopic process of passivation behavior at the atomic scale. The characteristics of typical metal kinetics models are also discussed, including High-Field Model, Atomic Position Exchange Model and Point Defect Model, and some of the new models developed thereby are briefly mentioned. The first two models mainly serve for initial stage models of the growth of passivation films, explaining the process of forming passivation films on the surface without a film, while the Point Defect Model is a physical model that integrates microscopic particle migration mechanism and long-range defect movement, describing the steady-state process of passivation films gradually increasing in thickness from the initial stage to dynamic equilibrium. Since the passivation process of titanium alloys is essentially the result of the synergistic effect of the material and the medium environment, researches also pay attention to the effect of two major dimensions that intrinsic properties of the material and the external environmental conditions on the passivation behavior of titanium alloys. Combined with the future application and promotion of titanium alloys in marine environment, the specific affecting factors are the material intrinsic parameters such as the elemental composition and microstructure morphology of titanium alloys for marine, as well as the marine environmental parameters. Therefore, the effect laws of the composition and microstructure of titanium alloys for marine engineering, as well as the major factors of marine environment such as chloride ions, pH value, dissolved oxygen content and hydrostatic pressure on passivation film structure and corrosion resistance are analyzed based on the point defect model. This provides theoretical support for studying the passivation kinetics behavior in marine environment and the corrosion resistance of titanium alloys.

导出引用

王泽政, 查小琴, 房坤, 孙晓栋, 徐阳, 罗先甫, 王佳, 孙绪鲁, 张欣耀. 钛合金钝化膜结构及钝化动力学机理研究进展[J]. 表面技术. 2026, 55(1): 157-176

WANG Zezheng, ZHA Xiaoqin, FANG Kun, SUN Xiaodong, XU Yang, LUO Xianfu, WANG Jia, SUN Xulu, ZHANG Xinyao. Research Progress on the Structure and Passivation Kinetic Mechanism of Titanium Alloy Passivation Films[J]. Surface Technology. 2026, 55(1): 157-176

中图分类号： TG174

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