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

WANG Zezheng; ZHA Xiaoqin; FANG Kun; SUN Xiaodong; XU Yang; LUO Xianfu; WANG Jia; SUN Xulu; ZHANG Xinyao

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

PDF(11931 KB)

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

Equipment Surface Engineering

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 +

History +

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.

Key words

titanium alloy / passivation film / passivation kinetics mechanism / corrosion resistance / marine environment

Cite this article

EndNote

Ris (Procite)

Bibtex

Download Citations

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

References

[1] REVIE R W.Uhlig’s Corrosion Handbook[M]. Hoboken: Wiley, 2011.
[2] CARLEY A F, CHALKER P R, RIVIERE J C, et al.The Identification and Characterisation of Mixed Oxidation States at Oxidised Titanium Surfaces by Analysis of X-Ray Photoelectron Spectra[J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1987, 83(2): 351.
[3] POUILLEAU J, DEVILLIERS D, GARRIDO F, et al.Structure and Composition of Passive Titanium Oxide Films[J]. Materials Science and Engineering: B, 1997, 47(3): 235-243.
[4] MARCUS P.Corrosion Mechanisms in the Theory and Practice[M]. New York: Marcel Dekker Inc., 2002.
[5] 李金龙, 赖思颖, 董敏鹏. 海洋环境钛金属的应用现状及其防护技术研究[J]. 表面技术, 2023, 52(5): 1-13.
LI J L, LAI S Y, DONG M P.Application Status and Corresponding Protection Technology of Titanium Alloy in Marine Environment[J]. Surface Technology, 2023, 52(5): 1-13.
[6] BOYER R R.An Overview on the Use of Titanium in the Aerospace Industry[J]. Materials Science and Engineering: A, 1996, 213(1/2): 103-114.
[7] 蒋成禹, 赵勇. 钛材在海军工程中的应用及需要解决的问题[J]. 中国材料进展, 2010, 29(5): 25-29.
JIANG C Y, ZHAO Y.Titanium in Navy Engineering Applications and Problems to Be Solved[J]. Materials China, 2010, 29(5): 25-29.
[8] 于宇, 李嘉琪. 国内外钛合金在海洋工程中的应用现状与展望[J]. 材料开发与应用, 2018, 33(3): 111-116.
YU Y, LI J Q.Current Application and Prospect of Titanium Alloys in Marine Engineering[J]. Development and Application of Materials, 2018, 33(3): 111-116.
[9] WANG L, WANG S Y.Quantitative Analysis of Self- Healing Properties and Microstructure of Ti-5Al-5Mo- 5V-1Cr-1Fe Alloy by Quasi-in-Situ XPS[J]. Journal of Alloys and Compounds, 2025, 1012: 178509.
[10] 张雅妮, 王思敏, 樊冰. TC4钛合金在O₂+CO₂气氛的高温高压模拟水沉积液中表面形成的钝化膜研究[J]. 中国腐蚀与防护学报, 2024, 44(6): 1518-1528.
ZHANG Y N, WANG S M, FAN B.Corrosion and Passivation Behavior of TC4 Ti-Alloy in a Simulated Downhole Liquid in High-Temperature and High-Pressed O₂+CO₂ Environment[J]. Journal of Chinese Society for Corrosion and Protection, 2024, 44(6): 1518-1528.
[11] CHEN J, ZHANG Q.Effect of Electrochemical State on Corrosion-Wear Behaviors of TC4 Alloy in Artificial Seawater[J]. Transactions of Nonferrous Metals Society of China, 2016, 26(4): 1011-1018.
[12] BRIGGS D, SEAH M P.Surface Analysis Techniques[M]. Chichester: Wiley, 1990: 35-78.
[13] SMITH J.Passive Films and Their Breakdown[M]. New York: Springer, 2012: 120-150.
[14] 唐占梅, 郭伟, 蒋榕培, 等. 工业纯钛TA2在液体推进剂单推-3中的耐蚀机理[J]. 中国表面工程, 2023, 36(5): 123-130.
TANG Z M, GUO W, JIANG R P, et al.Corrosion- Resistance Mechanism of Commercially Pure Titanium TA2 in Liquid Propellant DT-3[J]. China Surface Engineering, 2023, 36(5): 123-130.
[15] WANG L, YU H Y, WANG S Y, et al.In-Situ XAFS and SERS Study of Self-Healing of Passive Film on Ti in Hank's Physiological Solution[J]. Applied Surface Science, 2019, 496: 143657.
[16] KOTNALA R K, SHAH J, MATHPAL M C, et al.Influence of Annealing on Humidity Response of RF Sputtered Nanocrystalline MgFe₂O₄ Thin Films[J]. Thin Solid Films, 2011, 519(18): 6135-6139.
[17] 高尚. 纳米尺度薄膜的制备及其光学性质的椭偏研究[D]. 济南: 山东大学, 2013.
GAO S.Deposition of Nanoscale Films and Ellipsomctry Study[D]. Jinan: Shandong University, 2013.
[18] VAN GILS S, MAST P, STIJNS E, et al.Colour Properties of Barrier Anodic Oxide Films on Aluminium and Titanium Studied with Total Reflectance and Spectroscopic Ellipsometry[J]. Surface and Coatings Technology, 2004, 185(2/3): 303-310.
[19] ROH B, MACDONALD D D.The Passivity of Titanium: PartⅢ: Characterization of the Anodic Oxide Film[J]. Journal of Solid State Electrochemistry, 2019, 23(7): 2001-2008.
[20] BOTHA S J.Surface Properties and Bio-Acceptability of Ti₂O₃ Surfaces[J]. Materials Science and Engineering: A, 1998, 243(1/2): 221-230.
[21] MCCAFFERTY E, WIGHTMAN J P.An X-Ray Photoelectron Spectroscopy Sputter Profile Study of the Native Air-Formed Oxide Film on Titanium[J]. Applied Surface Science, 1999, 143(1/2/3/4): 92-100.
[22] EDA Y, MANAKA T, HANAWA T, et al.X-Ray Photoelectron Spectroscopy-Based Valence Band Spectra of Passive Films on Titanium[J]. Surface and Interface Analysis, 2022, 54(8): 892-898.
[23] XU H S, WANG L, SUN D B, et al.The Passive Oxide Films Growth on 316L Stainless Steel in Borate Buffer Solution Measured by Real-Time Spectroscopic Ellipsometry[J]. Applied Surface Science, 2015, 351: 367-373.
[24] 钟世德, 王书运. 材料表面分析技术综述[J]. 山东轻工业学院学报(自然科学版), 2008, 22(2): 59-64.
ZHONG S D, WANG S Y.The Summany of Analytical Technology of Material Surface[J]. Journal of Shandong Institute of Light Industry (Natural Science Edition), 2008, 22(2): 59-64.
[25] 黄惠忠. 表面化学分析[M]. 上海: 华东理工大学出版社, 2007.
HUANG H Z.Surface Chemical Analysis[M]. Shanghai: East China University of Science and Technology Press, 2007.
[26] MILOŠEV I, METIKOŠ-HUKOVIĆ M, STREHBLOW H H. Passive Film on Orthopaedic TiAlV Alloy Formed in Physiological Solution Investigated by X-Ray Photoelectron Spectroscopy[J]. Biomaterials, 2000, 21(20): 2103-2113.
[27] GAI X, BAI Y, LI J, et al.Electrochemical Behaviour of Passive Film Formed on the Surface of Ti-6Al-4V Alloys Fabricated by Electron Beam Melting[J]. Corrosion Science, 2018, 145: 80-89.
[28] ONG J L, LUCAS L C, RAIKAR G N, et al.Spectroscopic Characterization of Passivated Titanium in a Physiologic Solution[J]. Journal of Materials Science: Materials in Medicine, 1995, 6(2): 113-119.
[29] ZHANG R, AI X, WAN Y, et al.Surface Corrosion Resistance in Turning of Titanium Alloy[J]. International Journal of Corrosion, 2015, 2015: 823172.
[30] 张录平, 李晖, 刘亚平. 俄歇电子能谱仪在材料分析中的应用[J]. 分析仪器, 2009(4): 14-17.
ZHANG L P, LI H, LIU Y P.Applications of Auger Electron Spectrometer in Material Analysis[J]. Analytical Instrumentation, 2009(4): 14-17.
[31] TANAKA Y, NAKAI M, AKAHORI T, et al.Characterization of Air-Formed Surface Oxide Film on Ti-29Nb-13Ta-4.6Zr Alloy Surface Using XPS and AES[J]. Corrosion Science, 2008, 50(8): 2111-2116.
[32] HEALY K E, DUCHEYNE P.The Mechanisms of Passive Dissolution of Titanium in a Model Physiological Environment[J]. Journal of Biomedical Materials Research, 1992, 26(3): 319-338.
[33] OSWALD S, GOSTIN P F, HELTH A, et al.XPS and AES Sputter-Depth Profiling at Surfaces of Biocompatible Passivated Ti-Based Alloys: Concentration Quantification Considering Chemical Effects[J]. Surface and Interface Analysis, 2014, 46(10/11): 683-688.
[34] DAVENPORT A J, ISAACS H S, BARDWELL J A, et al.In Situ Studies of Passive Film Chemistry Using X-Ray Absorption Spectroscopy[J]. Corrosion Science, 1993, 35(1/2/3/4): 19-25.
[35] WANG L, YU H Y, WANG K, et al.Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium[J]. ACS Applied Materials & Interfaces, 2016, 8(28): 18608-18619.
[36] WANG L, YU H Y, WANG S Y, et al.Quantitative Analysis of Local Fine Structure on Diffusion of Point Defects in Passive Film on Ti[J]. Electrochimica Acta, 2019, 314: 161-172.
[37] LÓPEZ M F, SORIANO L, PALOMARES F J, et al. Soft X-Ray Absorption Spectroscopy Study of Oxide Layers on Titanium Alloys[J]. Surface and Interface Analysis, 2002, 33(7): 570-576.
[38] THAIR L, KAMACHI MUDALI U, RAJAGOPALAN S, et al.Surface Characterization of Passive Film Formed on Nitrogen Ion Implanted Ti-6Al-4V and Ti-6Al-7Nb Alloys Using SIMS[J]. Corrosion Science, 2003, 45(9): 1951-1967.
[39] 周强, 李金英, 梁汉东, 等. 二次离子质谱(SIMS)分析技术及应用进展[J]. 质谱学报, 2004, 25(2): 113-120.
ZHOU Q, LI J Y, LIANG H D, et al.Recent Developments on Secondary Ion Mass Spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2004, 25(2): 113-120.
[40] DE WITTE H, CONARD T, VANDERVORST W, et al.Ion-Bombardment Artifact in TOF-SIMS Analysis of ZrO₂/SiO₂/Si Stacks[J]. Applied Surface Science, 2003, 203: 523-526.
[41] HOFMANN S.Profile Reconstruction in Sputter Depth Profiling[J]. Thin Solid Films, 2001, 398: 336-342.
[42] WILKE M, TEICHERT G, GEMMA R, et al.Glow Discharge Optical Emission Spectroscopy for Accurate and Well Resolved Analysis of Coatings and Thin Films[J]. Thin Solid Films, 2011, 520(5): 1660-1667.
[43] SUL Y T, JOHANSSON C B, RÖSER K, et al. Qualitative and Quantitative Observations of Bone Tissue Reactions to Anodised Implants[J]. Biomaterials, 2002, 23(8): 1809-1817.
[44] KUMAR S, SANKARA NARAYANAN T S N, GANESH SUNDARA RAMAN S, et al. Thermal Oxidation of Ti6Al4V Alloy: Microstructural and Electrochemical Characterization[J]. Materials Chemistry and Physics, 2010, 119(1/2): 337-346.
[45] LIU R, CUI Y, ZHANG B, et al.Unveiling the Effect of Hydrostatic Pressure on the Passive Films of the Deformed Titanium Alloy[J]. Corrosion Science, 2021, 190: 109705.
[46] LIU R, XIE Y S, JIN Y, et al.Stress Corrosion Cracking of the Titanium Alloys under Hydrostatic Pressure Resulting from the Degradation of Passive Films[J]. Acta Materialia, 2023, 252: 118946.
[47] BLACKWOOD D J, GREEF R, PETER L M.An Ellipsometric Study of the Growth and Open-Circuit Dissolution of the Anodic Oxide Film on Titanium[J]. Electrochimica Acta, 1989, 34(6): 875-880.
[48] PANKUCH M, BELL R, MELENDRES C A.Composition and Structure of the Anodic Films on Titanium in Aqueous Solutions[J]. Electrochimica Acta, 1993, 38(18): 2777-2779.
[49] POUILLEAU J, DEVILLIERS D, GARRIDO F, et al.Structure and Composition of Passive Titanium Oxide Films[J]. Materials Science and Engineering: B, 1997, 47(3): 235-243.
[50] ZHU Y C.Electrochemical and Surface Analysis of Anodic Oxide Film on Titanium and Stochastic Analysis of Pit Generation Processes on Anodized Titanium[D]. Osaka: The University of Osaka, 1995.
[51] EL-BASIOUNY M S, MAZHAR A A. Electrochemical Behavior of Passive Layers on Titanium[J]. Corrosion, 1982, 38(5): 237-240.
[52] ROH B, MACDONALD D D.Passivity of Titanium: PartⅡ, the Defect Structure of the Anodic Oxide Film[J]. Journal of Solid State Electrochemistry, 2019, 23(7): 1967-1979.
[53] 张雅妮, 王思敏, 樊冰. TC4钛合金在O2+CO₂气氛的高温高压模拟水沉积液中表面形成的钝化膜研究[J]. 中国腐蚀与防护学报, 2024, 44(6): 1518-1528.
ZHANG Y N, WANG S M, FAN B.Corrosion and Passivation Behavior of TC4 Ti-Alloy in a Simulated Downhole Liquid in High-Temperature and High-Pressed O₂+CO₂ Environment[J]. Journal of Chinese Society for Corrosion and Protection, 2024, 44(6): 1518-1528.
[54] 郭荻子, 杨英丽, 赵彬, 等. 钛在沸腾硝酸介质中腐蚀表面的分析[J]. 中国有色金属学报, 2010, 20(S1): 881-885.
GUO D Z, YANG Y L, ZHAO B, et al.Analysis of the Corrosion Surface of Titanium in Boiling Nitric Acid Medium[J]. The Chinese Journal of Nonferrous Metals, 2010, 20(S1): 881-885.
[55] 郭荻子, 杨英丽, 赵彬, 等. Ti35合金在沸腾硝酸中钝化膜及过渡层形成及组成分析[J]. 钛工业进展, 2015, 32(1): 38-41.
GUO D Z, YANG Y L, ZHAO B, et al.Passive Film and Transition Layer on Ti35 Alloy after Exposure to Boiling Nitric Acid Solution[J]. Titanium Industry Progress, 2015, 32(1): 38-41.
[56] 王光耀, 王浩. 钛钼合金在盐酸溶液中形成的钝化膜研究[J]. 中国腐蚀与防护学报, 1997, 17(2): 121-128.
WANG G Y, WANG H.A Study of Passive Films Formed on Ti-15Mo Alloy in HCl Solutions[J]. Journal of Chinese Society for Corrosion and Protection, 1997, 17(2): 121-128.
[57] OHTSUKA T, NISHIKATA A, SAKAIRI M, et al.Electrochemistry for Corrosion Fundamentals[M]. Singapore: Springer Singapore, 2018.
[58] 刘鑫鑫, 崔雨薇, 姚增健, 等. 钛合金表面钝化膜特性及其生长机理研究评述[J]. 江苏科技大学学报(自然科学版), 2022, 36(1): 26-31.
LIU X X, CUI Y W, YAO Z J, et al.Review on the Properties of Passive Films Formed on Titanium Alloys[J]. Journal of Jiangsu University of Science and Technology (Natural Science Edition), 2022, 36(1): 26-31.
[59] 滕琳琳, 陈永君, 钟嘉彬, 等. 增强不锈钢表面耐蚀性的研究进展[J]. 辽宁科技大学学报, 2021, 44(4): 320.
TENG L L, CHEN Y J, ZHONG J B, et al.Research Progress on Corrosion Resistance Enhancement of Stainless Steel[J]. Journal of University of Science and Technology Liaoning, 2021, 44(4): 320.
[60] 曹楚南. 腐蚀电化学原理[M]. 第3版. 北京: 化学工业出版社, 2008.
CAO C N.Principles of Electrochemistry of Corrosion [M]. 3rd Edition. Beijing: Chemical Industry Press, 2008.
[61] MOTT N F.The Theory of the Formation of Protective Oxide Films on Metals, Ⅱ[J]. Transactions of the Faraday Society, 1940, 35: 472.
[62] ELEY D D, WILKINSON P R.Adsorption and Oxide Formation on Aluminium Films[J]. Proceedings of the Royal Society of London Series A, Mathematical and Physical Sciences, 1960, 254(1278): 327-342.
[63] MACDONALD D D.Some Personal Adventures in Passivity—A Review of the Point Defect Model for Film Growth[J]. Russian Journal of Electrochemistry, 2012, 48(3): 235-258.
[64] CABRERA N, MOTT N F.Theory of the Oxidation of Metals[J]. Reports on Progress in Physics, 1949, 12(1): 163.
[65] BURSTEIN G T, NEWMAN R C.Anodic Behaviour of Scratched Silver Electrodes in Alkaline Solution[J]. Electrochimica Acta, 1980, 25(8): 1009-1013.
[66] VETTER K J.Das Elektrische Feld Innerhalb Der Passivschicht des Eisens[J]. Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft für Physikalische Chemie, 1954, 58(4): 230-237.
[67] WEIL K G.Die Beziehung Zwischen Ionenstrom Und Spannung Innerhalb Der Oxydschicht Auf Passivem Eisen[J]. Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft für Physikalische Chemie, 1955, 59(7/8): 711-715.
[68] LOHRENGEL M M.Thin Anodic Oxide Layers on Aluminium and Other Valve Metals: High Field Regime[J]. Materials Science and Engineering: R: Reports, 1993, 11(6): 243-294.
[69] ZHANG L, MACDONALD D D, SIKORA E, et al.On the Kinetics of Growth of Anodic Oxide Films[J]. Journal of the Electrochemical Society, 1998, 145(3): 898-905.
[70] ELLERBROCK D, MACDONALD D D.Passivity of Titanium, Part 1: Film Growth Model Diagnostics[J]. Journal of Solid State Electrochemistry, 2014, 18(5): 1485-1493.
[71] MAO F X, LU P, MACDONALD D.Diagnosis of the Mechanism of Anodic Oxide FilmGrowth on Platinum in KOH[J]. Zeitschrift für Physikalische Chemie, 2016, 230(1): 79-95.
[72] TOOR I U H, PARK K J, KWON H. Manganese Effects on Repassivation Kinetics and SCC Susceptibility of High Mn-N Austenitic Stainless Steel Alloys[J]. Journal of the Electrochemical Society, 2007, 154(9): C494.
[73] ELEY D D, WILKINSON P R.Adsorption and Oxide Formation on Aluminium Films[J]. Proceedings of the Royal Society of London Series A, Mathematical and Physical Sciences, 1960, 254(1278): 327-342.
[74] SATO N, COHEN M.The Kinetics of Anodic Oxidation of Iron in Neutral Solution[J]. Journal of the Electrochemical Society, 1964, 111(5): 512.
[75] CHO E A, KIM C K, KIM J S, et al.Quantitative Analysis of Repassivation Kinetics of Ferritic Stainless Steels Based on the High Field Ion Conduction Model[J]. Electrochimica Acta, 2000, 45(12): 1933-1942.
[76] WANG J Z, HAN E H, WANG J Q.The Repassivation Kinetics Study of Alloy 800 in High-Temperature Pressurized Water[J]. Electrochemistry Communications, 2015, 60: 100-103.
[77] FEHLNER F P, MOTT N F.Low-Temperature Oxidation[J]. Oxidation of Metals, 1970, 2(1): 59-99.
[78] CHAO C Y, LIN L F, MACDONALD D D.A Point Defect Model for Anodic Passive Films: I. Film Growth Kinetics[J]. Journal of the Electrochemical Society, 1981, 128(6): 1187-1194.
[79] MACDONALD D D.The History of the Point Defect Model for the Passive State: A Brief Review of Film Growth Aspects[J]. Electrochimica Acta, 2011, 56(4): 1761-1772.
[80] MACDONALD D D.The Point Defect Model for the Passive State[J]. Journal of the Electrochemical Society, 1992, 139(12): 3434-3449.
[81] MACDONALD D D.Passivity—The Key to Our Metals- Based Civilization[J]. Pure and Applied Chemistry, 1999, 71(6): 951-978.
[82] MACDONALD D D, AL RIFAIE M, ENGELHARDT G R.New Rate Laws for the Growth and Reduction of Passive Films[J]. Journal of the Electrochemical Society, 2001, 148(9): B343.
[83] ZHANG L, MACDONALD D D, SIKORA E, et al.On the Kinetics of Growth of Anodic Oxide Films[J]. Journal of the Electrochemical Society, 1998, 145(3): 898-905.
[84] NAGY T O, WEIMERSKIRCH M J J, PACHER U, et al. Repassivation Investigations on Aluminium: Physical Chemistry of the Passive State[J]. Zeitschrift für Physikalische Chemie, 2016, 230(9): 1303-1327.
[85] 黄建中, 左禹. 材料的耐蚀性和腐蚀数据[M]. 北京: 化学工业出版社, 2003.
HUANG J Z, ZUO Y.Corrosion Resistance and Corrosion Data of Materials[M]. Beijing: Chemical Industry Press, 2003.
[86] 付艳艳, 宋月清, 惠松骁, 等. 航空用钛合金的研究与应用进展[J]. 稀有金属, 2006, 30(6): 850-856.
FU Y Y, SONG Y Q, HUI S X, et al.Research and Application of Typical Aerospace Titanium Alloys[J]. Chinese Journal of Rare Metals, 2006, 30(6): 850-856.
[87] NAJAFIZADEH M, YAZDI S, BOZORG M, et al.Classification and Applications of Titanium and Its Alloys: A Review[J]. Journal of Alloys and Compounds Communications, 2024, 3: 100019.
[88] 柳皓晨, 范林, 张海兵, 等. 钛合金深海应力腐蚀研究进展[J]. 中国腐蚀与防护学报, 2022, 42(2): 175-185.
LIU H C, FAN L, ZHANG H B, et al.Research Progress of Stress Corrosion Cracking of Ti-Alloy in Deep Sea Environments[J]. Journal of Chinese Society for Corrosion and Protection, 2022, 42(2): 175-185.
[89] PERINI N, CORRADINI P G, NASCIMENTO V P, et al.Characterization of AISI 1005 Corrosion Films Grown under Cyclic Voltammetry of Low Sulfide Ion Concentrations[J]. Corrosion Science, 2013, 74: 214-222.
[90] YANG X J, DU C W, WAN H X, et al.Influence of Sulfides on the Passivation Behavior of Titanium Alloy TA2 in Simulated Seawater Environments[J]. Applied Surface Science, 2018, 458: 198-209.
[91] 刘二勇, 曾志翔, 赵文杰. 海水环境中金属材料腐蚀磨损及耐磨防腐一体化技术的研究进展[J]. 表面技术, 2017, 46(11): 149-157.
LIU E Y, ZENG Z X, ZHAO W J.Corrosive Wear and Integrated Anti-Wear & Anti-Corrosion Technology Metallic Materials in Seawater[J]. Surface Technology, 2017, 46(11): 149-157.
[92] CUI Y W, CHEN L Y, QIN P, et al.Metastable Pitting Corrosion Behavior of Laser Powder Bed Fusion Produced Ti-6Al-4V in Hank’s Solution[J]. Corrosion Science, 2022, 203: 110333.
[93] TAN H, CHEN J, ZHANG F Y, et al.Microstructure and Mechanical Properties of Laser Solid Formed Ti-6Al-4V from Blended Elemental Powders[J]. Rare Metal Materials and Engineering, 2009, 38(4): 574-578.
[94] LIU R, HUI S X, YE W J, et al.Dynamic Stress-Strain Properties of Ti-Al-V Titanium Alloys with Various Element Contents[J]. Rare Metals, 2013, 32(6): 555-559.
[95] 常辉, 董月成, 淡振华, 等. 我国海洋工程用钛合金现状和发展趋势[J]. 中国材料进展, 2020, 39(7): 585-590.
CHANG H, DONG Y C, DAN Z H, et al.Current Status and Development Trend of Titanium Alloy for Marine Engineering in China[J]. Materials China, 2020, 39(7): 585-590.
[96] YU S Y, BRODRICK C W, RYAN M P, et al.Effects of Nb and Zr Alloying Additions on the Activation Behavior of Ti in Hydrochloric Acid[J]. Journal of the Electrochemical Society, 1999, 146(12): 4429-4438.
[97] XIA C Q, ZHANG Z G, FENG Z H, et al.Effect of Zirconium Content on the Microstructure and Corrosion Behavior of Ti-6Al-4V-xZr Alloys[J]. Corrosion Science, 2016, 112: 687-695.
[98] ZHANG Y, DAVENPORT A J, BURKE B, et al.Effect of Zr Addition on the Corrosion of Ti in Acidic and Reactive Oxygen Species (ROS)-Containing Environments[J]. ACS Biomaterials Science & Engineering, 2018, 4(3): 1103-1111.
[99] MARTINS D Q, OSÓRIO W R, SOUZA M E P, et al. Effects of Zr Content on Microstructure and Corrosion Resistance of Ti-30Nb-Zr Casting Alloys for Biomedical Applications[J]. Electrochimica Acta, 2008, 53(6): 2809-2817.
[100] 王清瑞. Ti-Al-V系钛合金钝化行为及其影响因素的实验研究[D]. 北京: 北京科技大学, 2023.
WANG Q R.Experimental Investigation on Passivation Behavior of Ti-Al-V Titanium Alloys and Its Influencing Factors[D]. Beijing: University of Science and Technology Beijing, 2023.
[101] LEE W H, HYUN C Y.XPS Study of Porous Dental Implants Fabricated by Electro-Discharge-Sintering of Spherical Ti-6Al-4V Powders in a Vacuum Atmosphere[J]. Applied Surface Science, 2006, 252(12): 4250-4256.
[102] HUANG F F, QIN Y, WANG Q R, et al.Insight into Relationship between Composition, Thickness and Electrochemistry Behavior of Oxide Film Formed on TA15 under Different Potentials in 0.5 mol/L H₂SO₄[J]. Rare Metals, 2023, 42(5): 1760-1772.
[103] HUANG F F, QIN Y, ZHANG H B, et al.Potential Dependent Mechanism of the Composition and Electrochemical Property of Oxide Films of Ti-6Al-3Nb-2Zr- 1Mo[J]. Corrosion Science, 2023, 213: 110978.
[104] WANG S H, WEI W, GAO Y H, et al.Characterization of Ti-Zr-V Thin Films Deposited by DC and Unipolar Pulsed DC Magnetron Sputtering[J]. Vacuum, 2021, 188: 110200.
[105] FRAYRET J P, CAPRANI A, JASZAY T, et al.Influence of Aluminum and Vanadium on the Anodic Dissolution of Ti-Al and Ti-V Binary Alloys in Concentrated Hydrochloric Acid[J]. Corrosion, 1985, 41(11): 656-664.
[106] 吴俊宇, 徐建平, 刘后龙, 等. 合金元素对Ti-5Ta合金耐硝酸腐蚀性能的影响[J]. 钛工业进展, 2023, 40(4): 13-18.
WU J Y, XU J P, LIU H L, et al.Effect of Alloying Elements on Nitric Acid Corrosion Resistance of Ti-5Ta Alloy[J]. Titanium Industry Progress, 2023, 40(4): 13-18.
[107] 屈定荣, 武显亮, 王光耀. XPS研究Ti32Mo在浓盐酸溶液中钝化膜结构[J]. 腐蚀科学与防护技术, 2003, 15(3): 130-133.
QU D R, WU X L, WANG G Y.XPS Studies on Passive Films Formed on Ti32Mo Alloy in HCl Solution[J]. Corrosion Science and Protection Technology, 2003, 15(3): 130-133.
[108] LEE E B, HAN M K, KIM B J, et al.Effect of Molybdenum on the Microstructure, Mechanical Properties and Corrosion Behavior of Ti Alloys[J]. International Journal of Materials Research, 2014, 105(9): 847-853.
[109] ZHAO H, XIE L F, XIN C, et al.Effect of Molybdenum Content on Corrosion Resistance and Corrosion Behavior of Ti-Mo Titanium Alloy in Hydrochloric Acid[J]. Materials Today Communications, 2023, 34: 105032.
[110] TANJI A, GAPSARI F, SYAHROM A, et al.Effect of Mo Addition on the Pitting Resistance of TiMn Alloys in Hanks' Solution[J]. Journal of Alloys and Compounds, 2021, 871: 159582.
[111] YANG J Y, SONG Y W, DONG K H, et al.Research Progress on the Corrosion Behavior of Titanium Alloys[J]. Corrosion Reviews, 2023, 41(1): 5-20.
[112] HU B, JIN C G, XIE J, et al.Experimental Investigation and Calphad Modeling of Thermal Conductivities of the Cu-Ag-Cr-Zr System[J]. Materials Today Physics, 2024, 46: 101502.
[113] 王乐, 易丹青, 刘会群, 等. Ru对Ti-6Al-4V合金腐蚀行为的影响及机理研究[J]. 中国腐蚀与防护学报, 2020, 40(1): 25-30.
WANG L, YI D Q, LIU H Q, et al.Effect of Ru on Corrosion Behavior of Ti-6Al-4V Alloy and Its Mechanism[J]. Journal of Chinese Society for Corrosion and Protection, 2020, 40(1): 25-30.
[114] 赵平平. 钝化膜对钛合金不同腐蚀形态的影响机制研究[D]. 合肥: 中国科学技术大学, 2021.
ZHAO P P.Study on the Influence of Passive Film on Different Corrosion Forms of Titanium Alloys[D]. Hefei: University of Science and Technology of China, 2021.
[115] ZHAO H, XIE L F, XIN C, et al.Effect of Molybdenum Content on Corrosion Resistance and Corrosion Behavior of Ti-Mo Titanium Alloy in Hydrochloric Acid[J]. Materials Today Communications, 2023, 34: 105032.
[116] TANJI A, GAPSARI F, SYAHROM A, et al.Effect of Mo Addition on the Pitting Resistance of TiMn Alloys in Hanks' Solution[J]. Journal of Alloys and Compounds, 2021, 871: 159582.
[117] 刘俪. 钛合金显微组织对其超声参量及耐蚀性能的影响[D]. 南昌: 南昌航空大学, 2012.
LIU L.Influence of Microstructures of Titanium Alloy on Ultrasound Parameters and Corrosion-Resistance[D]. Nanchang: Nanchang Hangkong University, 2012.
[118] 董京京. 钛合金钝化膜深海耐蚀性及裂纹尖端溶解与自愈合行为研究[D]. 哈尔滨: 哈尔滨工程大学, 2020.
DONG J J.Research on Deep Sea Corrosion Resistance and Crack Tip Dissolution and Self-Healing Behavior of Passive Film of Titanium Alloy[D]. Harbin: Harbin Engineering University, 2020.
[119] MYTHILI R, RAVI SHANKAR A, SAROJA S, et al.Influence of Microstructure on Corrosion Behavior of Ti-5%Ta-1.8%Nb Alloy[J]. Journal of Materials Science, 2007, 42(15): 5924-5935.
[120] WEI Y, PAN Z M, FU Y, et al.Effect of Annealing Temperatures on Microstructural Evolution and Corrosion Behavior of Ti-Mo Titanium Alloy in Hydrochloric Acid[J]. Corrosion Science, 2022, 197: 110079.
[121] YANG Y H, XIA C Q, FENG Z H, et al.Corrosion and Passivation of Annealed Ti-20Zr-6.5Al-4V Alloy[J]. Corrosion Science, 2015, 101: 56-65.
[122] 郭为民, 李文军, 陈光章. 材料深海环境腐蚀试验[J]. 装备环境工程, 2006, 3(1): 10-15.
GUO W M, LI W J, CHEN G Z.Corrosion Testing in the Deep Ocean[J]. Equipment Environmental Engineering, 2006, 3(1): 10-15.
[123] MA F Y.Corrosive Effects of Chlorides on Metals[M]. NewYork: InTech, 2012.
[124] 刘贵立. 钛的腐蚀与钝化机理电子理论研究[J]. 物理学报, 2008, 57(7): 4441-4445.
LIU G L.Electronic Theoretical Study on the Corrosion and Passivation Mechanism of Ti Metal[J]. Acta Physica Sinica, 2008, 57(7): 4441-4445.
[125] MUNIRATHINAM B, NARAYANAN R, NEELAKANTAN L.Electrochemical and Semiconducting Properties of Thin Passive Film Formed on Titanium in Chloride Medium at Various pH Conditions[J]. Thin Solid Films, 2016, 598: 260-270.
[126] JIANG Z L, DAI X, MIDDLETON H.Investigation on Passivity of Titanium under Steady-State Conditions in Acidic Solutions[J]. Materials Chemistry and Physics, 2011, 126(3): 859-865.
[127] 李波. 新型高强韧高耐蚀Ti6Al7Nb-xZr生物医用合金的制备及组织和性能[D]. 秦皇岛: 燕山大学, 2023.
LI B. Preparation, Microstructure,Properties of a Novel High-Strength, High-Toughness, and High-Corrosion- Resistant Ti6Al7Nb-xZr Biomedical Alloy[D]. Qinhuangdao: Yanshan University, 2023.
[128] NATISHAN P M, O’GRADY W E, MARTIN F J, et al. Chloride Interactions with the Passive Films on Stainless Steel[J]. Journal of the Electrochemical Society, 2011, 158(2): C7.
[129] HEUER A H, KAHN H, NATISHAN P M, et al.Electrostrictive Stresses and Breakdown of Thin Passive Films on Stainless Steel[J]. Electrochimica Acta, 2011, 58: 157-160.
[130] 王育武. 不同因素对316L不锈钢钝化膜化学结构与性能的影响研究[D]. 北京: 北京化工大学, 2018.
WANG Y W.The Effect of Different Factors on the Characteristics and Chemical Composition of Passive Film Formed on 316L Stainless Steel[D]. Beijing: Beijing University of Chemical Technology, 2018.
[131] ZHANG Y X, YAN T T, FAN L, et al.Effect of pH on the Corrosion and Repassivation Behavior of TA2 in Simulated Seawater[J]. Materials, 2021, 14(22): 6764.
[132] KOLMAN D G, SCULLY J R.Understanding the Potential and pH Dependency of High-Strength Β-Titanium Alloy Environmental Crack Initiation[J]. Metallurgical and Materials Transactions A, 1997, 28(12): 2645-2656.
[133] SOUZA M E P, LIMA L, LIMA C R P, et al. Effects of pH on the Electrochemical Behaviour of Titanium Alloys for Implant Applications[J]. Journal of Materials Science: Materials in Medicine, 2009, 20(2): 549-552.
[134] 南榕, 蔡建华, 杨健, 等. 钛及钛合金腐蚀行为研究进展[J]. 钛工业进展, 2023, 40(5): 40-48.
NAN R, CAI J H, YANG J, et al.A Review of Corrosion Resistance of Titanium and Titanium Alloys[J]. Titanium Industry Progress, 2023, 40(5): 40-48.
[135] 刘丽, 毛英杰, 陈志红. 钛合金在不同pH值人工唾液中耐腐蚀性能的研究[J]. 中国生物医学工程学报, 2006, 25(2): 166-169.
LIU L, MAO Y J, CHEN Z H.The Effect on the Corrosion Resistance of Ti Alloy in the Artificial Saliva with Different pH Value[J]. Chinese Journal of Biomedical Engineering, 2006, 25(2): 166-169.
[136] 杨专钊, 刘道新, 张晓化. 钛及钛合金的缝隙腐蚀行为[J]. 腐蚀与防护, 2013, 34(4): 295-297.
YANG Z Z, LIU D X, ZHANG X H.Crevice Corrosion Behavior of Titanium and Tiatanium Alloys[J]. Corrosion & Protection, 2013, 34(4): 295-297.
[137] SCHIFF N, GROSGOGEAT B, LISSAC M, et al.Influence of Fluoride Content and pH on the Corrosion Resistance of Titanium and Its Alloys[J]. Biomaterials, 2002, 23(9): 1995-2002.
[138] KOVAČEVIĆ N, PIHLAR B, ŠELIH V S, et al. The Effect of pH Value of a Simulated Physiological Solution on the Corrosion Resistance of Orthopaedic Alloys[J]. Acta Chimica Slovenica, 2012, 59(1): 144-155.
[139] BAYRAMOĞLU G, ALEMDAROĞLU T, KEDICI S, et al. The Effect of pH on the Corrosion of Dental Metal Alloys[J]. Journal of Oral Rehabilitation, 2000, 27(7): 563-575.
[140] HUANG Y Z, BLACKWOOD D J.The Influence of Dissolved Oxygen in Solution on the Titanium Oxide Growth at Different Sweep Rates[J]. Electrochimica Acta, 2006, 51(17): 3521-3525.
[141] BERTHAUD M, POPA I, CHASSAGNON R, et al.Study of Titanium Alloy Ti6242S Oxidation Behaviour in Air at 560 ℃: Effect of Oxygen Dissolution on Lattice Parameters[J]. Corrosion Science, 2020, 164: 108049.
[142] LI X Q, WANG L W, FAN L, et al.Effect of Temperature and Dissolved Oxygen on the Passivation Behavior of Ti-6Al-3Nb-2Zr-1Mo Alloy in Artificial Seawater[J]. Journal of Materials Research and Technology, 2022, 17: 374-391.
[143] REN P W, TANG X Y, QIN Z A, et al.Coupling Effect of Hydrostatic Pressure and Erosion on Corrosion Behavior of X70 Steel in Simulated Seawater[J]. ACS Omega, 2022, 7(48): 44033-44046.
[144] ENNS T, SCHOLANDER P F, BRADSTREET E D.Effect of Hydrostatic Pressure on Gases Dissolved in Water[J]. The Journal of Physical Chemistry, 1965, 69(2): 389-391.
[145] 刘叡. 静水压力环境Ti-6Al-4V合金应力腐蚀机理研究[D]. 合肥: 中国科学技术大学, 2021.
LIU R.Effect of Hydrostatic Pressure on the Stress Corrosion of Ti-6Al-4V Alloy[D]. Hefei: University of Science and Technology of China, 2021.
[146] SHIBATA T, ZHU Y C.The Effect of Film Formation Conditions on the Structure and Composition of Anodic Oxide Films on Titanium[J]. Corrosion Science, 1995, 37(2): 253-270.
[147] LI D G, WANG J D, CHEN D R, et al.Influence of Passive Potential on the Electronic Property of the Passive Film Formed on Ti in 0.1 mol/L HCl Solution during Ultrasonic Cavitation[J]. Ultrasonics Sonochemistry, 2016, 29: 48-54.
[148] BECCARIA A M, POGGI G, CASTELLO G.Influence of Passive Film Composition and Sea Water Pressure on Resistance to Localised Corrosion of Some Stainless Steels in Sea Water[J]. British Corrosion Journal, 1995, 30(4): 283-287.
[149] ZHANG C, ZHANG Z W, LIU L.Degradation in Pitting Resistance of 316L Stainless Steel under Hydrostatic Pressure[J]. Electrochimica Acta, 2016, 210: 401-406.
[150] SOUZA E C, ROSSITTI S M, ROLLO J M D A. Influence of Chloride Ion Concentration and Temperature on the Electrochemical Properties of Passive Films Formed on a Superduplex Stainless Steel[J]. Materials Characterization, 2010, 61(2): 240-244.
[151] PARK K, AHN S, KWON H.Effects of Solution Temperature on the Kinetic Nature of Passive Film on Ni[J]. Electrochimica Acta, 2011, 56(3): 1662-1669.