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

doi:10.11902/1005.4537.2024.054

中国腐蚀与防护学报

2024, Vol. 44

Issue (6): 1518-1528 CSTR: 32134.14.1005.4537.2024.054 DOI: 10.11902/1005.4537.2024.054

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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

张雅妮(

), 王思敏, 樊冰

西安石油大学材料科学与工程学院西安 710065

Corrosion and Passivation Behavior of TC4 Ti-alloy in a Simulated Downhole Liquid in High-temperature and High-pressed O₂ + CO₂ Environment

ZHANG Yani(

), WANG Simin, FAN Bing

School of Materials Science and Engineering, Xi'an Shiyou University, Xi'an 710065, China

引用本文:

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.
Yani ZHANG, Simin WANG, Bing FAN. 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.

全文: PDF(8403 KB) HTML

摘要:

采用高温高压腐蚀实验及电化学测试手段研究了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膜层情况。TC4钛合金在实验条件下具有良好的耐蚀性。在O₂ + CO₂气氛中，TC4钛合金表面膜层为n型半导体型，主要由TiO₂和Al₂O₃组成。随着膜层中Al₂O₃含量的增加，膜层对基体的保护性减弱。循环极化测试结果显示，阳极极化可以改善钛合金表面膜层的质量；但随着腐蚀系统中O₂含量的降低，膜层中的缺陷增多，致密性变差，膜层对基体的保护性减弱。

关键词 ： TC4钛合金, 钝化膜层, O₂ + CO₂气氛, 电化学

Abstract：

The corrosion of oil tube goods related with the oil enhanced recovery technology of air injection is very serious issue. Herewith, the corrosion and passivation behavior of TC4 Ti-alloy in a simulated downhole liquid in high-temperature and high-pressed O₂ + CO₂ environment were studied via a high temperature autoclave with electrochemical measurements. The investigation shows that TC4 alloy has good corrosion resistance in high temperature and high pressure O₂ + CO₂ environment. The passive film of TC4 alloy has n-type semiconductor characteristic, which is mainly composed of TiO₂ and Al₂O₃. The protective property of the passive film formed on the substrate is weakened with the increase of Al₂O₃ content in the film. The results of electrochemical tests show that anodic polarization improve the quality of the passive film formed on the surface of TC4 Ti-alloy. With the decreasing O₂ content in the system, the defects in the passive film increase, while the compactness of film decrease, and thereby the protective property of the film is weakened.

Key words： TC4 Ti-alloy passive film O₂ + CO₂ solution environment electrochemistry

收稿日期: 2024-02-21 32134.14.1005.4537.2024.054

ZTFLH:

TG172

基金资助:陕西省自然科学基础研究计划(2022JM-269)

通讯作者: 张雅妮，E-mail: zhangyn@xsyu.edu.cn，研究方向为金属材料的腐蚀与防护

Corresponding author: ZHANG Yani, E-mail: zhangyn@xsyu.edu.cn

作者简介: 张雅妮，女，1977年生，博士，副教授

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https://www.jcscp.org/CN/10.11902/1005.4537.2024.054 或 https://www.jcscp.org/CN/Y2024/V44/I6/1518

表1 失重腐蚀实验参数

图1 TC4钛合金C组实验前后宏观形貌

No.	S / cm²	t / h	∆M / g	V_corr / mm‧a^-1	$V ¯$ _corr / mm‧a^-1
A1	13.3143	24	0.0001	0.0061	0.0061
A2	13.3155	24	0.0001	0.0061
A3	13.1520	24	0.0001	0.0062
B1	13.2453	24	0.0001	0.0061	0.0061
B2	13.1883	24	0.0001	0.0061
B3	13.4093	24	0.0001	0.0060
C1	13.5079	72	0.0001	0.0020	0.0027
C2	13.4029	72	0.0002	0.0040
C3	13.5868	72	0.0001	0.0020

表2 TC4钛合金在3种气氛环境下的腐蚀速率

图2 TC4钛合金腐蚀实验后的腐蚀产物形貌

表3 TC4钛合金表面标记处腐蚀产物的EDS分析结果 (atomic fraction / %)

图3 不同环境下腐蚀后的TC4钛合金表面AFM图

图4 不同环境中试样表面产物的XRD谱

图5 不同环境下TC4钛合金的循环极化曲线

表4 不同环境下TC4循环极化正扫段曲线拟合结果

图6 不同环境下TC4钛合金的阻抗图谱

图7 不同环境下TC4钛合金的阻抗谱等效电路图

表5 TC4钛合金在不同环境中的阻抗谱拟合参数

图8 TC4钛合金C组试样形成的腐蚀产物膜的XPS分析

图9 TC4钛合金试样在不同环境下形成的腐蚀产物膜中O峰的精细分析

表6 TC4钛合金试样在不同环境下形成的腐蚀产物膜XPS分析结果

图10 TC4钛合金在不同腐蚀环境中的Mott-Schottky曲线图

表7 TC4钛合金钝化膜半导体的掺杂浓度和平带电位

1	Yang X F. Research on the safety of casing in steam-assisted air stimulation [J]. Contemp. Chem. Ind., 2015, 44: 2179
1	(杨雪峰. 注空气辅助蒸汽吞吐油套管安全性研究与应用 [J]. 当代化工, 2015, 44: 2179)
2	Geng S J, Chen H. Integrated anticorrosion technology for adjusting displacement injection system of air foam [J]. Oil-Gas Field Surf. Eng., 2010, 29(7): 79
2	(耿师江, 陈华. 用于空气泡沫调驱注入系统的综合防腐技术 [J]. 油气田地面工程, 2010, 29(7): 79)
3	Lin W M, Li X F, Chen X L, et al. Corrosion and protection in air-foam injection process [J]. Oilfield Chem., 2010, 27: 342
3	(林伟民, 李雪峰, 陈秀玲等. 注空气泡沫驱油过程中的腐蚀与防护研究 [J]. 油田化学, 2010, 27: 342)
4	Sui G Y. Protecting corrosion in Zheng-408 oil displacement well by in-situ combustion [J]. Corros. Prot. Petrochem. Ind., 2007, 24(3): 4
4	(隋国勇. 郑408火烧驱油注气井油管腐蚀与防护 [J]. 石油化工腐蚀与防护, 2007, 24(3): 4)
5	Pastorek F, Hadzima B, Fintová S, et al. Influence of anodic oxidation on the polarization resistance of Ti6Al4V alloy after shot peening [J]. Mater. Sci. Forum, 2015, 811: 59
6	Tsai Y T, Hou K H, Bai C Y, et al. The influence on immersion time of titanium conversion coatings on electrogalvanized steel [J]. Thin Solid Films, 2010, 518: 7541
7	Kofstad P, Anderson P B, Krudtaa O J. Oxidation of titanium in the temperature range of 800-1200^oC [J]. J. Less-Com. Met., 1961, 3: 89
8	Zhu M, Wang H T, Keller A A, et al. The effect of humic acid on the aggregation of titanium dioxide nanoparticles under different pH and ionic strengths [J]. Sci. Total Environ., 2014, 487: 375
9	Jerkiewicz G, Strzelecki H, Wieckowski A. A new procedure of formation of multicolor passive films on titanium: compositional depth profile analysis [J]. Langmuir, 1996, 12: 1005
10	Wang S B, Pan L, Song J J, et al. Titanium-defected undoped anatase TiO₂ with p-type conductivity, room-temperature ferromagnetism, and remarkable photocatalytic performance [J]. J. Am. Chem. Soc., 2015, 137: 2975
11	Müller A, Benninghoven A. Investigation of surface reactions by the static method of secondary ion mass spectrometry: V. The oxidation of titanium, nickel, and copper in the monolayer range [J]. Surf. Sci., 1974, 41: 493
12	Platau A, Johansson L I, Hagström A L, et al. Oxidation of cerium and titanium studied by photoelectron spectroscopy [J]. Surf. Sci., 1977, 63: 153
13	Pouilleau J, Devilliers D, Garrido F, et al. Structure and composition of passive titanium oxide films [J]. Mater. Sci. Eng., 1997, 47B: 235
14	Mccafferty E, Wightman J P. An X-ray photoelectron spectroscopy sputter profile study of the native air-formed oxide film on titanium [J]. Appl. Surf. Sci., 1999, 143: 92
15	Lv C X. Research on the thermal oxidation behavior of TC4、TA19 and Ti17 titanium alloys [D]. Shenyang: Liaoning University, 2022
15	(吕彩霞. TC4、TA19、Ti17钛合金的氧化行为研究 [D]. 沈阳: 辽宁大学, 2022)
16	Liu Y, Yang D Z, He S Y, et al. Process and properties of thermal oxidation layer on surface of titanium alloy [J]. Mater. Mech. Eng., 2003, 27(9): 27
16	(刘勇, 杨德庄, 何世禹等. 钛合金表面的热氧化层工艺及性能 [J]. 机械工程材料, 2003, 27(9): 27)
17	Yan W, Wang X X. Characterization of the surface oxygen-diffusion zone of the thermally oxidized titanium [J]. Rare Metal Mat. Eng., 2005, 34: 471
17	(严伟, 王小祥. 热氧化处理钛表面渗氧层的组织与性能研究 [J]. 稀有金属材料与工程, 2005, 34: 471)
18	Zhang C Y, Li C T, Zhang J. Study on effect of thermal oxidation treatment on wear resistance of titanium alloy [J]. Surf. Technol., 2008, 37(6): 18
18	(张春艳, 李春天, 张津. 热氧化处理对钛合金表面耐磨性能影响的研究 [J]. 表面技术, 2008, 37(6): 18)
19	Ahn S, Kim D, Kwon H. Analysis of repassivation kinetics of Ti based on the point defect model [J]. J. Electrochem. Soc., 2006, 153: B370
20	Pray H A, Schweickert C E, Minnich B H. Solubility of hydrogen, oxygen, nitrogen, and helium in water at elevated temperatures [J]. Ind. Eng. Chem., 1952, 44(5): 1146

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