钢基热障涂层酸性盐雾腐蚀行为研究

赵聪; 韦国科; 姜春竹; 崔向中; 高巍; 周国栋

doi:10.16490/j.cnki.issn.1001-3660.2026.09.021

PDF(40302 KB)

表面技术 ›› 2026, Vol. 55 ›› Issue (9) : 257-269. DOI: 10.16490/j.cnki.issn.1001-3660.2026.09.021

装备表面工程

钢基热障涂层酸性盐雾腐蚀行为研究

赵聪^*, 韦国科, 姜春竹, 崔向中, 高巍, 周国栋

作者信息 +

Acid Salt Spray Corrosion Behaviors of Thermal Barrier Coatings on Steel Substrates

ZHAO Cong^*, WEI Guoke, JIANG Chunzhu, CUI Xiangzhong, GAO Wei, ZHOU Guodong

Author information +

文章历史 +

摘要

目的探究酸性盐雾腐蚀实验条件下,钢基热障涂层（TBCs）的腐蚀行为。方法在钢基体表面,采用大气等离子喷涂（APS）制备TBCs,包括YSZ陶瓷层和NiCrAl金属黏结层。开展了酸性盐雾腐蚀实验,分析了腐蚀前后涂层的形貌、相组成、微观结构、化学成分、晶体结构类型,并与无涂层试样的腐蚀结果进行对比。结果腐蚀后,涂层表面出现红褐色斑点,但是未出现无涂层试样中的锈层剥落等现象。涂层表面出现微小团絮状组织,其中Fe、O元素含量很高（质量分数分别为15.65%、51.52%）,表明形成了Fe的氧化产物。涂层截面确认了Fe元素外扩散到涂层表层并富集。透射电子显微镜（TEM）观察发现,涂层中含有少量Fe元素,未出现晶体结构类型的变化。结论 pH值为3.5的酸性盐雾循环试验192 h后,钢基体表面被严重腐蚀,生成大量红褐色锈层,锈层出现开裂、剥落等现象。涂覆APS制备的TBCs后,腐蚀破坏程度明显减弱,表面开裂、剥落等现象消失,涂层和钢基体界面处也未出现分离。腐蚀过程中以涂层为介质实现了离子扩散,腐蚀介质内扩散到钢基体,生成的Fe离子外扩散到涂层表面。腐蚀后涂层中存在少量来自钢基体的Fe元素,但是未引起晶格的扩散重组。

Abstract

This work aims to investigate the corrosion behaviors of thermal barrier coatings (TBCs) on steel substrates under acid salt spray corrosion test conditions.
TBCs are prepared on steel substrates surfaces by air plasma spray (APS) technology, including 8.0wt.% Y₂O₃ partially stabilized ZrO₂ (YSZ) ceramic top layers and NiCrAl metallic bond layers (composition: Cr 17.0wt.%, Al 5.0wt.%, Ni balance). The acid salt spray corrosion test is carried out according to the GJB 150.11A—2 009 standard, adopting a cyclic regime consisting of 24 h continuous salt spray exposure followed by 24 h drying. Four such cycles are performed, resulting in a total test period of 192 h. After each cycle, the exposed surfaces are gently rinsed under ambient conditions with flowing deionized water to remove residual salt deposits for convenient photographic documentations of the results. The changes before and after corrosion are analyzed. The morphologies are characterized by ultra-depth Optical Microscopy (OM). The phase compositions are characterized by X-Ray Diffractometer (XRD). The microstructures are characterized by Scanning Electron Microscope (SEM). The chemical compositions are characterized by Energy Dispersive Spectroscopy (EDS) belonging to SEM. The crystal structure types are characterized by Transmission Electron Microscope (TEM). Comparative corrosion behavior analyses of uncoated samples are also conducted.
The experimental results demonstrate that after corrosion reddish-brown spots are observed on the coating surface, while rust spalling observed in uncoated sample does not occur. The surface roughness of coated sample increases, yet the growth amplitude is much lower than that of the uncoated sample, accounting for less than 1/10 of the latter's. Tiny flocculent microstructures appear on the coating surface. The content of Fe and O elements of the flocculent microstructures are both especially high (15.65wt.% and 51.52wt.%, respectively), which indicates that Fe oxidations form. Cross-sectional views show that coating thickness remains almost unchanged and no separation is observed at the interface between the coating and the steel substrate. Elemental mapping results reveal that the elements Zr, Y, Hf, O from the ceramic top layer remain localized within the ceramic top layer region and the elements Ni, Cr, Al from the metallic bond layer remain confined to the metallic bond layer region. While the element Fe from the steel substrate diffuses outward to the coating surface and accumulates. TEM results also show that small amounts of Fe element appear in the coating, while no crystal type changes are induced.
The results can be concluded that the steel substrate suffers severe corrosion after a 192 h acid salt spray cycle test with a pH value of 3.5, resulting in thick reddish-brown rust layers with visible cracking and spalling. APS-deposited TBCs can substantially reduce the corrosion damage. Surface crackings and spallings induced by corrosion disappear in coating samples, and no separation occurs at the coating/substrate interface. During the corrosion process, ion diffusion happens via the coating. The corrosive substances infiltrate to the steel substrate surface, while the generated ferri ions diffuse outward to the coating surface. Small amounts of Fe originating from the steel substrate exists in the corrosion-exposed coating, however which does not induce diffusional lattice reorganization.

导出引用

赵聪, 韦国科, 姜春竹, 崔向中, 高巍, 周国栋. 钢基热障涂层酸性盐雾腐蚀行为研究[J]. 表面技术. 2026, 55(9): 257-269

ZHAO Cong, WEI Guoke, JIANG Chunzhu, CUI Xiangzhong, GAO Wei, ZHOU Guodong. Acid Salt Spray Corrosion Behaviors of Thermal Barrier Coatings on Steel Substrates[J]. Surface Technology. 2026, 55(9): 257-269

中图分类号： TG174.4

参考文献

[1] 樊会涛, 吕长起, 林忠贤, 等. 空空导弹系统总体设计[M]. 北京: 国防工业出版社, 2007: 148-211.
FAN H T, LYU C Q, LIN Z X, et al.Air-to-Air Missile Systems Overall Design[M]. Beijing: National Defense Industry Press, 2007: 148-211.
[2] 罗楚养, 孙毓凯, 王文博, 等. 空空导弹结构技术的研究进展[J]. 航空兵器, 2019, 26(5): 1-10.
LUO C Y, SUN Y K, WANG W B, et al.Research Progress on Structure Technology of Air-to-Air Missile[J]. Aero Weaponry, 2019, 26(5): 1-10.
[3] 肖军, 廖志忠, 吴连锋. 空空导弹弹体结构海洋环境腐蚀防护[J]. 航空兵器, 2019, 26(6): 86-92.
XIAO J, LIAO Z Z, WU L F.Study on Corrosion Protection on Structure of Air-to-Air Missiles in Marine Environment[J]. Aero Weaponry, 2019, 26(6): 86-92.
[4] 房雷. 复合材料壳体在空空导弹固体火箭发动机中的应用研究[J]. 航空兵器, 2013, 20(2): 42-45.
FANG L.Study on Application of Composite Case in Solid Rocket Motor in Airborne Missile[J]. Aero Weaponry, 2013, 20(2): 42-45.
[5] 王虎干. 空空导弹固体火箭发动机舰用化关键技术分析[J]. 弹箭与制导学报, 2015, 35(2): 88-92.
WANG H G.Analysis of the Key Technologies of Marine Air-to-Air Missile Solid Rocket Motor[J]. Journal of Projectiles, Rockets, Missiles and Guidance, 2015, 35(2): 88-92.
[6] 张艳辉, 史明丽. 空空导弹工作温度分析[J]. 装备环境工程, 2015, 12(2): 99-103.
ZHANG Y H, SHI M L.Analysis on Operating Temperature for Air-to-Air Missiles[J]. Equipment Environmental Engineering, 2015, 12(2): 99-103.
[7] 黄智腾. 陶瓷热障涂层材料在超燃冲压发动机中的应用[D]. 长沙: 湖南大学, 2019: 32-34.
HUANG Z T.Thermal Barrier Coating Material Application in the Scramjet Engine[D]. Changsha: Hunan University, 2019: 32-34.
[8] 邱叶. 钢表面激光熔覆热障涂层性能研究[D]. 天津: 中国民航大学, 2022.
QIU Y.Study on Properties of Laser Cladding Thermal Barrier Coating on Steel Surface[D]. Tianjin: Civil Aviation University of China, 2022.
[9] GOWARD G W.Recent Developments in High Temperature Coatings for Gas Turbine Airfoils[C].// NACE International Conference on High Temperature Corrosion. Los Angeles: National Association of Corrosion Engineers, 1983: 553-560.
[10] 唐治虎. 航空发动机热障涂层材料体系的研究[J]. 新型工业化, 2022, 12(1): 172-173.
TANG Z H.Study on Thermal Barrier Coating Material System of Aero-Engine[J]. The Journal of New Industrialization, 2022, 12(1): 172-173.
[11] 史天杰, 张鑫, 彭浩然, 等. 热障涂层材料体系研究现状及展望[J]. 热喷涂技术, 2023, 15(2): 1-12.
SHI T J, ZHANG X, PENG H R, et al.Research Status and Prospect of Thermal Barrier Coating Materials System[J]. Thermal Spray Technology, 2023, 15(2): 1-12.
[12] GOWARD G W.Progress in Coatings for Gas Turbine Airfoils[J]. Surface and Coatings Technology, 1998, 108: 73-79.
[13] 张晗, 刘轩溱, 黄爱辉, 等. 热障涂层金属黏结层制备与研究进展[J]. 中国腐蚀与防护学报, 2025, 45(1): 20-32.
ZHANG H, LIU X (Q /Z), HUANG A H, et al. Manufacturing and Research Progress in Metallic Bond Coats for Thermal Barrier Coatings[J]. Journal of Chinese Society for Corrosion and Protection, 2025, 45(1): 20-32.
[14] 赵云松, 张迈, 戴建伟, 等. 航空发动机涡轮叶片热障涂层研究进展[J]. 材料导报, 2023, 37(6): 73-79.
ZHAO Y S, ZHANG M, DAI J W, et al.Research Progress of Thermal Barrier Coatings for Aeroengine Turbine Blades[J]. Materials Reports, 2023, 37(6): 73-79.
[15] 牟仁德, 何利民, 陆峰, 等. 热障涂层制备技术研究进展[J]. 机械工程材料, 2007, 31(5): 1-4.
MOU R D, HE L M, LU F, et al.Development in Research on TBC Deposition Technologies[J]. Materials for Mechanical Engineering, 2007, 31(5): 1-4.
[16] 牟仁德, 陆峰, 何利民, 等. 热障涂层技术在航空发动机上的应用与发展[J]. 热喷涂技术, 2009, 1(1): 53-58.
MU R D, LU F, HE L M, et al.Application and Development of Thermal Barrier Coatings on Aero Engines[J]. Thermal Spray Technology, 2009, 1(1): 53-58.
[17] 张松婷, 赵世贤, 李虹屿, 等. 大气等离子喷涂纳米粉体热障涂层及其抗热震性能研究[J/OL]. 耐火材料, https://link.cnki.net/urlid/41.1136.TF.20250213.0936.006.
ZHANG S T, ZHAO S X, LI H Y, et al. Research on Thermal Shock Resistance of Nanostructured 8YSZ Thermal Barrier Coatings Sprayed by Air Plasma[J/OL]. Refractories, https://link.cnki.net/urlid/41.1136.TF.20250213. 0936.006.
[18] 袁宝涵, 王卫泽, 方焕杰, 等. 大气等离子喷涂制备的不同结构热障涂层抗CMAS腐蚀性能[J]. 热加工工艺, 2025, 54(20): 143-147.
YUAN B H, WANG W Z, FANG H J, et al.Comparison of CMAS Corrosion Resistance of Different Structure Thermal Barrier Coatings Prepared by Atmospheric Plasma Spraying[J]. Hot Working Technology, 2025, 54(20): 143-147.
[19] 李荣斌, 程治军, 张志玺. 喷距对大气等离子喷涂8YSZ热障涂层组织结构及性能的影响[J]. 材料导报, 2024, 38(S2): 112-117.
LI R B, CHENG Z J, ZHANG Z X.Effect of Spray Distance on Microstructure and Properties of Atmospheric Plasma Sprayed 8YSZ Thermal Barrier Coatings[J]. Materials Reports, 2024, 38(S2): 112-117.
[20] 高元明, 马文, 冯雪英, 等. 热障涂层材料制备技术的研究进展及失效分析[J]. 陶瓷学报, 2024, 45(2): 248-268.
GAO Y M, MA W, FENG X Y, et al.Research Progress in Preparation Techniques and Failure Analysis of Thermal Barrier Coating Materials[J]. Journal of Ceramics, 2024, 45(2): 248-268.
[21] 张艳辉. 浅析舰载武器海洋环境适应性验证要求[J]. 装备环境工程, 2017, 14(5): 8-11.
ZHANG Y H.Requirement on Suitability Verification of Shipborne Weapons in Marine Environment[J]. Equipment Environmental Engineering, 2017, 14(5): 8-11.
[22] THEE C, HAO L, DONG J H, et al.Atmospheric Corrosion Monitoring of a Weathering Steel under an Electrolyte Film in Cyclic Wet-Dry Condition[J]. Corrosion Science, 2014, 78: 130-137.
[23] CORVO F, HACES C, BETANCOURT N, et al.Atmospheric Corrosivity in the Caribbean Area[J]. Corrosion Science, 1997, 39(5): 823-833.
[24] MA Y T, LI Y, WANG F H.Corrosion of Low Carbon Steel in Atmospheric Environments of Different Chloride Content[J]. Corrosion Science, 2009, 51(5): 997-1006.
[25] CANO H, NEFF D, MORCILLO M, et al.Characterization of Corrosion Products Formed on Ni2.4wt.%- Cu0.5wt.%-Cr0.5wt.% Weathering Steel Exposed in Marine Atmospheres[J]. Corrosion Science, 2014, 87: 438-451.
[26] MORCILLO M, de la FUENTE D, DÍAZ I, et al. Atmospheric Corrosion of Mild Steel[J]. Revista de Metalurgia, 2011, 47(5): 426-444.
[27] 笪光杰. Ni-Cr系耐蚀钢开发及耐海洋环境腐蚀机理研究[D]. 北京: 北京科技大学, 2025: 9-13.
DA G J.The Development of Ni-Cr Corrosion Resistant Steel and Research on the Mechanism of Corrosion Resistance in Marine Environment[D]. Beijing: University of Science and Technology Beijing, 2025: 9-13.
[28] 杨建炜, 蔡宁, 姜杉, 等. 高温高Cl?环境中含Ni、Cr耐蚀钢的腐蚀行为[J]. 腐蚀与防护, 2022, 43(4): 13-18.
YANG J W, CAI N, JIANG S, et al.Corrosion Behavior of Ni, Cr-Containing Corrosion Resistant Steel in High Temperature and High Cl? Environment[J]. Corrosion & Protection, 2022, 43(4): 13-18.
[29] 彭瑾. 等离子喷涂纳米ZrO₂热障涂层的耐盐雾腐蚀性能[J]. 热喷涂技术, 2012, 4(3): 19-22.
PENG J.Salt Spray Corrosion Resistance of Nano ZrO₂ Thermal Barrier Coatings Fabricated by Plasma Spraying Technology[J]. Thermal Spray Technology, 2012, 4(3): 19-22.
[30] 曹沁, 袁洁燕, 王进双, 等. 热障涂层表面腐蚀斑点的形成机理研究[J]. 热喷涂技术, 2019, 11(1): 9-22.
CAO Q, YUAN J Y, WANG J S, et al.Formation Mechanism of Corrosion Spots on Thermal Barrier Coatings[J]. Thermal Spray Technology, 2019, 11(1): 9-22.
[31] 李琰琰. 模拟海洋环境下Pt改性铝化物涂层和MCrAlY涂层的腐蚀行为研究[D]. 合肥: 中国科学技术大学, 2024: 4-8.
LI Y Y.The Corrosion Behavior of Pt-Modified Aluminide and MCrAlY Coatings in Simulated Marine Environment[D]. Hefei: University of Science and Technology of China, 2024: 4-8.
[32] GRABKE H J, REESE E, SPIEGEL M.The Effects of Chlorides, Hydrogen Chloride, and Sulfur Dioxide in the Oxidation of Steels below Deposits[J]. Corrosion Science, 1995, 37(7): 1023-1043.
[33] MCNALLAN M J, LIANG W W, KIM S H, et al.Acceleration of the High Temperature Oxidation of Metals by Chlorine[J]. In International Corrosion Conference Series, 1983, 15: 316-321.
[34] 刘英坤, 陈和兴, 余志明, 等. NiCoCrAlY涂层的抗中性盐雾腐蚀性能[J]. 机械工程材料, 2008, 32(10): 52-55.
LIU Y K, CHEN H X, YU Z M, et al.Salt Spray Corrosion Performance of NiCoCrAlY Coating[J]. Materials for Mechanical Engineering, 2008, 32(10): 52-55.
[35] 李淑青, 王纯, 李其连, 等. 激光-等离子复合热源喷涂NiCrAlY 涂层的抗盐雾腐蚀性能[J]. 材料保护, 2010, 43(10): 1-3.
LI S Q, WANG C, LI Q L, et al.Corrosion Resistance to Salt Spray of Laser-Plasma Hybrid Thermally Sprayed NiCrAlY Coating[J]. Materials Protection, 2010, 43(10): 1-3.
[36] ZHANG Q, TIE X X, LIN W L, et al.Variability of SO₂ in an Intensive Fog in North China Plain: Evidence of High Solubility of SO₂[J]. Particuology, 2013, 11(1): 41-47.
[37] 朱金阳, 李明, 程丛高. 美海军舰载航空装备 “盐雾- SO₂” 试验方法发展历程及启示[J]. 装备环境工程, 2017, 14(3): 33-38.
ZHU J Y, LI M, CHENG C G.Development and Enlightenment of “Salt Spray-SO₂” Test Method for Carrier- Based Aircraft of US Navy[J]. Equipment Environmental Engineering, 2017, 14(3): 33-38.
[38] 乔立捷, 袁帅, 孟一凡, 等. 热障涂层的高温氧化及水氧腐蚀行为研究[J]. 材料导报, 2025, 39(22): 176-181.
QIAO L J, YUAN S, MENG Y F, et al.Performance of Thermal Barrier Coatings under High-Temperature Oxidative and Water-Oxygen Corrosive Environments[J]. Materials Reports, 2025, 39(22): 176-181.
[39] SCOTT H G.Phase Relationships in the Zirconia-Yttria System[J]. Journal of Materials Science, 1975, 10(9): 1527-1535.
[40] 高丽华. 等离子物理气相沉积制备及微观组织调控机制研究[D]. 北京: 北京航空航天大学, 2016: 42-52.
GAO L H.Study on Preparation and Microstructural Control Mechanisms of Plasma Spray-Physical Vapor Deposition (PS-PVD)[D]. Beijing: Beihang University, 2016: 42-52.
[41] 王喆锦, 王丽爽, 麻忠宇, 等. 高温热暴露对等离子喷涂YSZ孔隙结构和力学性能的影响[J]. 材料导报, 2025, 39(4): 147-153.
WANG Z J, WANG L S, MA Z Y, et al.Effect of High Temperature Thermal Exposure on Pore Structure and Mechanical Properties of Plasma Sprayed YSZ[J]. Materials Reports, 2025, 39(4): 147-153.
[42] 刘飞洋, 李田科, 王睿鑫, 等. 稀有金属对钢海洋大气腐蚀行为影响的研究进展[J]. 稀有金属材料与工程, 2025, 54(3): 791-802.
LIU F Y, LI T K, WANG R X, et al.Research Progress on Effects of Rare Metals on Marine Atmospheric Corrosion Behavior of Steel[J]. Rare Metal Materials and Engineering, 2025, 54(3): 791-802.
[43] 王建涛, 郭云龙, 金涛. 3.5%NaCl盐雾条件下Q235A- Z35钢的腐蚀行为研究[J]. 材料保护, 2020, 53(4): 89-92.
WANG J T, GUO Y L, JIN T.Corrosion Behavior of Q235A-Z35 Steel under 3.5% NaCl Salt Spray Condition[J]. Materials Protection, 2020, 53(4): 89-92.
[44] 朱宇杰. 高温水蒸气及氢渗透对YSZ/MCrAlY热障涂层界面氧化行为及机理研究[D]. 北京: 北京科技大学, 2025: 16-20.
ZHU Y J.Research on Oxidation Behavior and Mechanism of YSZ/MCrAlY Thermal Barrier Coating Interface under High Temperature Water Vapor and Hydrogen Permeation[D]. Beijing: University of Science and Technology Beijing, 2025: 16-20.
[45] 蔡杰. 强流脉冲电子束作用下热障涂层热生长氧化物生长行为与应力状态[D]. 镇江: 江苏大学, 2015: 9-13.
CAI J.Growth Behavior and Stress Characteristics of Thermally Growth Oxide in Thermal Barrier Coatings Irradiated by High Current Pulsed Electron Beam[D]. Zhenjiang: Jiangsu University, 2015: 9-13.
[46] WAGNER C.Passivity and Inhibition during the Oxidation of Metals at Elevated Temperatures[J]. Corrosion Science, 1965, 5(11): 751-764.
[47] WAGNER C.Theoretical Analysis of the Diffusion Processes Determining the Oxidation Rate of Alloys[J]. Journal of the Electrochemical Society, 1952, 99(10): 369.
[48] 徐昌盛. 合金结构钢、不锈钢及其表面陶瓷涂层耐蚀性能研究[D]. 北京: 机械科学研究总院, 2012. : 110-112?.
XU C S. Research on the Corrosion Resistance of Alloy Construction Steels, Stainless Steels and Their Surface Ceramic Coatings[D]. Beijing: Wuhan Research Institute of Materials Protection, 2012. : 110-112?.
[49] 雒晓涛. 冷喷涂纳米结构cBN-NiCrAl金属陶瓷涂层的显微结构与力学性能的研究[D]. 西安: 西安交通大学, 2017: 96-98.
LUO X T.Microstructure and Mechanical Properties of Cold Sprayed Nanostructured CBN-NiCrAl Cermet Coatings[D]. Xi’an: XI’an Jiaotong University, 2017: 96-98.
[50] 刘吉宸. 42CrMo钢超声滚压加工表面完整性及耐腐蚀性能研究[D]. 大连: 大连海事大学, 2022.
LIU J C.Study on Surface Integrity and Corrosion Resistance of 42CrMo Steel after Ultrasonic Surface Rolling Process[D]. Dalian: Dalian Maritime University, 2022.
[51] 吴俊. 面向中性盐雾环境强化研磨对GCr15轴承钢耐腐蚀性能研究[D]. 广州: 广州大学, 2022: 47-74.
WU J.Study on the Corrosion Resistance of GCr15 Bearing Steel after Strengthened Grinding in Neutral Salt Spray Environment[D]. Guangzhou: Guangzhou University, 2022: 47-74.