热带海洋大气环境316不锈钢及其PVD防护涂层的腐蚀行为与性能演变研究OA
Corrosion Behavior and Performance Evolution of 316 Stainless Steel and Its PVD Protective Coatings in a Tropical Marine Atmospheric Environment
目的 探究 316 不锈钢及多弧离子镀 PVD 不同防护涂层在热带海洋大气环境中的腐蚀行为与失效机制.方法 将316 不锈钢基体及多弧离子镀制备的 TiN、TiAlN、TiSiN-Ag、CrN(沉积6 h和 12 h)及 Cr/CrN多层涂层试样,在永兴岛热带海洋大气腐蚀试验站暴晒 3.5 年.对暴晒后不锈钢进行扫描电镜及能谱分析(SEM/EDS)、X 射线光电子能谱(XPS)、激光共聚焦显微镜(CLSM)、纳米压痕、摩擦磨损及电化学测试,对暴晒后涂层进行扫描电镜及能谱分析(SEM/EDS)、摩擦磨损及电化学测试,并对比不锈钢基体暴晒前后的力学性能、摩擦学性能及电化学性能.结果 316 不锈钢发生典型点蚀,最大点蚀深度为 8.91 μm,平均深度约为6.70 μm,腐蚀产物以Fe2O3和 Cr2O3为主;暴晒后其表面硬度、耐磨性能及耐腐蚀性能均下降.涂层经暴晒后,TiN与 CrN单层涂层易发生贯穿性失效,Cr/CrN、TiAlN与 TiSiN-Ag 涂层完整性较好.CrN涂层失效机制为腐蚀介质首先沿涂层大颗粒缺陷渗入膜基界面,诱发基体不锈钢的点蚀并沿膜基界面横向扩展,腐蚀产物体积膨胀产生内应力,最终导致涂层鼓包、塌陷乃至剥落.结论 TiN 和 CrN 单层涂层防护效果不佳,TiAlN 和 TiSiN-Ag 涂层次之,Cr/CrN 涂层防腐蚀性能最优.多层多界面 PVD 涂层结构设计能有效延缓腐蚀介质渗透,在热带海洋环境中表现出优异的耐腐蚀性能,适用于该环境下的长效防护涂层设计.
A 3.5-year field atmospheric exposure test was conducted on the Yongxing Island,South China Sea,to investigate the corrosion behavior and failure mechanisms of 316 stainless steel(316 SS)and six PVD coatings deposited by multi-arc ion plating.The coatings comprised TiN,TiAlN,TiSiN-Ag,CrN-6 h,CrN-12 h,and a Cr/CrN multilayer.The objective was to provide experimental evidence for the design of protective coatings intended for service in tropical marine environments,where high humidity,salinity,and temperature pose severe challenges to metallic components,and to identify the dominant degradation mechanisms and key factors governing coating performance. 316 SS substrates and the six coatings were exposed at the Yongxing Island corrosion test station for 3.5 years.Coating deposition consisted of target cleaning,substrate etching by Ar+,deposition of the respective coatings,and cooling.For the unexposed 316 SS,nanoindentation,tribological testing,and electrochemical measurements were performed as baselines.For the exposed 316 SS,a comprehensive characterization was performed using SEM/EDS,XPS,CLSM,nanoindentation,tribological testing,and electrochemical measurements in artificial seawater(ASTM D1141-98)to evaluate corrosion morphology,corrosion product composition,tribological properties,and corrosion resistance.For the exposed coatings,a systematic characterization program was carried out,incorporating SEM/EDS for morphological and compositional analysis,tribological testing,and electrochemical measurements. After 3.5 years of exposure,the uncoated 316 SS exhibited typical pitting corrosion,with a maximum pit depth of 8.91 μm and an average depth of approximately 6.70 μm.XPS analysis confirmed that the predominant corrosion products consisted of Fe2O3 and Cr2O3.The exposure led to measurable degradation in surface properties,including mechanical,tribological,and electrochemical aspects:hardness decreased from 5.48 GPa to 4.78 GPa,the H/E ratio declined from 0.024 85 to 0.021 29,and the corrosion current density increased from 4.10×10-6 A/cm2 to 4.57×10-6 A/cm2.Among the PVD coatings,TiN and CrN monolayer coatings suffered from penetrating failure,with dense rust spots and exposure of the underlying steel.In contrast,the Cr/CrN multilayer,TiAlN,and TiSiN-Ag coatings maintained substantially better integrity.Electrochemical measurements after exposure demonstrated that the Cr/CrN multilayer coating retained the lowest corrosion current density(4.47×10-7 A/cm2),outperforming TiAlN(2.66×10-6 A/cm2)and TiSiN-Ag(1.15×10-6 A/cm2)coatings.In severely corroded regions of TiN and CrN monolayer coatings,the corrosion current density escalated to the 10-5 A/cm2 range,indicating near-total loss of protective capability. Cross-sectional SEM examination of failed CrN coatings revealed that large macroparticles,intrinsic to the multi-arc ion plating process,acted as preferential penetration pathways for the chloride-containing electrolyte.The corrosive medium infiltrated along these defect channels to the coating/substrate interface,initiating pitting of the underlying steel.Subsequent lateral propagation of interfacial corrosion,coupled with volume expansion from Fe2O3 and Cr2O3 formation,generated sufficient internal stress to induce coating bulging,collapse,and eventual spallation.For the Cr/CrN multilayer coating,the abundant layer interfaces effectively deflected crack propagation,and the dense structure extended the diffusion path of corrosive media through a tortuous-path effect,thereby imparting superior resistance to penetration and failure.In conclusion,this study identifies macroparticle defects as the primary failure initiation sites,interfacial corrosion as the dominant degradation mechanism,and multilayer architecture as an effective strategy for long-term corrosion protection in aggressive tropical marine environments.
蔡刚毅;徐桉;李金龙
河南工业大学 机电工程学院,郑州 450001中国科学院宁波材料技术与工程研究所 海洋关键材料全国重点实验室,浙江 宁波 315201||中国科学院宁波材料技术与工程研究所 全省极端环境材料表面与界面重点实验室,浙江 宁波 315201中国科学院宁波材料技术与工程研究所 海洋关键材料全国重点实验室,浙江 宁波 315201||中国科学院宁波材料技术与工程研究所 全省极端环境材料表面与界面重点实验室,浙江 宁波 315201
矿业与冶金
316不锈钢PVD涂层热带海洋大气环境耐候性腐蚀机理
316 stainless steelPVD coatingtropical marine atmospheric environmentweathering resistancecorrosion mechanism
《表面技术》 2026 (18)
48-57,100,11
浙江省领雁项目(2024C01159) Lingyan Project of Zhejiang Province(2024C01159)
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