STL6/TiN复合涂层对F347不锈钢耐腐蚀性能的影响

于华明; 谷金龙; 吴小康; 朱刚贤; 张星; 王传洋; 李加强

doi:10.16490/j.cnki.issn.1001-3660.2026.12.007

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表面技术 ›› 2026, Vol. 55 ›› Issue (12) : 95-108. DOI: 10.16490/j.cnki.issn.1001-3660.2026.12.007

腐蚀与防护

STL6/TiN复合涂层对F347不锈钢耐腐蚀性能的影响

于华明¹, 谷金龙², 吴小康^2*, 朱刚贤¹, 张星¹, 王传洋¹, 李加强^1*

作者信息 +

Effect of STL6/TiN Composite Coating on Corrosion Resistance of F347 Stainless Steel

YU Huaming¹, GU Jinlong², WU Xiaokang^2*, ZHU Gangxian¹, ZHANG Xing¹, WANG Chuanyang¹, LI Jiaqiang^1*

Author information +

文章历史 +

摘要

目的提高F347不锈钢的耐腐蚀性能。方法采用等离子堆焊技术和化学气相沉积技术,制备了一种与基材结合良好的STL6/TiN复合涂层,并开展了异质界面的微观结构特征、组织演变、耐腐蚀性能研究。结果试验结果表明：堆焊层与基体呈现良好的冶金结合,等离子堆焊层组织由底部的平面晶、等轴晶,中部的树枝状枝晶和顶部的等轴晶组成,无缺陷且与基体冶金结合良好,堆焊层中氧化物含量少。腐蚀测试表明,STL6/TiN复合涂层的腐蚀电流密度显著降低至0.37 μA/cm²,腐蚀反应速率降低,提高了样品的耐腐蚀性能。STL6/TiN复合涂层样品的钝化电位最高,表面形成的钝化膜稳定性最佳（939 mV）且∣Z∣值最大,其抗电化学腐蚀性能显著提高。STL6堆焊层因可以形成致密的Cr₂O₃钝化膜,显著提高了耐腐蚀性能。STL6/TiN复合涂层的钝化电位最高,形成的表面钝化膜稳定性更好。结论其抗电化学腐蚀性能相比F347基材和单一STL6堆焊涂层均有进一步提升。在STL6/TiN复合涂层的保护下降低了F347不锈钢的腐蚀速率,提高了不锈钢的耐腐蚀性。相关研究成果为在苛刻环境下工作的F347不锈钢提高耐蚀性提供了技术路线和理论支撑。

Abstract

The effect of the STL6-TiN composite coating on the corrosion resistance of F347 stainless steel is studied. A STL6/TiN composite coating with good bonding with the substrate is prepared by plasma welding and chemical vapor deposition technology, which improves the corrosion resistance of the stainless steel.
Austenitic stainless steel ASTM A182 F347 with dimensions of 100×50×10 mm³ is selected as the substrate. The surface is meticulously ground using silicon carbide sandpaper and cleaned with ethanol. Under argon gas protection, a layer of Stellite6 is deposited onto the substrate via plasma welding. The deposited layer is then polished to a smooth finish, which serves as the base for preparing a TiN coating through chemical vapor deposition (CVD). The surface and sides are cut through wire cutting, followed by inlaying and polishing. The sample is polished to a scratch-free finish using a vibration polishing machine. The sample is then etched with aqua regia (a corrosive solution prepared at a 1∶3 ratio of HNO₃ to HCl). Microscopic morphology of the substrate, deposited layer, and CVD layer is observed with an optical microscope (OM, Olympus GX71) and a FEI Quanta-250 field emission scanning electron microscope (FEI). The chemical composition of the coating is analyzed with an energy dispersive spectrometer (EDS) integrated with the microscope. The porosity and other defects in the deposited layer are evaluated with a Zeiss Sradia 620 three-dimensional industrial CT scanner. Oxygen content in the deposited layer is measured with an EMGA-830E03-021 oxygen-nitrogen-hydrogen analyzer. Electrochemical corrosion experiments are conducted with a CS350 electrochemical workstation from Wuhan Kost Instrument Company. The experimental solution is a 3.5%NaCl solution, and the tests are performed at room temperature with a three-electrode system, with each experiment repeated at least five times. The samples of F347 matrix, F347-STL6 and F347-STL6-TiN (denoted as T₁, T₂and T₃ respectively) are cut by wire cutting machine with the diameter of 15mm and the thickness of 5mm, and the corrosion resistance of the coating is evaluated.
A well-structured STL6/TiN composite coating is successfully fabricated through plasma welding and chemical vapor deposition. The welding layer exhibits a microstructure composed of equiaxed grains at the base, columnar grains in the middle, and fine equiaxed grains at the top, demonstrating defect-free morphology and excellent metallurgical bonding with the substrate. On-site nuclear hydrogenation (ONH) analysis of the STL6 welding layer reveals an average oxygen content of 0.00325%. Corrosion tests show a significant reduction in corrosion current density from 1.526 μA/cm² to 0.37 μA/cm². The TiN coating effectively prevents corrosion reactions, thereby enhancing the sample's corrosion resistance. The STL6/TiN composite coating exhibits the highest passivation potential, indicating superior stability of the formed passivation film and the maximum |Z| value, which significantly improves its electrochemical corrosion resistance. The STL6 welding layer's ability to form a dense Cr₂O₃ passivation film further enhances its corrosion resistance. The STL6/TiN composite coating not only achieves the highest passivation potential but also demonstrates superior surface passivation film stability. Its corrosion current density is further improved compared with both the F347 substrate and the single STL6 welding layer. High concentrations of chromium and cobalt elements facilitate the formation of dense passivation films, effectively suppressing continuous damage from chloride ions. During the initial corrosion stage, the cobalt-based coating forms a highly bonded chromium-rich passivation film, significantly reducing the coating's corrosion rate. Therefore, stable oxide films exhibit greater resistance to chloride ions in electrolytes than unstable passivation films. The STL6/TiN composite coating significantly improves the corrosion resistance of stainless steel and reduces its corrosion rate. The results provide a technical route and theoretical support for improving the corrosion resistance of F347 stainless steel under harsh environment.

导出引用

于华明, 谷金龙, 吴小康, 朱刚贤, 张星, 王传洋, 李加强. STL6/TiN复合涂层对F347不锈钢耐腐蚀性能的影响[J]. 表面技术. 2026, 55(12): 95-108

YU Huaming, GU Jinlong, WU Xiaokang, ZHU Gangxian, ZHANG Xing, WANG Chuanyang, LI Jiaqiang. Effect of STL6/TiN Composite Coating on Corrosion Resistance of F347 Stainless Steel[J]. Surface Technology. 2026, 55(12): 95-108

中图分类号： TG174.4

参考文献

[1] SEN-BRITAIN S, CHO S, KANG S, et al.Critical Role of Slags in Pitting Corrosion of Additively Manufactured Stainless Steel in Simulated Seawater[J]. Nature Communications, 2024, 15: 867.
[2] GAIN S, KALYAN DAS S, SANYAL D, et al.Exploring Friction Stir Welding for Joining 316L Steel Pipes for Industrial Applications: Mechanical and Metallurgical Characterization of the Joint and Analysis of Failure[J]. Engineering Failure Analysis, 2023, 150: 107331.
[3] MONTES L, RICO V, NUÑEZ-GALVEZ F, et al. Long- Lasting Low Fluorinated Stainless Steel Hierarchical Surfaces for Omniphobic, Anti-Fouling and Anti-Icing Applications[J]. Surfaces and Interfaces, 2024, 46: 104167.
[4] GANESH KUMAR J, GANESAN V, LAHA K, et al.Time Dependent Design Curves for a High Nitrogen Grade of 316LN Stainless Steel for Fast Reactor Applications[J]. Nuclear Engineering and Design, 2013, 265: 949-956.
[5] MALHOTRA D, SHAHI A S.Metallurgical Behavior and Corrosion Performance of Ti + Nb Stabilized Austenitic Stainless Steel Welds[J]. Journal of Materials Engineering and Performance, 2023, 32(2): 544-561.
[6] WANG Y, WANG Z H, WANG W, et al.Effect of Nitrogen Content on Mechanical Properties of 316L(N) Austenitic Stainless Steel[J]. Materials Science and Engineering: A, 2023, 884: 145549.
[7] YANG R X, MA S C, CAI X, et al.Influence of Cerium on Creep Properties of 316LN Austenitic Stainless Steel[J]. Chinese Journal of Materials Research, 2024, 38: 23-32.
[8] BORGIOLI F, GALVANETTO E, BACCI T.Low Temperature Nitriding of AISI 300 and 200 Series Austenitic Stainless Steels[J]. Vacuum, 2016, 127: 51-60.
[9] BORGIOLI F, GALVANETTO E, BACCI T.Corrosion Behaviour of Low Temperature Nitrided Nickel-Free, AISI 200 and AISI 300 Series Austenitic Stainless Steels in NaCl Solution[J]. Corrosion Science, 2018, 136: 352-365.
[10] FOSSATI A, GALVANETTO E, BACCI T, et al.Improvement of Corrosion Resistance of Austenitic Stainless Steels by Means of Glow-Discharge Nitriding[J]. Corrosion Reviews, 2011, 29(5/6): 209-221.
[11] DI SCHINO A, BARTERI M, KENNY J M.Grain Size Dependence of Mechanical, Corrosion and Tribological Properties of High Nitrogen Stainless Steels[J]. Journal of Materials Science, 2003, 38(15): 3257-3262.
[12] DI SCHINO A, BARTERI M, KENNY J M.Effects of Grain Size on the Properties of a Low Nickel Austenitic Stainless Steel[J]. Journal of Materials Science, 2003, 38(23): 4725-4733.
[13] ZHANG Q L, SHAO L, LI W S, et al.Comparative Study of Anti-Corrosion Properties in Different CRN/WC-Co Duplex Coatings Processed by PVD/HVOF[J]. Surface and Coatings Technology, 2024, 483: 130799.
[14] MENG X N, DING L X, XIAO H, et al.A Study of Microstructures and Corrosion Behavior of HVOF/PVD Duplex Coating Against 10 Vol% HCl Solution[J]. Surface and Coatings Technology, 2024, 476: 130227.
[15] WANG X L, YE J W.Interface Characteristics of CVD Diamond Coating on WC-Co Cemented Carbide Substrate[J]. Surface and Coatings Technology, 2024, 485: 130886.
[16] BERDOYES I, PLAISANTIN H, DANET J, et al.The Corrosion Behavior of Various CVD SiC Coatings in Molten Silicon[J]. Ceramics International, 2024, 50(2): 3877-3886.
[17] ZHANG J, XUE Q, LI S X.Microstructure and Corrosion Behavior of TiC/Ti(CN)/TiN Multilayer CVD Coatings on High Strength Steels[J]. Applied Surface Science, 2013, 280: 626-631.
[18] XI K, WU H, ZHOU C L, et al.Improved Corrosion and Wear Resistance of Micro-Arc Oxidation Coatings on the 2024 Aluminum Alloy by Incorporation of Quasi-Two- Dimensional Sericite Microplates[J]. Applied Surface Science, 2022, 585: 152693.
[19] GAO Y X, CHEN Y N, XIAO S, et al.Effects and Mechanism of Zn on the Structure and Corrosion Resistance of Microarc Oxidation Coatings on Aluminum Alloy[J]. Applied Surface Science, 2024, 659: 159909.
[20] WANG Y, NORTHWOOD D O.Effect of Substrate Material on the Corrosion of TiN-Coated Stainless Steels in Simulated Anode and Cathode Environments of Proton Exchange Membrane Fuel Cells[J]. Journal of Power Sources, 2009, 191(2): 483-488.
[21] SUBRAMANIAN B, JAYACHANDRAN M.Electrochemical Corrosion Behavior of Magnetron Sputtered TiN Coated Steel in Simulated Bodily Fluid and Its Hemocompatibility[J]. Materials Letters, 2008, 62(10/11): 1727-1730.
[22] BALZER M.Identification of the Growth Defects Responsible for Pitting Corrosion on Sputter-Coated Steel Samples by Large Area High Resolution Mapping[J]. Thin Solid Films, 2015, 581: 99-106.
[23] SHI S H, XU A Q, FAN J W, et al.Study of Cobalt-Free, Fe-Based Alloy Powder Used for Sealing Surfaces of Nuclear Valves by Laser Cladding[J]. Nuclear Engineering and Design, 2012, 245: 8-12.
[24] HADIAN KAFFASH N, MARANDI S, BEIDOKHTI B, et al.Effect of Heat Treatment on Microstructure and Wear Properties of Laser Additively Manufactured 316 L Stainless Steel/Co-Cr-W Alloy Part Using Directed Energy Deposition Method[J]. Materials Today Communications, 2024, 38: 107865.
[25] 邵延凡, 王泽华, 李潇, 等. 双相不锈钢表面激光熔覆钴基合金组织和性能研究[J]. 表面技术, 2020, 49(4): 299-305.
SHAO Y F, WANG Z H, LI X, et al.Microstructure and Properties of Laser Cladding Cobalt-based Alloy on Duplex Stainless Steel Surface[J]. Surface Technology, 2020, 49(4): 299-305.
[26] 彭玉杰, 张建利, 李永华, 等. 激光熔覆钴基合金涂层组织结构与耐磨性研究[J]. 应用激光, 2023, 43: 11.
PENG Y J, ZHANG J L, LI Y H, et al.Microstructure and Wear Resistance of Laser Cladding Cobalt-based Alloy Coating[J]. Journal of Applied Laser, 2023, 43: 11.
[27] 张永超, 魏鹏宇, 朱琦, 等. 激光熔覆钴基合金涂层的组织与耐蚀性能研究[J]. 材料导报, 2021, 35: 8121.
ZHANG Y C, WEI P Y, ZHU Q, et al.Microstructure and Corrosion Resistance of Laser Cladding Cobalt-based Alloy Coating[J]. Materials Review, 2021, 35: 8121.
[28] 王伟东, 曹永胜, 周文浩,等. 脉冲激光熔覆钴基合金涂层的形貌与性能[J]. 焊接技术, 2023, 22: 29.
WANG W D, CAO Y S, ZHOU W H, et al.Morphology and Properties of Pulsed Laser Cladding Cobalt-based Alloy Coating[J]. Welding Technology, 2023, 22: 29.
[29] 王智勇, 林杰, 雷玉萍, 等. 激光熔覆钴基合金涂层的组织与耐磨性研究[J]. 激光与红外, 2020, 50: 1172.
WANG Z Y, LIN J, LEI Y P, et al.Microstructure and Wear Resistance of Laser Cladding Cobalt-based Alloy Coating[J]. Laser & Infrared, 2020, 50: 1172.
[30] 于诗晴. 不同温度下Stellite6与Stellite21堆焊层组织与性能研究[D]. 沈阳: 沈阳工业大学, 2022.
YU S Q.Study on Microstructure and Properties of Stellite6 and Stellite21 Welding Layers at Different Temperatures[D]. Shenyang: Shenyang University of Technology, 2022.
[31] 米大为, 卜佳炜, 郭宝超. 堆内构件钴基合金熔覆层组织及性能研究[J]. 精密成形工程, 2024, 16(6): 145-152.
MI D W, BU J W, GUO B C.Microstructure and Properties of Cobalt-Based Alloy Coatings on Nuclear Internal Components by Cladding[J]. Journal of Netshape Forming Engineering, 2024, 16(6): 145-152.
[32] 纪薇. 气相沉积TiN基硬质涂层力学性能及耐蚀性研究[D]. 石家庄: 石家庄铁道大学, 2022.
JI W.Mechanical Properties and Corrosion Resistance of Vapor-deposited TiN-based Hard Coatings[D]. Shijiazhuang: Shijiazhuang Tiedao University, 2022.
[33] DE ASSIS S L, WOLYNEC S, COSTA I. Corrosion Characterization of Titanium Alloys by Electrochemical Techniques[J]. Electrochimica Acta, 2006, 51(8/9): 1815-1819.
[34] YU Q F, ZHANG W, SHANG J L, et al.Comparative Investigation on the Microstructure and Corrosion Properties of Surfacing Cobalt Alloys by Various Methods[J]. Surface and Coatings Technology, 2024, 494: 131386.
[35] GÓRKA J, POLOCZEK T, JANICKI D, et al. Microstructure and Erosion Wear of in Situ TiC-Reinforced Co-Cr- W-C (Stellite 6) Laser-Cladded Coatings[J]. Materials, 2024, 17(13): 3101.
[36] KUBOTA R, TANEMURA S, KAWANAKA H, et al.Development of Laser Hardfacing Method of Cobalt Based Alloys for Valve Seat[C]//Proceedings of the International Conference on Nuclear Engineering (ICONE). 2023, 30: 1506.
[37] DA SILVA F G, BRAGA E M, FERRARESI V A, et al. Coating Weld Cavitation Erosion Resistance Using Austenitic Stainless Steel and Cobalt Alloys Deposited by GMAW and CW-GMAW[J]. Journal of the Brazilian Society of Mechanical Sciences and Engineering, 2022, 44(11): 569.
[38] VICTORIA F A, AGRIENETH R M, OLUKAYODE S A, et al.Corrosion Studies of Sintered Cobalt-based Alloys in Sodium Chloride[J]. Advances in Science and Technology, 2021, 617: 2144-148.
[39] XUE H T, ZHOU D, GUO W B, et al.Cobalt-Based Alloy Surfacing Process Optimization and Surfacing Material Performance Analysis[J]. Materials Research Express, 2021, 8(2): 026505.
[40] HONDA S.Inter Granular Corrosion Properties of the Cobalt Base Alloy Stellite No.6[J]. Proceedings of the 1992 Annual Meeting of JSME, 2003, 2003: 723-724.
[41] AWAN A, PASHA R A, BUTT M S, et al.Corrosion and Wear Behavior of TiN PVD Coated 304 Stainless-Steel[J]. Journal of Mechanical Science and Technology, 2020, 34(8): 3227-3232.
[42] CHEN J F, DING X P, WANG J F, et al.Corrosion Behavior, Metal Ions Release and Wear Resistance of TiN Coating Deposited on SLM CoCrMo Alloy by Magnetron Sputtering[J]. Journal of Alloys and Compounds, 2024, 1002: 175318.
[43] SUN X H, ZHAO Y H, YE C C, et al.The Effect of AlCrN, TiN and Ni-Cr-Nb Coatings on the Wear and Corrosion Performance of 45 # Steel in 3.5 % Sodium Chloride Solution[J]. International Journal of Electrochemical Science, 2024, 19(7): 100608.
[44] CHEN K, PAN Y T, TANG G B, et al.Facile Fabrication of TiN Coatings to Enhance the Corrosion Resistance of Stainless Steel[J]. Surface and Coatings Technology, 2024, 494: 131450.
[45] HUSSEIN M, ADESINA A, KUMAR M, et al.Investigations of In vitro Corrosion, and Wear Properties of TiN PVD Coating on Ti₆Al₄V Alloy for Dental Application[J]. Key Engineering Materials, 2019, 813: 1-6.
[46] DALIBÓN E L, PECINA J N, MOSCATELLI M N, et al. Mechanical and Corrosion Behaviour of DLC and TiN Coatings Deposited on Martensitic Stainless Steel[J]. Journal of Bio- and Tribo-Corrosion, 2019, 5(2): 34.
[47] LI R Z, WANG S H, PU J B, et al.Study of NaCl-Induced Hot-Corrosion Behavior of TiN Single-Layer and TiN/Ti Multilayer Coatings at 500 ℃[J]. Corrosion Science, 2021, 192: 109838.
[48] NAEEM M, AWAN S, SHAFIQ M, et al.Wear and Corrosion Studies of Duplex Surface-Treated AISI-304 Steel by a Combination of Cathodic Cage Plasma Nitriding and PVD-TiN Coating[J]. Ceramics International, 2022, 48(15): 21473-21482.
[49] XU X, LU H F, SU Y Y, et al.Comparing Corrosion Behavior of Additively Manufactured Cr-Rich Stainless Steel Coating between Conventional and Extreme High- Speed Laser Metal Deposition[J]. Corrosion Science, 2022, 195: 109976.
[50] JIN F, ZHANG S, WU C L, et al.Comparative Study on the Microstructure, Wear Behavior, and Corrosion Performance of Iron-Based and Cobalt-Based Coatings Fabricated by Laser Cladding[J]. Journal of Materials Engineering and Performance, 2024, 33(22): 12398-12412.
[51] DI C B, WANG J H, YAN E H, et al.Microstructure and Corrosion Resistance of Nb-Ti-Co Hydrogen Separation Alloy[J]. Materials Review, 2021, 35: 18109-18115.
[52] WANG X L, ZHANG Z X, ZHAO Y Q, et al.Macroscopic Morphology and Properties of Cobalt-Based Laser Cladding Layers on Rail Steel Based on Pulse Shaping[J]. Optics & Laser Technology, 2024, 168: 109940.