Cu-Ni-Sn-xSi合金静态腐蚀及冲刷腐蚀行为研究

常卫卫; 陈明营; 武忠宇; 袁峰; 任京涛; 钱鸿昌; 李卫东; 刘新华; 张达威

doi:10.16490/j.cnki.issn.1001-3660.2026.04.002

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表面技术 ›› 2026, Vol. 55 ›› Issue (4) : 18-27. DOI: 10.16490/j.cnki.issn.1001-3660.2026.04.002

腐蚀与防护

Cu-Ni-Sn-xSi合金静态腐蚀及冲刷腐蚀行为研究

常卫卫^1a,2, 陈明营^1a,1b, 武忠宇^1a,2, 袁峰^1a,2, 任京涛^1a,2, 钱鸿昌^1a,2,*, 李卫东^1b, 刘新华^1a,3, 张达威^1a,1b,2

作者信息 +

Investigation of Static Corrosion and Erosion Corrosion Behaviour in Cu-Ni-Sn-xSi Alloy

Chang Weiwei^1a,2, CHEN Mingying^1a,1b, WU Zhongyu^1a,2, YUAN Feng^1a,2, REN Jingtao^1a,2, QIAN Hongchang^1a,2,*, LI Weidong^1b, LIU Xinhua^1a,3, ZHANG Dawei^1a,1b,2

Author information +

文章历史 +

摘要

目的研究不同Si含量的低Sn铜合金在模拟海水介质中的静态腐蚀行为以及冲刷腐蚀行为。方法制备Cu-12Ni-5Sn-0.25Mn-xSi（x=0.3,0.7）两种铜合金并进行后续冷轧和高温固溶处理,结合扫描电子显微镜（SEM）、能谱分析（EDS）观察合金中金属间化合物及腐蚀形貌。通过电化学阻抗谱（EIS）和动电位极化（PDP）分析合金的静态腐蚀行为,借助冲刷腐蚀试验机研究两种合金在不同流速腐蚀介质中的冲刷腐蚀行为差异。结果在Cu-12Ni-5Sn-0.25Mn-0.3Si合金中没有观察到元素的偏析,而Cu-12Ni-5Sn-0.25Mn-0.7Si合金中过量的Si成分与Ni在高温下形成片状Ni₂Si金属间化合物。Cu-12Ni-5Sn-0.25Mn-0.7Si合金表现出更高的硬度（高21HV）以及在3.5%（质量分数）NaCl溶液中更弱的耐蚀性能,这归因于硬质的析出相与基体间形成微电偶,促进基体的溶解。两种合金在静态的NaCl溶液中随着浸泡时间延长,耐蚀性能逐渐提升。在3 m/s及6 m/s流速介质冲刷腐蚀过程中,合金表面未观察到氧化物膜层或大量的腐蚀产物堆积,且合金的腐蚀速率明显提升,失重量可达静态介质中服役合金的5倍以上。此外,两种合金的失重量差异在低流速下更为显著。结论两种铜合金在静态NaCl溶液中能够形成完整且致密的氧化物膜层,对基体起到保护作用。而在3 m/s及6 m/s流速冲刷腐蚀过程中,两种合金表面刚形成的氧化膜层会因外力作用而脱落,导致基体的持续暴露和溶解。合金的腐蚀速率随流速增大、冲刷腐蚀时间延长而逐渐增大。Cu-12Ni-5Sn-0.25Mn-0.7Si合金在低流速下长时间冲刷后的失重率更高,归因于析出相诱导的局部腐蚀。而在高流速下,这种微电偶腐蚀导致的差异被减弱,归因于高流速能够促进腐蚀介质进入两种合金的点蚀坑中促进点蚀的扩展。

Abstract

Copper and its alloys have broad application prospects in the fields of ship components, offshore platforms and marine industrial materials due to their excellent corrosion resistance in seawater and resistance to corrosion fatigue. However, due to the complex and harsh service environment in the ocean, copper alloys inevitably undergo corrosion failures during long-term service. High seawater flow rates exert significant mechanical forces on the surface of copper alloys, leading to the detachment of corrosion product layers and promoting further corrosion. Currently, research on the erosion corrosion behavior of copper alloys remains relatively limited. Cu-Ni-Sn alloys offer advantages such as high strength, wear resistance, corrosion resistance and good electrical conductivity, while excessively high Sn contents in copper alloys often leads to a tendency for Sn segregation during the solidification. Microalloying is commonly employed to address this issue. To date, there have been numerous reports on the effects of microalloying on the microstructure and mechanical properties of Cu-Ni-Sn alloys, but research on changes in their corrosion performance still remains limited. This work investigated the static corrosion and erosion corrosion behavior of Cu-Ni-Sn alloys with different Si contents in 3.5wt.% NaCl solution. Two copper alloys, Cu-12Ni-5Sn-0.25Mn-xSi (x=0.3 and 0.7), were fabricated and subject to cold rolling and high-temperature solution treatment. The scanning electron microscopy (SEM) was employed in combination with energy dispersive spectroscopy (EDS) to observe the intermetallic compounds and corrosion morphology. The corrosion behavior was analyzed through electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP), while the differences in the erosion corrosion behavior of the two alloys in 3.5wt.% NaCl solution at different flow rates were investigated with an erosion corrosion tester. No significant elemental aggregation was observed in the 0.3Si alloy, whereas the excessive Si content in the 0.7Si alloy formed Ni₂Si intermetallic compounds with Ni. The 0.7Si alloy exhibited higher hardness (21HV higher) but inferior corrosion resistance in a 3.5wt.% NaCl solution, which was attributed to the micro-galvanic corrosion between the hard precipitates and the matrix, promoting matrix dissolution. Both alloys demonstrated relatively good corrosion resistance in a static NaCl solution due to the formation of an oxide film during prolonged immersion. However, when the copper alloys were exposed to flowing media, no dense oxide layer or widely distributed corrosion products were observed on the surface. The shear stress from the fluid flow disrupted the newly formed oxide layer, re-exposing the matrix to the corrosive medium. As a result, the weight loss of the copper alloys in flowing media was 4-5 times greater than that in static conditions. The 0.7Si alloy exhibited a higher weight loss rate than the 0.3Si alloy after prolonged exposure to low-flow conditions, primarily due to localized micro-galvanic corrosion induced by the precipitates. At high flow velocities, this difference in micro-galvanic corrosion was mitigated, as the high flow rate would promote the penetration of corrosive media into the pits of both alloys, accelerating pit propagation.

导出引用

常卫卫, 陈明营, 武忠宇, 袁峰, 任京涛, 钱鸿昌, 李卫东, 刘新华, 张达威. Cu-Ni-Sn-xSi合金静态腐蚀及冲刷腐蚀行为研究[J]. 表面技术. 2026, 55(4): 18-27

Chang Weiwei, CHEN Mingying, WU Zhongyu, YUAN Feng, REN Jingtao, QIAN Hongchang, LI Weidong, LIU Xinhua, ZHANG Dawei. Investigation of Static Corrosion and Erosion Corrosion Behaviour in Cu-Ni-Sn-xSi Alloy[J]. Surface Technology. 2026, 55(4): 18-27

中图分类号： TG172.5

参考文献

[1] MOUSAVI M, BAGHGOLI T.Application of Interaction Energy in Quantitative Structure-Inhibition Relationship Study of Some Benzenethiol Derivatives on Copper Corrosion[J]. Corrosion Science, 2016, 105: 170-176.
[2] HE Z B, WU Z, GAO Z M, et al.Erosion-Corrosion Behavior of Ni-Al-Cu Coating on Nickel-Aluminium Bronze Alloy in 3.5wt% NaCl Solution[J]. Corrosion Science, 2024, 238: 112380.
[3] LI Y H, WANG Y C, LV Y, et al.Localized Corrosion of Friction Stir Welded Al-Cu-Li Alloy: The Influence of Grain-Stored Energy on Grain Boundary Micro-Chemistry[J]. Journal of Materials Research and Technology, 2025, 37: 3880-3894.
[4] XIE J X.Prospects of Materials Genome Engineering Frontiers[J]. Materials Genome Engineering Advances, 2023, 1(2): e17.
[5] YUAN Y, ZHAO Y Z, ZHANG W J, et al.Enhancing Erosion-Corrosion Resistance of Cupronickel Alloys via Al-Addition on Microstructure and Mechanistic[J]. Materials & Design, 2025, 256: 114304.
[6] RAMÍREZ C G, MONSALVE A, MONTERO C, et al. Microbiologically Influenced Corrosion of Al-Cu-Li Alloy by Pseudomonas Aeruginosa[J]. Journal of Materials Research and Technology, 2025, 36: 5286-5297.
[7] BARIK R C, WHARTON J A, WOOD R J K, et al. Erosion and Erosion-Corrosion Performance of Cast and Thermally Sprayed Nickel-Aluminium Bronze[J]. Wear, 2005, 259(1/2/3/4/5/6): 230-242.
[8] LIANG S Y, LIU L, WANG X Y, et al.Subgrain Boundary Engineering Enables Synergistic Improvement of Strength and Corrosion Resistance in an Al-Cu-Li Alloy[J]. Materials & Design, 2025, 256: 114330.
[9] HWANG H J, LEE C G, KAYANI S H, et al.Effect of Retrogression Treatment on Microstructure, Mechanical Properties, and Corrosion Behavior in Al-Zn-Mg-Cu Alloy[J]. Journal of Materials Research and Technology, 2025, 36: 10577-10590.
[10] MOHAN S, RAJASEKARAN N.Influence of Electrolyte pH on Composition, Corrosion Properties and Surface Morphology of Electrodeposited Cu-Ni Alloy[J]. Surface Engineering, 2011, 27(7): 519-523.
[11] TANG S L, ZHOU M, ZHANG Y, et al.Improved Microstructure, Mechanical Properties and Electrical Conductivity of the Cu-Ni-Sn-Ti-Cr Alloy Due to Ce Micro-Addition[J]. Materials Science and Engineering: A, 2023, 871: 144910.
[12] PLEWES J T.High-Strength Cu-Ni-Sn Alloys by Thermomechanical Processing[J]. Metallurgical Transactions A, 1975, 6(3): 537.
[13] MOUSAVI S E, NAGHSHEHKESH N, AMIRNEJAD M, et al.Wear and Corrosion Properties of Stellite-6 Coating Fabricated by HVOF on Nickel-Aluminium Bronze Substrate[J]. Metals and Materials International, 2021, 27(9): 3269-3281.
[14] MENON S K, PIERCE F A, ROSEMARK B P, et al.Strengthening Mechanisms in NiAl Bronze: Hot Deformation by Rolling and Friction-Stir Processing[J]. Metallurgical and Materials Transactions A, 2012, 43(10): 3687-3702.
[15] ORZOLEK S M, SEMPLE J K, FISHER C R.Influence of Processing on the Microstructure of Nickel Aluminum Bronze (NAB)[J]. Additive Manufacturing, 2022, 56: 102859.
[16] OUYANG Y, GAN X P, LI Z, et al.Microstructure Evolution of a Cu-15Ni-8Sn-0.8Nb Alloy during Prior Deformation and Aging Treatment[J]. Materials Science and Engineering: A, 2017, 704: 128-137.
[17] GUO C J, SHI Y F, XIAO X P, et al.Enhanced Softening Resistance and Mechanical Properties of Cu-Ni-Sn Alloy with Al, Zn and Si Micro-Alloying[J]. Journal of Alloys and Compounds, 2022, 923: 166410.
[18] GAO M Q, CHEN Z N, KANG H J, et al.Effects of Nb Addition on the Microstructures and Mechanical Properties of a Precipitation Hardening Cu-9Ni-6Sn Alloy[J]. Materials Science and Engineering: A, 2018, 715: 340-347.
[19] YOU Y Q, LI C J, JIN K, et al.Microstructure and Property Evolution of Cu-9Ni-6Sn-xCr Alloys during Thermo-Mechanical Treatment Process[J]. Journal of Materials Research and Technology, 2024, 30: 2642-2652.
[20] FANG S F, WANG M P, WANG Y H, et al.Evolutionary Artificial Neural Network Approach for Predicting Properties of Cu-15Ni-8Sn-0.4Si Alloy[J]. Transactions of Nonferrous Metals Society of China, 2008, 18(5): 1223-1228.
[21] YU Q X, LI X N, WEI K R, et al.Cu-Ni-Sn-Si Alloys Designed by Cluster-Plus-Glue-Atom Model[J]. Materials & Design, 2019, 167: 107641.
[22] LEI Q, XIAO Z, HU W P, et al.Phase Transformation Behaviors and Properties of a High Strength Cu-Ni-Si Alloy[J]. Materials Science and Engineering: A, 2017, 697: 37-47.
[23] CHANG W W, GAO J G, QIAN H C, et al.Microbiologically Influenced Corrosion of Friction-Surfaced 630 Stainless Steel Coating in the Presence of Pseudomonas Aeruginosa[J]. Corrosion Science, 2025, 245: 112708.
[24] SAH S P.Evolution of Corrosion Resistance of 310S Stainless Steel in Carbonates Melt at 650 ℃[J]. Corrosion Science, 2024, 226: 111663.
[25] WANG M Q, YANG L H, WU S, et al.Research on Marine Atmospheric Corrosion Behavior of Carbon Steel during Western Pacific Voyage[J]. Journal of Materials Research and Technology, 2025, 36: 9678-9691.
[26] CHANG W W, LI Y Y, LI Z Y, et al.The Effect of Riboflavin on the Microbiologically Influenced Corrosion of Pure Iron by Shewanella Oneidensis MR-1[J]. Bioelectrochemistry, 2022, 147: 108173.
[27] XU C, PENG Y, CHEN L Y, et al.Corrosion Behavior of Wire-Arc Additive Manufactured and As-Cast Ni-Al Bronze in 3.5 Wt% NaCl Solution[J]. Corrosion Science, 2023, 215: 111048.
[28] TORRES BAUTISTA B E, CARVALHO M L, SEYEUX A, et al. Effect of Protein Adsorption on the Corrosion Behavior of 70Cu-30Ni Alloy in Artificial Seawater[J]. Bioelectrochemistry, 2014, 97: 34-42.
[29] MELCHERS R E.Nonlinear Trending of Corrosion of High Nickel Alloys in Extended Marine and Atmospheric Exposures[J]. Corrosion Reviews, 2020, 38(6): 515-528.
[30] QIN Z B, XIA D H, ZHANG Y W, et al.Microstructure Modification and Improving Corrosion Resistance of Laser Surface Quenched Nickel-Aluminum Bronze Alloy[J]. Corrosion Science, 2020, 174: 108744.
[31] JIN T Z, ZHANG W F, LI N, et al.Surface Characterization and Corrosion Behavior of 90/10 Copper-Nickel Alloy in Marine Environment[J]. Materials, 2019, 12(11): 1869.
[32] CHEN D H, ZHOU W J, JI Y C, et al.Applications of Density Functional Theory to Corrosion and Corrosion Prevention of Metals: A Review[J]. Materials Genome Engineering Advances, 2025, 3(1): e83.
[33] SAUD S N, HAMZAH E, ABUBAKAR T, et al.Effects of Mn Additions on the Structure, Mechanical Properties, and Corrosion Behavior of Cu-Al-Ni Shape Memory Alloys[J]. Journal of Materials Engineering and Performance, 2014, 23(10): 3620-3629.