To address the problem that the stainless steel metal is prone to corrosion failure in breeding environments, the work aims to propose a laser micro-additive copper-embedded surface functionalization process. The SS304L stainless steel was used as the substrate, and the Cu foil with a thickness of 0.12 µm was used as the micro-additive material. A 355 nm nanosecond laser was adopted to carry out laser processing under the conditions of an average power of 60 W, a repetition rate of 40 kHz, and a pulse width of 16 ns. Three process routes, namely single-layer coating, double-layer coating, and double-pass coating, were designed, and three groups of scanning speeds of 400, 800, and 1 200 mm/s were set to prepare different surface- functionalized samples. Three-dimensional profilometry, scanning electron microscopy, energy-dispersive spectroscopy(EDS), X-ray photoelectron spectroscopy(XPS), and electrochemical tests were used to systematically analyze the physicochemical characteristics and corrosion-resistant behavior of the sample surfaces under different process conditions, and the corrosion resistance was systematically evaluated in combination with potentiodynamic polarization and electrochemical impedance spectroscopy in 3.5wt.% NaCl solution. The results showed that, after laser micro-additive treatment, regular grooves and micro-concave structures with higher sides and a lower middle were formed on the sample surfaces. The surface height difference increased from 0.1 µm for the untreated sample to 1.6-3.8 µm, among which the maximum value of the double-pass coating samples could reach 3.8 µm. EDS results showed that different process parameters significantly affected the Cu deposition behavior. Under the conditions of 400, 800, and 1 200 mm/s, the Cu contents on the sample surfaces reached 5.4%-19.3%, 22.2%-31.0%, and 8.2%-29.1%, respectively. Among them, sample b2 with the double-pass coating at 800 mm/s had the highest Cu content, reaching 31.0%. XPS results further showed that Cu particles were successfully embedded into the surface layer of the stainless steel, and a composite oxide layer mainly composed of CuO and Cu2O was formed on the surface. Among them, the proportion of copper oxides in the double-pass coating sample was as high as 97%, and the residual elemental copper was only about 3%. Electrochemical test results showed that, after laser micro-additive treatment, the corrosion potential of the sample shifted positively by about 0.020-0.032 V as a whole, and the corrosion current density decreased significantly. Compared with the untreated sample, the corrosion potentials of all coated samples shifted positively by about 0.020-0.032 V as a whole. The corrosion potential of the sample b2 increased from -0.964 V to -0.927 V, the corrosion current density decreased from 2.35×10-4 A/cm² to 8.24×10-5 A/cm2, and the charge transfer resistance increased from 4 620 Ω·cm2 to 6 954 Ω·cm2, showing the best corrosion resistance. Combined polarization and impedance results showed that the double-pass coating was overall better than the single-layer coating and the double-layer coating, indicating that the secondary laser action could promote more sufficient melting, embedding, and densification of the copper foil, thereby forming a more stable protective layer. Mechanism analysis showed that the surface micro/nano textures induced by the nanosecond laser provided anchoring sites for the embedding of Cu particles and enhanced the structural stability of the surface layer. Meanwhile, the synergistic shielding effect of the CuO and Cu2O composite oxide layer and the passive film on stainless steel effectively inhibited the diffusion of corrosive media such as Cl- toward the substrate, reduced the electrochemical corrosion reaction rate on the surface, and thus significantly improved the corrosion resistance of the material surface.
Key words
laser surface modification /
micro-additive materials /
physico-chemical properties of surfaces /
corrosion- resistant surfaces /
anti-corrosion mechanisms
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References
[1] BASTIDAS D M.Corrosion and Protection of Metals[J]. Metals, 2020, 10(4): 458.
[2] LV X Q, WANG C, LIU J, et al.The Microbiologically Influenced Corrosion and Protection of Pipelines: A Detailed Review[J]. Materials, 2024, 17(20): 4996.
[3] MAJI K, LAVANYA M.Microbiologically Influenced Corrosion in Stainless Steel by Pseudomonas Aeruginosa: An Overview[J]. Journal of Bio- and Tribo-Corrosion, 2024, 10(1): 16.
[4] LIU P, ZHANG H T, FAN Y Q, et al.Microbially Influenced Corrosion of Steel in Marine Environments: A Review from Mechanisms to Prevention[J]. Microorganisms, 2023, 11(9): 2299.
[5] 张蕾涛, 刘德鑫, 张伟樯, 等. 钛合金表面激光熔覆涂层的研究进展[J]. 表面技术, 2020, 49(8): 97-104.
ZHANG L T, LIU D X, ZHANG W Q, et al.Research Progress of Laser Cladding Coating on Titanium Alloy Surface[J]. Surface Technology, 2020, 49(8): 97-104.
[6] 肖荣诗, 张寰臻, 黄婷. 飞秒激光加工最新研究进展[J]. 机械工程学报, 2016, 52(17): 176-186.
XIAO R S, ZHANG H Z, HUANG T.Recent Progress in Femtosecond Pulsed Laser Processing Research[J]. Journal of Mechanical Engineering, 2016, 52(17): 176-186.
[7] S.A, D.D W R, JAIN A, et al. Laser Processing Techniques for Surface Property Enhancement: Focus on Material Advancement[J]. Surfaces and Interfaces, 2023, 42: 103293.
[8] LI S, ZHANG K, CHEN T Q, et al.Corrosion Resistance of Femtosecond Laser Induced Periodic Surface Structures on 7075 Aluminum Alloy[J]. Materials Today Communications, 2025, 48: 113670.
[9] OUTÓN J, CÓRDOBA T, GALLERO E, et al. Corrosion Behavior of Nanostructured Ferritic Stainless Steel by the Generation of LIPSS with Ultrashort Laser Pulses[J]. Journal of Materials Research and Technology, 2023, 27: 7422-7433.
[10] ALENCAR L M, FALCÃO S S, DE MELO H G, et al. The Influence of Laser Surface Texturing Parameters on the Surface of Lean Duplex Stainless Steel 2101 on Microstructure and Corrosion Properties[J]. Surface and Coatings Technology, 2025, 518: 132908.
[11] SECK G S, HACHE E, BONNET C, et al.Copper at the Crossroads: Assessment of the Interactions between Low-Carbon Energy Transition and Supply Limitations[J]. Resources, Conservation and Recycling, 2020, 163: 105072.
[12] VATANI R, ZAMANI-MEYMIAN M R, GHAFFARINEJAD A, et al. Corrosion Protection of CrCu Alloy Coating on Stainless Steel[J]. Surface and Coatings Technology, 2023, 474: 130106.
[13] DOMÍNGUEZ-JAIMES L P, ARENAS VARA M Á, CEDILLO-GONZÁLEZ E I, et al. Corrosion Resistance of Anodic Layers Grown on 304L Stainless Steel at Different Anodizing Times and Stirring Speeds[J]. Coatings, 2019, 9(11): 706.
[14] GATEMAN S M, HALIMI I, COSTA NASCIMENTO A R, et al. Using Macro and Micro Electrochemical Methods to Understand the Corrosion Behavior of Stainless Steel Thermal Spray Coatings[J]. npj Materials Degradation, 2019, 3: 25.
[15] 邢智慧, 雷利, 谭政, 等. 纳秒激光诱导黄铜超疏水光滑涂层的抗盐腐蚀性能研究[J]. 激光与红外, 2023, 53(12): 1855-1860.
XING Z H, LEI L, TAN Z, et al.Research on Salt Corrosion Resistance Performance of Nanosecond Laser- Induced Slippery Super-Hydrophobic Coating of Brass[J]. Laser & Infrared, 2023, 53(12): 1855-1860.
[16] QI Z W, CHEN C Y, WANG C Y, et al.Effect of Different Laser Wavelengths on Laser Cladding of Pure Copper[J]. Surface and Coatings Technology, 2023, 454: 129181.
[17] 章泽斌, 花银群, 叶云霞, 等. 基于皮秒激光的超疏水镍铝青铜合金表面的制备[J]. 中国激光, 2019, 46(3): 0302013.
ZHANG Z B, HUA Y Q, YE Y X, et al.Fabrication of Superhydrophobic Nickel-Aluminum Bronze Alloy Surfaces Based on Picosecond Laser Pulses[J]. Chinese Journal of Lasers, 2019, 46(3): 0302013.
[18] HAO J B, LIU Y Y, YANG S, et al.Numerical Simulation and Morphological Analysis of Laser Cladded 316L Stainless Steel on Inclined Substrates[J]. Optics & Laser Technology, 2024, 177: 111137.
[19] DENG C Y, ZHU Y X, CHEN W.Numerical Investigation of the Effects of Process Parameters on Temperature Distribution and Cladding-Layer Height in Laser Cladding[J]. Coatings, 2024, 14(8): 1020.
[20] MOSKAL D, MARTAN J, HONNER M.Scanning Strategies in Laser Surface Texturing: A Review[J]. Micromachines, 2023, 14(6): 1241.
[21] ZHENG L, LUO S, YANG S J.Preparation of Cu/CuO@Stearic Acid Layer with Superhydrophobicity to Provide Multiple Barriers for Corrosion Protection of Carbon Steel[J]. Materials Chemistry and Physics, 2023, 306: 128048.
[22] LI H J, JIANG Q T, LIU X B, et al.Corrosion Behavior and Electrochemical Properties of Heat-Treated Fe-20Cr-18Ni-6Mo-0.8Cu-0.2N-La Alloys in Alkaline Seawater[J]. npj Materials Degradation, 2025, 9: 136.
[23] LI X, LU L K, FANG J S, et al.Laser-Cladding Cu-Cr-X Coating on Cu Alloy for Longer Service Life in Electrical Applications[J]. Materials, 2025, 18(5): 1103.
[24] HERATH I, DAVIES J, WILL G, et al.Anodization of Medical Grade Stainless Steel for Improved Corrosion Resistance and Nanostructure Formation Targeting Biomedical Applications[J]. Electrochimica Acta, 2022, 416: 140274.
[25] AHUIR-TORRES J I, BURGESS A, SHARP M C, et al. A Study of the Corrosion Resistance of 316L Stainless Steel Manufactured by Powder Bed Laser Additive Manufacturing[J]. Applied Sciences, 2024, 14(17): 7471.
[26] RAHAL C, MASMOUDI M, ABDELMOULEH M, et al.An Environmentally Friendly Film Formed on Copper: Characterization and Corrosion Protection[J]. Progress in Organic Coatings, 2015, 78: 90-95.
[27] ALFIERI V, ARGENIO P, CAIAZZO F, et al.Reduction of Surface Roughness by Means of Laser Processing over Additive Manufacturing Metal Parts[J]. Materials, 2017, 10(1): 30.
Funding
The National Key Research and Development Program of China (2024YFD1300904)
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