目的 采用一种激光微增材工艺,有效提高SS304L不锈钢表面抗腐蚀性能。方法 本研究通过激光表面改性技术,创新提出了激光微增材表面功能化工艺,将铜膜完全铺展在不锈钢金属表面,通过纳秒激光将铜膜覆在表面,设置三组覆膜方式进行对比,即单层覆膜,双次覆膜和双层覆膜,基于激光表面纹理化、表面铜颗粒和表面氧化膜的三重作用,有效提升了不锈钢表面抗腐蚀性能。结果 实验结果表明,利用激光微颗粒技术处理后,通过SEM观察到Cu颗粒,并且EDS和XPS在样品表面成功检测到Cu元素,表面微颗粒成功嵌入SS304L不锈钢表面。进一步观察发现,表面三维结构呈现规则的沟槽,同时伴随形成CuO和Cu2O的氧化膜;电化学腐蚀测试结果表明,激光微增材处理后样品的腐蚀电流较未处理样品降低了一个数量级,腐蚀电位提高0.03 V,表明该工艺显著增强了不锈钢的抗腐蚀能力。结论 通过激光微增材技术将铜颗粒嵌入不锈钢表面,融合了铜优秀的抗腐蚀性能和不锈钢固有的耐蚀性,从而有效提升了不锈钢的抗腐蚀能力。
Abstract
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.
关键词
激光表面改性 /
微增材 /
表面理化特性 /
抗腐蚀表面 /
防腐机理
Key words
laser surface modification /
micro-additive materials /
physico-chemical properties of surfaces /
corrosion- resistant surfaces /
anti-corrosion mechanisms
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基金
国家重点研发计划（2024YFD1300904）
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