腐蚀失效是制约铜基金属材料应用和发展的瓶颈。超疏水表面作为一种耐腐蚀性功能改良新技术,为解决铜金属腐蚀问题提供了有效途径。通过电火花线切割加工-硬脂酸表面修饰制备了超疏水铜表面,采用扫描电镜观察了其表面微观形貌,借助视频光学接触角仪测量其润湿性能,进一步通过电化学工作站对其腐蚀行为进行测试。结果表明:铜表面微米条形-纳米钟乳岩状分级复合结构被成功制备,并且该复合结构表面表现出优异的超疏水特性。此外,与基材相比,所制备的表面的耐腐蚀性提升了99.35%,并对该超疏水表面的防腐机理进行了系统研究分析,发现微纳复合结构的形成可有效捕获空气在试样表面形成固-气-液界面,其空气层的存在进一步阻碍了基底与电解质之间的电子传递和物质转移速度,从而抑制了基体电化学腐蚀速率,使得超疏水铜试样耐腐蚀性能显著提高。该方法简单高效用途广泛,制备过程环境友好,可适用大规模生产。
Corrosion failure is the bottleneck for restricting the application and development of copper-based metal materials. As a new technology of improving corrosion resistance, superhydrophobic surface provides an effective way to solve the problem of copper corrosion. In this work, the superhydrophobic copper surface was prepared by wire electrical discharge machining (WEDM) and surface modification with stearic acid. Subsequently, scanning electron microscope was used to observe the surface micro morphology, video optical contact angle meter was used to measure the wettability, and the corrosion behavior was further tested through the electrochemical workstation. Results showed that the micron strip nano stalactite graded composite structure on the copper surface had been successfully prepared, and the surface of the composite structure exihibited excellent superhydrophobic properties. In addition, compared with the substrate, the corrosion resistance of the prepared surface was increased by 99.35%. The corrosion prevention mechanism of the superhydrophobic surface was systematically studied and analyzed, and it was found that the formation of micro nano composite structure could effectively capture air to form a solid gas liquid interface on the surface of the sample, and the existence of the air layer further impeded the electron transfer and material transfer rate between the substrate and the electrolyte. Thereby, the electrochemical corrosion rate of the substrate was inhibited, and the corrosion resistance of the superhydrophobic copper sample was significantly improved. Overall, the method was simple, efficient and widely used, and the preparation process was environmentally friendly, which could be applied to large-scale production.
[1] 孙澄川, 卢 静, 解 路, 等. 冷喷涂制备铜基合金涂层研究进展[J]. 材料保护, 2022, 55(7): 165-176.
SUN C C, LU J,XIE L, et al. Progress in the preparation of copper-based alloy coatings by cold spraying[J]. Materials Protection, 2022, 55(7): 165-176.
[2] DING K K, FAN L, YU M J, et al. Sea water corrosion behaviour of T2 and 12832 copper alloy materials in different sea areas[J]. Corrosion Engineering, Science and Technology, 2019, 54(6): 476-484.
[3] 邓先钦, 徐群杰, 云 虹, 等. 具有超疏水表面的铜及铜合金耐蚀行为研究进展[J]. 腐蚀与防护, 2012, 33(1): 51-54.
DENG X Q, XU Q J, YUN H, et al. Progress in research on corrosion performance of copper and copper alloys with super-hydrophobic surface[J]. Corrosion & Protection, 2012, 33(1): 51-54.
[4] 刘爽爽, 付 超, 胡程程, 等. 混酸刻蚀制备X80钢超疏水涂层及其耐蚀性研究[J]. 焊管, 2022, 45(9): 16-21.
LIU S S, FU C, HU C C, et al. Preparation and corrosion resistance study of superhydrophobic coating on X80 steel by mixed acid etching[J]. Welded Pipe and Tube, 2022, 45(9): 16-21.
[5] 袁 冲, 张景文, 赖德林, 等. 超疏水石墨烯基材料的制备和自清洁防腐性能研究进展[J]. 材料保护, 2022, 55(6): 127-133.
YUAN C, ZHANG J W, LAI D L, et al. Research progress of preparation and self-cleaning anticorrosion properties of superhydrophobic graphene-based materials[J]. Materials Protection, 2022, 55(6): 127-133.
[6] TANG S K, CHANG X T, LI M Y, et al. Fabrication of calcium carbonate coated-stainless steel mesh for efficient oil-water separation via bacterially induced biomineralization technique[J]. Chemical Engineering Journal, 2021, 405: 126597.
[7] 刘戈辉, 邢 敏, 于 婷, 等. TSA协同HCl化学刻蚀铝片构筑低粘附超疏水表面及其稳定性[J]. 表面技术, 2019, 48(12): 140-149.
LIU G H, XING M, YU T, et al. Fabrication of low adhesion superhydrophobic surface on aluminum by TSA cooperates with HCl chemical etching method and its stability[J]. Surface Technology, 2019, 48(12): 140-149.
[8] 冯含宇, 邱会东, 彭 英, 等. 超双疏材料制备及其自修复性能的研究进展[J]. 材料保护, 2022, 55(6): 141-146.
FENG H Y, QIU H D, PENG Y, et al. Research progress of preparation and self-healing properties of super-amphiphobic materials[J]. Materials Protection, 2022, 55(6): 141-146.
[9] 庄明塔, 徐睿思, 刘灿森, 等. 阳极氧化法构筑的铝基超疏水表面及其耐蚀性能[J]. 金属热处理, 2021, 46(9): 241-246.
ZHUANG M T, XU R S, LIU C S, et al. Superhydrophobic surface of aluminum alloy prepared by anodic oxidation and its corrosion resistance[J]. Heat Treatment of Metals, 2021, 46(9): 241-246.
[10] ZHANG Y, ZHANG Z T, YANG J L, et al. Fabrication of superhydrophobic surface on stainless steel by two-step chemical etching[J]. Chemical Physics Letters, 2022, 797: 139567.
[11] WANG C V, TANG F, LI Q, et al. Spray-coated superhydrophobic surfaces with wear-resistance, drag-reduction and anti-corrosion properties[J]. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2017, 514: 236-242.
[12] GAO Y Z, SUN Y W, GUO D M. Facile fabrication of superhydrophobic surfaces with low roughness on Ti-6Al-4V substrates via anodization[J]. Applied Surface Science, 2014, 314: 754-759.
[13] 赵亚梅, 霍梦丹, 曹婷婷, 等. 提升超疏水材料力学耐久性的研究进展[J]. 复合材料学报,2023,40(4): 2 004-2 014.
ZHAO Y M, HUO M D, CAO T T, et al. Progress in improving the mechanical durability of superhydrophobic materials[J]. Acta Materiae Compositae Sinica, 2023,40(4): 2 004-2 014.
