目的 通过实验探究霉菌对单层Cu及多层Cu/Ni涂层（Cu、Cu/Ni、Cu/Ni/Cu和Cu/Ni/Cu/Ni）的腐蚀行为,研究Cu/Ni复合涂层在霉菌作用下的腐蚀过程。方法 采用化学镀与电镀相结合的工艺在碳纤维复合材料（CFRP）基体上制备Cu/Ni复合涂层。将制备好的霉菌混合孢子悬浮液均匀喷洒在样品表面后进行恒温恒湿实验,不同实验周期后采用SEM观察样品表面的腐蚀形貌和霉菌生长状况,采用XPS分析实验28 d的样品表面成分。结果 实验28 d后,Cu、Cu/Ni/Cu涂层样品表面霉菌数量多,有明显的龟裂和点蚀坑,表面被腐蚀产物覆盖,发生严重腐蚀。而Cu/Ni和Cu/Ni/Cu/Ni涂层只有Cu/Ni涂层表面有零星绿色腐蚀产物,与Cu、Cu/Ni/Cu涂层相比,表面有Ni涂层的样品均未发生大面积腐蚀,且镀层样品表面较平整,没有明显的龟裂和孔洞。结论 涂层的腐蚀结果与涂层的层状结构有关。Cu、Cu/Ni/Cu涂层样品容易受到霉菌的腐蚀,但随着腐蚀反应的进行,Cu涂层持续释放的铜离子会抑制霉菌的活性,使霉菌数量下降,在28 d腐蚀实验后,两者的腐蚀程度接近。Cu/Ni和Cu/Ni/Cu/Ni涂层样品有效减少了涂层表面霉菌的附着,同时腐蚀过程中形成的钝化膜对腐蚀介质起到了阻挡作用,延缓了霉菌对涂层的腐蚀,而Cu/Ni/Cu/Ni多层结构能更有效地减少孔隙等缺陷,使得其腐蚀程度低于Cu/Ni涂层。
Abstract
The continuous proliferation of electromagnetic wave applications in intelligent communication systems and microelectronics has driven the development of electromagnetic interference (EMI) shielding materials toward lightweight architectures, broadband absorption and high-efficiency shielding performance. Carbon fiber reinforced polymer (CFRP), as a high-performance substrate, has garnered significant attention due to its exceptional electrical conductivity, mechanical strength and low density. However, its inherent diamagnetic properties substantially limit magnetic loss capabilities, and it is usually necessary to prepare metal coatings on the surface to improve their electromagnetic shielding effectiveness. The work aims to explore the corrosion behavior of single-layer Cu and multi-layer Cu/Ni coatings (Cu, Cu/Ni, Cu/Ni/Cu and Cu/Ni/Cu/Ni) by mold and to study the corrosion process of Cu/Ni composite coatings under the action of mold. Firstly, Cu/Ni composite coatings (Cu, Cu/Ni, Cu/Ni/Cu and Cu/Ni/Cu/Ni) were prepared on the carbon fiber composite (CFRP) substrate by electroless plating and electroplating. Then, the prepared mixed spore suspension of mold (Aspergillus niger, Aspergillus flavus, Aspergillus versicolor, Penicillium funiculosum and Chaetomium globosum) was uniformly sprayed on the surface of the sample for constant temperature and humidity experiments. Finally, the corrosion morphology and mold growth of the samples were observed by scanning electron microscope (SEM) after different experimental cycles, and the local element analysis was carried out by energy dispersive spectrometer (EDS). The surface chemical state of the samples was analyzed by X-ray photoelectron spectroscopy. After 28 days of the experiment, a large number of white colonies were observed on the surface of Cu and Cu/Ni/Cu coating samples. The number of molds was large and there were obvious cracks and pitting pits. The surface was covered by corrosion products and serious corrosion occurred. However, the number of molds on the surface of Cu/Ni and Cu/Ni/Cu/Ni coating samples was small, and no obvious corrosion occurred. The surface of the coating was intact, and only the surface of Cu/Ni coating had sporadic green corrosion products. Compared with Cu and Cu/Ni/Cu coatings, the samples of Ni coating on the surface did not suffer from large-area corrosion and the surface of the coating sample was relatively flat, without obvious cracks and holes. The corrosion results of the coating were related to the layered structure of the coating. The Cu and Cu/Ni/Cu coating samples were susceptible to mold corrosion, but as the corrosion reaction progressed, the copper ions continuously released by the Cu coating inhibited the activity of the mold and reduced the number of the mold. After the 28 d corrosion experiment, the corrosion degree of the two was close. The Cu/Ni and Cu/Ni/Cu/Ni coating samples effectively reduced the adhesion of the mold on the coating surface. At the same time, the passivation film formed during the corrosion process acted as a barrier to the corrosive medium and alleviated the corrosion rate of the mold to the coating. The Cu/Ni/Cu/Ni multi-layer structure could more effectively reduce defects such as pores, making its corrosion degree lower than that of the Cu/Ni coating. These findings provide critical insights for developing advanced protective coatings that combine the antimicrobial properties of copper with the passivation capabilities of nickel in optimized multi-layer architectures.
关键词
Cu/Ni复合涂层 /
霉菌混合孢子 /
微生物腐蚀 /
腐蚀行为 /
腐蚀产物
Key words
Cu/Ni composite coating /
mold mixed spores /
microbial corrosion /
corrosion behavior /
corrosion products
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参考文献
[1] LIU S, QIN S H, JIANG Y, et al.Lightweight High- Performance Carbon-Polymer Nanocomposites for Electromagnetic Interference Shielding[J]. Composites Part A: Applied Science and Manufacturing, 2021, 145: 106376.
[2] ZHANG J, LIN G, VAIDYA U, et al.Past, Present and Future Prospective of Global Carbon Fibre Composite Developments and Applications[J]. Composites Part B: Engineering, 2023, 250: 110463.
[3] TUGIRUMUBANO A, VIJAY S J, GO S H, et al.Characterization of Electromagnetic Interference Shielding Composed of Carbon Fibers Reinforced Plastics and Metal Wire Mesh Based Composites[J]. Journal of Materials Research and Technology, 2019, 8(1): 167-172.
[4] 董言治, 任建存, 刘振杰. 霉菌和微生物对舰船的腐蚀及其涂料防护研究[J]. 现代涂料与涂装, 2006, 9(7): 30-32.
DONG Y Z, REN J C, LIU Z J.Study on the Mildew and Microbiological Corrosion of the Warship and the Relative Coating Protection[J]. Modern Paint & Finishing, 2006, 9(7): 30-32.
[5] XU D K, LI Y C, SONG F M, et al.Laboratory Investigation of Microbiologically Influenced Corrosion of C1018 Carbon Steel by Nitrate Reducing Bacterium Bacillus Licheniformis[J]. Corrosion Science, 2013, 77: 385-390.
[6] 宋博强, 陈旭, 马贵阳, 等. SRB对X70管线钢在近中性pH溶液中腐蚀行为的影响[J]. 中国腐蚀与防护学报, 2016, 36(3): 212-218.
SONG B Q, CHEN X, MA G Y, et al.Effect of SRB on Corrosion Behavior of X70 Pipeline Steel in Near-Neutral pH Solution[J]. Journal of Chinese Society for Corrosion and Protection, 2016, 36(3): 212-218.
[7] 姚蓉, 张秋利, 秦芳玲, 等. 铁细菌对J55钢腐蚀行为的影响[J]. 腐蚀与防护, 2016, 37(3): 206-209.
YAO R, ZHANG Q L, QIN F L, et al.Effect of Iron Bacteria on Corrosion Behavior of J55 Steel[J]. Corrosion & Protection, 2016, 37(3): 206-209.
[8] DEEN K M, YOUSAF M, AFZAL N, et al.Microbiological Influenced Corrosion Attack by Bacillus Megaterium Bacteria on Al-Cu Alloy[J]. Materials Technology, 2014, 29(5): 269-274.
[9] JAVED M A, STODDART P R, WADE S A.Corrosion of Carbon Steel by Sulphate Reducing Bacteria: Initial Attachment and the Role of Ferrous Ions[J]. Corrosion Science, 2015, 93: 48-57.
[10] KLINTWORTH R, REHER H J, VIKTOROV A N, et al.Biological Induced Corrosion of Materials II: New Test Methods and Experiences from Mir Station[J]. Acta Astronautica, 1999, 44(7/8/9/10/11/12): 569-578.
[11] ZHAI X F, REN Y D, WANG N, et al.Microbial Corrosion Resistance and Antibacterial Property of Electrodeposited Zn-Ni-Chitosan Coatings[J]. Molecules, 2019, 24(10): 1974.
[12] JUZELIŪNAS E, RAMANAUSKAS R, LUGAUSKAS A, et al. Microbially Influenced Corrosion Acceleration and Inhibition. EIS Study of Zn and Al Subjected for Two Years to Influence of Penicillium Frequentans, Aspergillus Niger and Bacillus Mycoides[J]. Electrochemistry Communications, 2005, 7(3): 305-311.
[13] JUZELIŪNAS E, RAMANAUSKAS R, LUGAUSKAS A, et al. Microbially Influenced Corrosion of Zinc and Aluminium - Two-Year Subjection to Influence of Aspergillus Niger[J]. Corrosion Science, 2007, 49(11): 4098-4112.
[14] 冯亚丽, 李雪鸣, 赵永, 等. 铜在含氯薄液膜和杂色曲霉作用下的腐蚀行为[J]. 表面技术, 2022, 51(9): 178-187.
FENG Y L, LI X M, ZHAO Y, et al.Corrosion Behaviour of Copper under the Action of Chlorine-Containing Thin Liquid Film and Aspergillus Versicolor[J]. Surface Technology, 2022, 51(9): 178-187.
[15] 孙彩霞, 戴景杰, 张红霞, 等. Q235碳钢表面镍铬合金化层的耐海水好氧菌腐蚀性能[J]. 表面技术, 2022, 51(5): 99-110.
SUN C X, DAI J J, ZHANG H X, et al.Corrosion Resistance of Ni-Cr Alloyed Layer on Q235 Carbon Steel to Seawater Aerobic Bacteria[J]. Surface Technology, 2022, 51(5): 99-110.
[16] HUANG H L, GUO X P, ZHANG G A, et al.The Effects of Temperature and Electric Field on Atmospheric Corrosion Behaviour of PCB-Cu under Absorbed Thin Electrolyte Layer[J]. Corrosion Science, 2011, 53(5): 1700-1707.
[17] XIAO K, GAO X, YAN L D, et al.Atmospheric Corrosion Factors of Printed Circuit Boards in a Dry-Heat Desert Environment: Salty Dust and Diurnal Temperature Difference[J]. Chemical Engineering Journal, 2018, 336: 92-101.
[18] YI P, XIAO K, DING K K, et al.Initial Corrosion Behavior of a Copper-Clad Plate in Typical Outdoor Atmospheric Environments[J]. Electronic Materials Letters, 2016, 12(1): 163-170.
[19] XIAO K, YI P, YAN L D, et al.Corrosion Behavior of Silver-Plated Circuit Boards in a Simulated Marine Environment with Industrial Pollution[J]. Materials, 2017, 10(7): 762.
[20] 易盼, 丁康康, 宋维锋, 等. 盐雾对喷锡和化金印制电路板腐蚀行为的影响[J]. 工程科学学报, 2015, 37(12): 1601-1609.
YI P, DING K K, SONG W F, et al.Effect of Salt Spray Environment on the Corrosion Behavior of PCB—HASL and PCB—ENIG[J]. Journal of University of Science and Technology Beijing, 2015, 37(12): 1601-1609.
[21] 朱武峰, 吴文海, 秦成. 舰载机液压系统霉菌综合环境试验研究[J]. 液压与气动, 2013, 37(11): 79-83.
ZHU W F, WU W H, QIN C.Fungus Synthesized Environment Experiment and Research of Carrier-Based Hydraulic System[J]. Chinese Hydraulics & Pneumatics, 2013, 37(11): 79-83.
[22] 殷宗莲, 黄波, 胥泽奇, 等. 某炮弹底塞表面防护工艺霉菌试验研究[J]. 装备环境工程, 2015, 12(4): 72-75.
YIN Z L, HUANG B, XU Z Q, et al.Mold Test of Surface Protection Technology for Base Plug of a Type of Bullet[J]. Equipment Environmental Engineering, 2015, 12(4): 72-75.
[23] 赵晓阳, 王允丽. 霉菌试验用菌种生长形态和特征[J]. 航空标准化与质量, 2005(3): 35-39.
ZHAO X Y, WANG Y L.Growth Morphology and Characteristics of Strains for Mold Test[J]. Aeronautic Standardization & Quality, 2005(3): 35-39.
[24] 江星新, 卢耀军, 李欣彤, 等. 脉冲电镀Ni镀层参数影响及耐腐蚀机理[J]. 有色金属科学与工程, 2022, 13(1): 52-59.
JIANG X X, LU Y J, LI X T, et al.Parameter Influence and Corrosion Resistance Mechanism of Ni Coatings under Pulse Electroplating[J]. Nonferrous Metals Science and Engineering, 2022, 13(1): 52-59.
[25] 罗芹. 纳米镍涂层对铜合金耐腐蚀性能的影响[J]. 腐蚀与防护, 2023, 44(1): 25-29.
LUO Q.Effect of Nanocrystalline Nickel Coating on Corrosion Resistance of Copper Alloys[J]. Corrosion and Protection, 2023, 44(1): 25-29.
[26] ZAMANZAD-GHAVIDEL M R, RAEISSI K, SAATCHI A. The Effect of Surface Morphology on Pitting Corrosion Resistance of Ni Nanocrystalline Coatings[J]. Materials Letters, 2009, 63(21): 1807-1809.
[27] 贺光辉, 周波, 陈镇海, 等. PCB化学镀铜界面失效微观形态研究[J]. 印制电路信息, 2023, 31(12): 59-65.
HE G H, ZHOU B, CHEN Z H, et al.Study on the Micromorphology of Interface Failure in PCB Electroless Copper Plating[J]. Printed Circuit Information, 2023, 31(12): 59-65.
[28] 鄢豪, 管英柱. 非金属材料化学镀铜研究进展[J]. 电镀与涂饰, 2022, 41(11): 791-796.
YAN H, GUAN Y Z.Research Progress of Electroless Copper Plating on Nonmetals[J]. Electroplating & Finishing, 2022, 41(11): 791-796.
[29] 刘炜, 沈强, 吉柏锋, 等. 梯度硬质刀具涂层的研究进展[J]. 中国表面工程, 2025, 38(2): 1-18.
LIU W, SHEN Q, JI B F, et al.Research Progress of Gradient Hard Tool Coatings[J]. China Surface Engineering, 2025, 38(2): 1-18.
[30] WANG B S, LI R Y, ZHANG Z Y, et al.Novel Au/Cu2O Multi-Shelled Porous Heterostructures for Enhanced Efficiency of Photoelectrochemical Water Splitting[J]. Journal of Materials Chemistry A, 2017, 5(27): 14415-14421.
[31] LI L, LEI J G, JI T H.Facile Fabrication of p-N Heterojunctions for Cu2O Submicroparticles Deposited on Anatase TiO2 Nanobelts[J]. Materials Research Bulletin, 2011, 46(11): 2084-2089.
[32] MAHMOUD M A, QIAN W, EL-SAYED M A. Following Charge Separation on the Nanoscale in Cu2O-Au Nanoframe Hollow Nanoparticles[J]. Nano Letters, 2011, 11(8): 3285-3289.
[33] YUAN S J, PEHKONEN S O.Surface Characterization and Corrosion Behavior of 70/30 Cu-Ni Alloy in Pristine and Sulfide-Containing Simulated Seawater[J]. Corrosion Science, 2007, 49(3): 1276-1304.
[34] KONG D C, DONG C F, FANG Y H, et al.Copper Corrosion in Hot and Dry Atmosphere Environment in Turpan, China[J]. Transactions of Nonferrous Metals Society of China, 2016, 26(6): 1721-1728.
[35] LEE K J, LEE Y I, SHIM I K, et al. Large-Scale Synthesis of Polymer-Stabilized Silver Nanoparticles[J]. Solid State Phenomena, 2007, 124/125/126: 1189-1192.
[36] PLYUTO I V, SHPAK A P, STOCH J, et al.XPS Characterisation of Carbon-Coated Alumina Support[J]. Surface and Interface Analysis, 2006, 38(5): 917-921.
[37] 吴念初, 李月, 王蕤. 浸泡时间对B10铜镍合金钼酸盐转化膜性能的影响[J]. 辽宁石油化工大学学报, 2024, 44(2): 55-62.
WU N C, LI Y, WANG R.Effect of Soaking Time on Properties of Molybdate Conversion Film of B10 Cu-Ni Alloy[J]. Journal of Liaoning University of Petroleum & Chemical Technology, 2024, 44(2): 55-62.
[38] 王家明, 杨昊东, 杜敏, 等. B10铜镍合金在高浓度NH4+污染海水中腐蚀研究[J]. 中国腐蚀与防护学报, 2021, 41(5): 609-616.
WANG J M, YANG H D, DU M, et al.Corrosion of B10 Cu-Ni Alloy in Seawater Polluted by High Concentration of NH4+[J]. Journal of Chinese Society for Corrosion and Protection, 2021, 41(5): 609-616.
[39] 刘天娇, 陈惠鹏, 张卫方, 等. B10铜镍合金海水加速腐蚀行为[J]. 材料工程, 2017, 45(5): 31-37.
LIU T J, CHEN H P, ZHANG W F, et al.Accelerated Corrosion Behavior of B10 Cu-Ni Alloy in Seawater[J]. Journal of Materials Engineering, 2017, 45(5): 31-37.
[40] 李雪鸣, 胡玉婷, 易盼, 等. 热带雨林环境中典型霉菌对PCB-HASL腐蚀行为的影响[J]. 表面技术, 2018, 47(9): 126-132.
LI X M, HU Y T, YI P, et al.Effect of Typical Molds on PCB-HASL Corrosion Behaviors in Tropical Rainforest Environment[J]. Surface Technology, 2018, 47(9): 126-132.
[41] 李慧艳, 董超芳, 邹士文, 等. 霉菌对超高强钢腐蚀行为的影响[J]. 北京科技大学学报, 2013, 35(6): 753-762.
LI H Y, DONG C F, ZOU S W, et al.Effect of Mold on Corrosion Behavior of Ultra High Strength Steels[J]. Journal of University of Science and Technology Beijing, 2013, 35(6): 753-762.
[42] 邹士文, 李晓刚, 董超芳, 等. 霉菌对裸铜和镀金处理的印制电路板腐蚀行为的影响[J]. 金属学报, 2012, 48(6): 687-695.
ZOU S W, LI X G, DONG C F, et al.Effect of Mold on Corrosion Behavior of Printed Circuit board-Copper and Enig Finished[J]. Acta Metallurgica Sinica, 2012, 48(6): 687-695.
[43] 张雅妮, 张成鑫, 宋伟, 等. Ni-Cu-P复合镀层在硫酸盐还原菌环境下的腐蚀特性[J]. 表面技术, 2025, 54(12): 72-84.
ZHANG Y N, ZHANG C X, SONG W, et al.Corrosion Characteristics of Ni-Cu-P Composite Coatings in Environments of Sulphate-Reducing Bacteria[J]. Surface Technology, 2025, 54(12): 72-84.
基金
中国航空科学基金（20220019052001）; 江苏省科研与实践创新计划（SJCX25_0154）; 南京航空航天大学研究生科研与实践创新计划（xcxjh20240503）; 南京航空航天大学分析测试中心大型仪器设备共享测试经费
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