| 引用本文: | 张美琪,董宇峰,程勇,谭诗瑶,王丽,王应泉,柯培玲,王振玉,汪爱英.氧等离子体处理对HiPIMS制备Cr涂层耐蚀性能的影响[J].中国表面工程,2024,37(6):236~246 |
| ZHANG Meiqi,DONG Yufeng,CHENG Yong,TAN Shiyao,WANG Li,WANG Yingquan,KE Peiling,WANG Zhenyu,WANG Aiying.Effect of Oxygen-plasma Treatment on Corrosion Resistance of Cr Coatings Deposited via HiPIMS[J].China Surface Engineering,2024,37(6):236~246 |
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| 氧等离子体处理对HiPIMS制备Cr涂层耐蚀性能的影响 |
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张美琪1，2，董宇峰2，程勇2，谭诗瑶2，王丽2，王应泉3，柯培玲2，王振玉2，汪爱英2
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1.宁波大学材料科学与化学工程学院 宁波 315211 ；2.中国科学院宁波材料技术与工程研究所海洋关键材料重点实验室 宁波 315201 ；3.宁波威霖住宅设施有限公司 宁波 315000
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| 摘要: |
| 金属 Cr 涂层因抗氧化、耐腐蚀、抗磨损、色泽明亮等，在严苛环境防护和功能装饰领域应用广泛。但物理气相沉积 （PVD）技术沉积的 Cr 涂层多以贯穿性柱状晶生长，耐腐蚀性能差，是科学界与产业界共同关注的难点挑战。与现有异质多层结构优化不同，采用高离化高功率脉冲磁控溅射（HiPIMS）同步脉冲偏压技术，在 316 不锈钢基体表面沉积 Cr 涂层，通过不同周期氧等离子体处理改性，于涂层内形成 Cr / Cr(O)多层结构，并进行研究。利用扫描电子显微镜（SEM）、扫描探针显微镜（SPM）、X 射线衍射（XRD）、能谱仪（EDS）、X 射线光电子能谱仪（XPS）等方法，表征涂层的相结构、表面粗糙度、表面/截面形貌、元素分布及化学键。利用 Gamry 电化学工作站和恒温盐雾腐蚀测试，研究涂层耐蚀性能。结果表明， 氧等离子体处理不改变 Cr 涂层的体心立方结构，但能够打断涂层柱状晶贯穿生长，使涂层表面更加光滑；经过两次等离子体处理的 Cr 涂层表面粗糙度约为未处理涂层的 1 / 4，腐蚀电流密度较未处理涂层降低了一个数量级，72 h 盐雾腐蚀后未探测到基体腐蚀粒子。该方法为解决 PVD 技术制备高性能耐腐蚀 Cr 涂层提供了新思路。 |
| 关键词: Cr 涂层 高功率脉冲磁控溅射(HiPIMS) 盐雾腐蚀 电化学腐蚀 |
| DOI：10.11933/j.issn.1007-9289.20231228002 |
| 分类号:TG178 |
| 基金项目:宁波市科技计划项目（2023QL049，2023Z110）；中国科学院青年创新促进会会员（2023312） |
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| Effect of Oxygen-plasma Treatment on Corrosion Resistance of Cr Coatings Deposited via HiPIMS |
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ZHANG Meiqi1，2，DONG Yufeng2，CHENG Yong2，TAN Shiyao2，WANG Li2，WANG Yingquan3，KE Peiling2，WANG Zhenyu2，WANG Aiying2
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1.School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 , China ；2.Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences, Ningbo 315201 , China ；3.Ningbo Runner Co., Ltd., Ningbo 315000 , China
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| Abstract: |
| Metallic chromium (Cr) coatings have garnered significant attention in demanding nuclear energy applications for safeguarding the surface of zirconium alloy fuel claddings as well as for functional modifications and embellishments on metals, polymers used in automobiles, sanitary hardware, and 3C (China compulsory certification) products. In contrast to the rigid limitations of the electroplating technique, Cr coatings can be easily deposited via various physical vapor deposition (PVD)technologies, thus rendering them increasingly important as a protective option. However, the main bottleneck of Cr coatings is their inevitable columnar structures with coarse morphology during PVD deposition, which facilitates the easy penetration of chloride solutions into the substrate and visually obscures the gloss under exposure to humid conditions. Consequently, PVD-Cr coatings exhibit degraded protective performance and undesired failures. In this study, high-power pulsed magnetron sputtering (HiPIMS) is employed to deposit Cr coatings on 316 stainless steel and YG8 substrates. Synchronized pulsed biasing is performed during coating deposition. A crucial aspect of this method is the introduction of oxygen-plasma treatment within the Cr coating to form a composite Cr(O) layer to enhance the adhesion strength and corrosion resistance of the subsequent Cr coatings. Oxygen-plasma treatment is performed using a linear anode-layer ion source following the periodic manipulation of the Cr layer via HiPIMS. The results show that the addition of oxygen plasma significantly suppresses the growth of columnar crystals within the monolayer of the Cr coating deposited via HiPIMS. This observation is evidenced by the distinct inhibition of galvanic coupling corrosion in the heterogeneous multilayered coatings. In addition to modifying the microstructures, the O plasma does not compromise the outstanding decorative properties of the Cr coatings. For clarity, the surface morphology, crystalline structure, and chemical composition of the coatings are comprehensively characterized using scanning electron microscopy (FEI Quanta FEG 250) equipped with energy-dispersive X-ray spectrometry (OXFORD X-Max), X-ray diffraction (Bruker D8 Advance Diffractometer), scanning probe microscopy (3100 SPM), and X-ray photoelectron spectroscopy (XPS, SUPRA). Additionally, the salt-spray corrosion resistance and electrochemical corrosion resistance of the coatings are assessed at a constant temperature of 35 ℃ using NaCl and a Gamry electrochemical workstation, respectively. The results show that the Cr coating maintains its body-centered cubic structure even after the oxygen-plasma treatment, without the formation of a distinct Cr oxide layer. However, owing to the treatment with oxygen plasma, the infiltrating columnar growth of Cr is significantly suppressed, thus reducing the surface roughness by approximately one-fourth compared with that of the pristine Cr coating. Based on XPS analysis, both Cr-O and Cr-O-Cr bonds are present in the coatings treated with oxygen plasma. This indicates that the oxygen-plasma treatment effectively promotes the combination of elemental oxygen with chromium, thus resulting in the formation of a dense and thin amorphous oxide layer. The presence of Cr-O-Cr bonds may indicate the hindered growth of columnar crystals within the Cr coatings deposited via PVD. Based on the results of salt-spray corrosion tests, although slight corrosion occurred on all the coating surfaces with and without O-plasma modification because of grain boundary defects in the coating, no delamination is observed. Nevertheless, Co originating from the YG8 substrate is not detected on the coating surface after the two oxygen-plasma treatments, thus demonstrating improved corrosion resistance. Consequently, the coatings subjected to multiple oxygen-plasma treatments exhibit enhanced corrosion resistance. This can be understood in terms of two aspects based on electrochemical studies. First, performing O-plasma treatment yields a coarse grain structure at the etching interface between the underlying layers and a fine grain size in the uppermost layer, thus resulting in a highly inhomogeneous structure that accelerates galvanic corrosion as compared with the pristine Cr coating. However, when two plasma-treatment cycles are performed, the crystal structure within the Cr coating becomes more homogeneous and dense. This results in a significantly reduced corrosion current density as well as the highest polarization resistance and impedance modulus compared with those afforded by the pure Cr coating without oxygen-plasma modification. |
| Key words: Cr coating high power impulse magnetron sputtering (HiPIMS) salt spray corrosion electrochemical corrosion |
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