谢馨媛,徐晨凯,董彦豪,邹敏敏,张优.基于硼掺杂碳量子点的镁合金腐蚀预警涂层及其性能研究[J].表面技术,2025,54(8):64-73.
XIE Xinyuan,XU Chenkai,DONG Yanhao,ZOU Minmin,ZHANG You.Corrosion Warning Coating of Mg Alloys Based on Boron-doped Carbon Dots and Its Properties[J].Surface Technology,2025,54(8):64-73 |
| 基于硼掺杂碳量子点的镁合金腐蚀预警涂层及其性能研究 |
| Corrosion Warning Coating of Mg Alloys Based on Boron-doped Carbon Dots and Its Properties |
| 投稿时间：2024-07-01 修订日期：2024-10-12 |
| DOI：10.16490/j.cnki.issn.1001-3660.2025.08.005 |
| 中文关键词: 硼掺杂碳量子点 镁合金 微弧氧化 溶胶凝胶 防腐 腐蚀预警 |
| 英文关键词:boron-doped carbon quantum dots Mg alloys micro-arc oxidation sol-gel anti-corrosion corrosion warning |
| 基金项目:国家自然科学基金(52471065);北京市属高等学校优秀青年人才培育计划项目(BPHR202203091);北京石油化工学院致远科研基金(2024001) |
| 作者 | 单位 |
| 谢馨媛 | 北京石油化工学院 新材料与化工学院，北京 102617 |
| 徐晨凯 | 北京石油化工学院 新材料与化工学院，北京 102617 |
| 董彦豪 | 北京石油化工学院 新材料与化工学院，北京 102617 |
| 邹敏敏 | 北京石油化工学院 新材料与化工学院，北京 102617 |
| 张优 | 北京石油化工学院 新材料与化工学院，北京 102617 |
|
| Author | Institution |
| XIE Xinyuan | School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China |
| XU Chenkai | School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China |
| DONG Yanhao | School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China |
| ZOU Minmin | School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China |
| ZHANG You | School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China |
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| 中文摘要: |
| 目的 提高镁合金的耐腐蚀性能且实现腐蚀预警，提高使用寿命，监测服役状态。方法 以AZ91D镁合金为基体，通过引入对Mg2+有高选择性的荧光探针硼掺杂碳量子点(Boron-doped Carbon Dots，BCDs)，制备了具有腐蚀预警性能的微弧氧化-溶胶凝胶碳量子点(Micro-Arc Oxidation-Sol-Gel-Boron-doped Carbon Dots，MAO-SG-BCDs)复合涂层。采用傅里叶红外光谱、拉曼光谱、荧光光谱等手段研究BCDs的结构、成分对镁离子及镁合金腐蚀表面的荧光性质。通过X射线衍射、扫描电子显微镜、荧光显微镜、电化学测试等方法对复合涂层的结构和性能进行研究。结果 随着在3.5%(质量分数)NaCl腐蚀溶液中浸泡时间的增加，与未掺杂BCDs的微弧氧化-溶胶凝胶(Micro-Arc Oxidation-Sol-Gel，MAO-SG)涂层样品相比，MAO-SG-BCDs表面在紫外光照射下逐渐呈现出蓝色荧光。浸泡7 d后，MAO-SG-BCDs复合涂层的腐蚀产物膜更加致密均匀，且低频区阻抗值高于未掺杂BCDs的样品，其腐蚀电位有所提升，腐蚀电流密度、腐蚀速率均降低2个数量级，表明BCDs可以有效提升涂层的耐蚀性能。结论 BCDs可作为镁合金腐蚀预警的荧光探针材料，将其添加到微弧氧化和溶胶凝胶复合涂层中，不仅可以提升镁合金AZ91D的耐蚀性能，还兼具对基体的腐蚀荧光预警响应。为开发有效的镁合金腐蚀预警材料及智能防腐涂层提供了新的思路。 |
| 英文摘要: |
| To enhance the corrosion resistance of Mg alloys, achieve effective corrosion warning, extend their service life, and monitor their service status, a Micro-Arc Oxidation-Sol-Gel-Boron-doped Carbon Dots (MAO-SG-BCDs) composite coating with advanced corrosion warning capability was developed on an AZ91D Mg alloy matrix. This was accomplished by incorporating Boron-doped Carbon Dots (BCDs) with high selectivity for Mg2+, ensuring targeted and efficient functionality. The structure, composition, and fluorescence properties of the BCDs, in relation to Mg2+ and the corroded surface of the Mg alloys, were meticulously studied with advanced analytical techniques such as Fourier transform infrared spectroscopy, Raman spectroscopy, and fluorescence spectroscopy. The structure and properties of the composite coating were comprehensively analyzed by X-ray diffraction, scanning electron microscopy, fluorescence microscopy, and electrochemical testing, providing a robust dataset for evaluation. The experimental results demonstrated that after a 7 d immersion in 3.5wt.% NaCl solution, the composite coating embedded with BCDs was denser and more uniform, exhibiting a higher impedance value in the low-frequency region compared to the sample without BCDs. This denser and more uniform structure indicated a more effective barrier against corrosive agents. The high impedance value in the low-frequency region is a crucial indicator of the ability of the coating to resist the ingress of corrosive ions, thereby prolonging the durability of the material in harsh environments. Furthermore, the MAO-SG-BCDs coating showed a significant increase in corrosion potential, and the corrosion current density and corrosion rate were reduced by two orders of magnitude, indicating that the incorporation of BCDs substantially enhanced the corrosion resistance of the coating. As immersion time increased, the surface of the MAO-SG-BCDs coating gradually exhibited blue fluorescence, in stark contrast to the MAO-SG coating sample that did not contain BCDs. This clear and observable response was attributed to the aggregation of BCDs, leading to strong complex formation between Mg2+ and the hydroxyl and phenolic oxygen atoms of the BCDs. This fluorescence provided a reliable method for real-time monitoring and early detection of corrosion, contributing to the development of smart anti-corrosion technologies. The blue fluorescence signal acted as an early warning system, indicating the onset of corrosion before significant material degradation occurred, thus enabling timely maintenance and intervention. XPS testing results indicated that, after 7 d of immersion, signals from BCO2 and BC2O were present in the BCDs-doped sample, confirming that physical adsorption occurred on the MAO layer of the Mg alloys, resulting in the formation of an adsorption film that effectively inhibited the erosion of the corrosive medium. The presence of these signals proved that BCDs were not only uniformly distributed within the coating but also actively engaged in the corrosion prevention process. The XPS spectra provided detailed insights into the chemical states of the elements within the coating, further validating the protective role of BCDs. BCDs function as fluorescent probe materials for corrosion warning in Mg alloys. When incorporated into MAO and sol-gel composite coatings, they significantly enhance the corrosion resistance of AZ91D Mg alloy while simultaneously providing a fluorescent warning response for substrate corrosion. This innovative approach not only improves the protective capabilities of the coating but also allows for real-time monitoring of corrosion processes. The findings of this research offer valuable new perspectives for the development of effective corrosion warning materials and smart anti-corrosion coatings specifically designed for Mg alloys. |
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