镁合金微弧氧化/MgLiAl-LDHs三元水滑石复合自修复涂层

焦佐军; 吴量; 郁富兵; 田珍珍; 周岩; 姚文辉; 袁媛; 谢治辉; 吴国志

doi:10.16490/j.cnki.issn.1001-3660.2025.15.003

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表面技术 ›› 2025, Vol. 54 ›› Issue (15) : 33-46. DOI: 10.16490/j.cnki.issn.1001-3660.2025.15.003

技术及应用

镁合金微弧氧化/MgLiAl-LDHs三元水滑石复合自修复涂层

焦佐军^1a, 吴量^1a,1b,*, 郁富兵^1a, 田珍珍^1a, 周岩^1a, 姚文辉^1a,1b, 袁媛^1a,1b, 谢治辉², 吴国志³

作者信息 +

Self-healing Micro-arc Oxidation/Ternary MgLiAl-LDHs Composite Coating on Magnesium Alloys

JIAO Zuojun^1a, WU Liang^1a,1b,*, YU Fubing^1a, TIAN Zhenzhen^1a, ZHOU Yan^1a, YAO Wenhui^1a,1b, YUAN Yuan^1a,1b, XIE Zhihui², WU Guozhi³

Author information +

文章历史 +

摘要

目的通过一步水热法在镁锂合金微弧氧化（MAO）涂层上搭建水滑石（LDHs）复合涂层,并通过低温水浴引入有机缓蚀剂分子,构建具有出色耐蚀性的智能自修复涂层。方法以Mg-8Li合金为基体,在偏铝酸盐体系电解质中制备MAO涂层。在水热溶液中引入NO₃^-,原位生长获得MgLiAl-LDHs三元水滑石涂层。在低温（50 ℃）水浴下,分别引入水杨酸（SA）和2-羟基-1,4-萘醌（HNQ）,制备自修复涂层（MgLiAl-LDHs-SA、MgLiAl-LDHs-HNQ）。采用SEM、EDS、XPS、FT-IR、XRD表征涂层的组成和结构,利用电化学实验、划伤实验和SVET测试涂层的耐腐蚀性能和自修复性能,并结合测试结果分析其耐蚀和自修复机理。结果复合涂层制备成功,它表现出LDHs结构(003)和(006)X射线特征衍射峰,在引入缓蚀剂后LDHs特征峰向小角度偏移。缓蚀剂分子成功结合到LDHs涂层表面。MAO呈现典型的火山口形貌,LDHs纳米片对MAO涂层具有良好的封孔效果,MgLiAl-LDHs三元水滑石结构更致密,缓蚀剂的加入进一步增大了复合涂层的致密度和厚度。电化学实验结果表明,复合涂层样品MgLiAl-LDHs-HNQ的腐蚀电流密度（J_corr）降至4.74×10^-7 A/cm²,电荷转移电阻达到5.7×10⁵ Ω·cm³,且析氢速率大幅下降。涂层划伤实验结果表明,LDHs涂层抑制了MAO划伤位置的扩展,缓蚀剂通过与游离金属离子形成了稳定沉淀物,并在裸露合金表面吸附成膜,实现了涂层的动态自修复。SVET实验结果表明,复合涂层划伤位置的自腐蚀电位经过浸泡后明显降低,进一步验证了涂层的自修复性能。结论所制备的MgLiAl-LDHs-HNQ复合涂层具有较好的耐蚀性和自修复效果,该研究对镁锂合金表面耐蚀自修复功能涂层的应用具有一定参考价值。

Abstract

Magnesium lithium (Mg-Li) alloy is the lightest structural metal, but the alloying of Li elements improves the chemical activity, which seriously limits its application. In order to improve the corrosion protection ability of Mg-Li alloy, this study constructs a layered double hydroxide (LDHs) composite layer based on a micro-arc oxidation (MAO) coating through the one-step hydrothermal method on Mg-Li alloy, and introduces organic corrosion inhibitor molecules salicylic acid (SA) and 2-hydroxy-1,4-naphthoquinone (HNQ) through a low-temperature water bath, thereby creating a corrosion resistant and intelligent self-healing coating. With Mg-8Li alloy as the substrate, an MAO coating is prepared in an aluminate electrolyte. NO₃^- ions are introduced into the hydrothermal solution to grow MgLiAl-LDHs ternary LDHs coating in situ. Self-healing coatings (MgLiAl-LDHs-SA and MgLiAl-LDHs-HNQ) are prepared by introducing SA and HNQ through a low-temperature (50 ℃) water bath, respectively. The structure and composition of the coatings are characterized by SEM, EDS, XPS, FT-IR, and XRD. The corrosion resistance and self-healing performances of the samples are evaluated through electrochemical experiments, scratch tests, and scanning vibrating electrode technique (SVET) measurements. The results exhibit that a composite coating is successfully prepared, exhibiting LDHs structures with (003) and (006) X-ray diffraction peaks. After the introduction of corrosion inhibitors, the characteristic peaks of LDHs shift to smaller angles, indicating the successful incorporation of inhibitor molecules into the LDHs coating surface. The MAO coating displays a typical crater-like morphology, while the LDHs nanosheets effectively cover the defects of the MAO coating. The ternary MgLiAl-LDHs structure is more compact than conventional MgAl-LDHs, and the dope of corrosion inhibitors further increases the thickness and density of the composite coating. Electrochemical experiments exhibit that the corrosion current density (J_corr) of the MgLiAl-LDHs-HNQ decreases to 4.74×10^-7 A/cm², with a charge transfer resistance (R_ct) of 5.7×10⁵ Ω·cm², and a significant reduction in hydrogen evolution rate. Scratch tests reveal that the LDHs coating inhibits the expansion of scratches on the MAO coating, and the corrosion inhibitors achieve self-healing effects by complexing with metal ions and chelating to the exposed metal substrate. SVET experiments demonstrate that the self-corrosion potential at the scratched sites of the composite coating significantly decreases after immersion, further confirming the self-healing ability of the coating. According to the experimental data, it is inferred that the corrosion resistance and self-healing performance of the coating are rooted in the following aspects: The introduction of Li⁺ replaces part of Mg²⁺, and grows perpendicular to the substrate to form a more compact ternary MgLiAl LDHs coating. The compact structure can be used as the first physical barrier to prevent the invasion of corrosive media. When the LDHs coating is eroded by Cl^- ions, the intercalated NO₃^- exchanges with Cl^- ions to form a high concentration of Cl^- ion on the coating surface, thus inhibiting its contact with the metal substrate. SA and HNQ are loaded into the LDHs coating in the form of intercalation anions. When the coating is corroded and degraded, the inhibitor releases and combines with free metal cations to form stable precipitation to participate in the formation of the corrosion product film, forming a self-healing effect. In conclusion, the prepared MgLiAl-LDHs-HNQ composite coating shows the best corrosion resistance and self-healing performance. This study provides valuable insights for the study and application of corrosion-resistant and self-healing functional coatings on Mg-Li alloy.

导出引用

焦佐军, 吴量, 郁富兵, 田珍珍, 周岩, 姚文辉, 袁媛, 谢治辉, 吴国志. 镁合金微弧氧化/MgLiAl-LDHs三元水滑石复合自修复涂层[J]. 表面技术. 2025, 54(15): 33-46 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.15.003

JIAO Zuojun, WU Liang, YU Fubing, TIAN Zhenzhen, ZHOU Yan, YAO Wenhui, YUAN Yuan, XIE Zhihui, WU Guozhi. Self-healing Micro-arc Oxidation/Ternary MgLiAl-LDHs Composite Coating on Magnesium Alloys[J]. Surface Technology. 2025, 54(15): 33-46 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.15.003

中图分类号： TG178

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