目的 为开发一种兼具物理屏蔽与自修复功能的环氧复合防腐涂层。方法 采用共沉淀法合成负载2-巯基苯并噻唑（MBT）的CaAl-MBT LDH@ZrP异质结复合纳米材料,并将其引入环氧树脂（EP）中制备复合涂层。通过扫描电镜（SEM）和X射线衍射（XRD）表征不同纳米填料（α-ZrP、CaAl LDH-ZrP、CaAl-MBT LDH@ZrP）的微观形貌和化学结构。结合紫外-可见吸收光谱分析MBT的释放行为。最后,利用电化学阻抗谱（EIS）和盐雾试验系统评价涂层的防腐性能。结果 CaAl-MBT LDH@ZrP复合纳米材料对MBT具有良好的负载能力。MBT的释放呈现两阶段特征：最初7 h内快速释放,之后速率减缓并趋于稳定,表明其能够实现长效的缓蚀效果。CaAl LDH的高表面能改善了α-ZrP与环氧树脂的界面相容性,使填料在基体中均匀分散,构建致密屏障结构。在3.5%（质量分数）NaCl溶液中浸泡60 d后,CaAl-MBT LDH@ZrP/EP涂层的低频阻抗值（|Z|0.01 Hz）较纯EP涂层提升4个数量级。盐雾实验显示该涂层能有效抑制腐蚀反应的进行,验证了MBT在碳钢表面的自修复效应。结论 通过构建CaAl-MBT LDH@ZrP异质结填料,实现了物理屏蔽与自修复的协同增效。该复合涂层在长期服役条件下表现出优异的阻隔性能和自修复能力,为开发智能长效防腐涂层提供了创新性策略。
Abstract
This study aims to develop a novel epoxy coating that integrates both physical shielding and active self-repairing effect to enhance long-term anti-corrosion ability. A heterojunction composite nanomaterial, CaAl-MBT LDH@ZrP, was synthesized via a co-precipitation method, in which calcium-aluminum layered double hydroxide (CaAl LDH) was intercalated with 2-mercaptobenzothiazole (MBT). The synthesized nanocomposite was then introduced into an epoxy (EP) matrix to fabricate a composite epoxy coating. The morphology and chemical composition of different nanofillers (α-ZrP, CaAl LDH-ZrP, CaAl-MBT LDH@ZrP) were characterized by scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD) and X-ray photoelectron spectroscopy (XPS). The release behavior of MBT molecular was monitored with an ultraviolet-visible absorption spectroscopy (UV-vis). The anti-corrosion properties of the coatings were systematically evaluated through electrochemical impedance spectroscopy (EIS) and salt spray test. SEM images revealed that the CaAl-MBT LDH@ZrP nanocomposites exhibited a distinct lamellar structure, affirming the successful assembly of the heterojunction. Importantly, the intercalation of MBT did not disrupt the original layered structure of CaAl LDH. The XPS high-resolution spectra of S2p revealed peaks positioned at 167.5 and 168.7 eV, respectively, attributable to C—S—C and C—S—O bonds. These signals confirmed the successful intercalation of MBT between the CaAl LDH layers. The release of MBT molecular exhibited two-stage features: an initial rapid release within the first 7 hours, followed by a sustained release phase, demonstrating its capability for long-term corrosion inhibition. SEM analysis of cross section for the ZrP/EP coating revealed severe aggregation of α-ZrP nanosheets due to poor interfacial compatibility with the epoxy matrix. The CaAl LDH-ZrP/EP coating exhibited a smooth and dense internal structure, which was attributed that the high surface energy and abundant polar functional groups of CaAl LDH significantly improved the interfacial compatibility between α-ZrP nanosheets and the epoxy matrix. EIS results demonstrated that after immersion in 3.5wt.% NaCl solution for 60 days, the low-frequency impedance modulus (|Z|0.01 Hz) of the CaAl-MBT LDH@ZrP/EP coating reached 2.3×109 Ω·cm2, which was four orders of magnitude higher than that of the pure EP coating (3.1×105 Ω·cm2), indicating significantly enhanced corrosion resistance. EDS elemental analysis showed that the surface on the carbon steel removing CaAl-MBT LDH@ZrP/EP coating had the highest iron content (89.29wt.%) and the lowest chlorine content (0.15wt.%), further demonstrating that the CaAl-MBT LDH@ZrP/EP coating has best barrier ability against corrosive media. Additionally, the |Z|0.01 Hz value of the scribed CaAl-MBT LDH@ZrP/EP coating remained above 106 Ω·cm2, and its |Z|0.01 Hz value rose to 1.8×106 Ω·cm2 at 48 h, suggesting that the MBT molecular released from the nanocomposite adsorbed onto the exposed carbon steel surface, effectively inhibiting electrochemical corrosion reaction. Even after 240 hours exposure of salt spray test, the scribed CaAl-MBT LDH@ZrP/EP coating showed only a small number of corroded areas, demonstrating that MBT molecular was able to adsorb onto the scratched area to inhibit the corrosion reaction. Synergistic enhancement of active corrosion inhibition and physical shielding was successfully achieved by constructing the CaAl-MBT LDH@ZrP heterojunction. The CaAl-MBT LDH@ZrP/EP composite coating exhibited excellent long-term barrier performance and self-repairing capability, providing an innovative strategy for the development of intelligent and durable anti-corrosion coatings.
关键词
环氧涂层 /
阻隔作用 /
自修复 /
α-ZrP /
CaAl LDH /
MBT
Key words
epoxy coating /
high barrier /
self-repairing /
α-ZrP /
CaAl LDH /
MBT
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基金
高端装备涂料全国重点实验室开放课题基金（GZ-23-009）
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