用于金属腐蚀探测的荧光探针研究进展

doi:10.12068/j.issn.1005-3026.2025.20240196

摘要/Abstract

摘要：

传统的金属腐蚀探测手段存在操作复杂、不能实时探测、价格昂贵等缺点，而荧光探针具有灵敏度高、结构简单、无损探测、原位探测、实时探测等优点，是一种有前景的金属早期腐蚀探测方法，可在金属早期腐蚀阶段自主指示涂层损伤和金属腐蚀.根据金属的腐蚀过程综述了荧光探针探测腐蚀的原理，将其分为对pH敏感、对金属离子敏感、对涂层损伤敏感3类，这些探针能根据pH变化、金属离子存在和涂层损伤显示荧光反应，作为腐蚀开始的早期预警.总结了不同种类荧光探针的应用场景和优缺点，最后对荧光探针探测技术的发展前景进行了展望.

关键词: 荧光, 探针, 腐蚀探测, 金属, 涂层

Abstract:

The traditional methods of metal corrosion detection have the disadvantages of complex operation， inability to perform real-time monitoring， and high costs， while the fluorescent probe has the advantages of high sensitivity， simple structure， non-destructive detection， in-situ detection， real-time detection， etc. It is a promising method for monitoring the early corrosion of metal， which can independently indicate the coating damage and metal corrosion in the early corrosion stage of metal. The principle of fluorescent probe in monitoring corrosion were reviewed according to the corrosion process of metal， and the fluorescent probes were classified into three categories： pH-sensitive， metal ion-sensitive， and coating damage-sensitive， which display fluorescent reaction according to the change in pH， the presence of metal ions， and the damage of coatings as an early warnings of the beginning of corrosion. The application scenarios， advantages， and disadvantages of different types of fluorescent probes were summarized， and finally， the development prospects of fluorescent probe monitoring technology were predicted.

Key words: fluorescence, probe, corrosion detection, metal, coating

中图分类号:

TG 174

朱琦, 丁超凡, 闫俊丽, 张涛. 用于金属腐蚀探测的荧光探针研究进展[J]. 东北大学学报（自然科学版）, 2025, 46(8): 93-104.

Qi ZHU, Chao-fan DING, Jun-li YAN, Tao ZHANG. Research Progress of Fluorescent Probes for Metal Corrosion Detection[J]. Journal of Northeastern University(Natural Science), 2025, 46(8): 93-104.

图/表 10

图1 金属腐蚀机制与探测机制[7]（a）—金属腐蚀机制；（b）—探测金属腐蚀的机制.

Fig.1 Mechanisms of metal corrosion and detection[7]

图2 负载酚酞和缓蚀剂的涂层的腐蚀抑制与预警机制[8]注：p（MMA-co-BA）为聚甲基丙烯酸甲酯-丙烯酸丁酯（a）—涂料设计方案；（b）—腐蚀传感涂层表面随浸泡时间t的变化情况；（c）—双功能涂层工作机理.

Fig.2 Corrosion inhibition and early warning mechanism of coatings loaded with phenolphthalein and corrosion inhibitors [8]

图3 负载Zr-MOF@CD@MBI纳米填料的智能涂层在金属腐蚀中的损伤预警与修复机制[17]（a）—涂层损伤预警（浅划痕）和及时报告/修复金属腐蚀（深划痕）的智能涂层示意图；（b）—浸泡1 h；（c）—浸泡6 h；（d）—浸泡12 h；（e）—浸泡24 h；（f）—浸泡48 h.

Fig.3 Damage warning and repair mechanism of intelligent coating loaded with Zr-MOF@CD@MBI nanofillers in metal corrosion [17]

图4 FD1在酸性环境下的荧光机制、荧光发射和含FD1的透明环氧涂层的Al 1052在3.5%NaCl溶液中浸泡不同天数后的图像[20]（a）—在低pH下FD1的荧光机制；（b）—酸性环境下的FD1在510 nm波长光激发下的荧光发射；（c）—浸泡2 d；（d）—浸泡3 d.

Fig.4 Fluorescence mechanism and fluorescence emission of FD1 in acidic environments and images of FD1-contain-ing transparent epoxy-coated Al 1052 after immersion in 3.5% NaCl solution for different days [20]

图5 Phen与Fe2+反应机理及其对涂层样品性能的影响[23]（a）—Phen与Fe²⁺反应机理及不同浓度下颜色变化；（b）—涂层样品环境放置9个月后的照片；（c）—紫外光和可见光下的性能示意图及划痕照片.

Fig.5 Reaction mechanism of Phen with Fe2+ and its effect on properties of coated samples[23]

图6 在不同光源下激发不同含量Fe3+的S-Rxbxja乙醇溶液[32]（a）—自然光；（b）—紫外光.

Fig.6 Excitation of ethanol solutions of S-Rxbxja different contents of Fe3+ under different light sources[32]

图7 RBA荧光开关机制及涂层腐蚀检测性能[30]（a）—荧光开关机制；（b）—无划痕；（c）—“—”形划痕；（d）—“X”形划痕；（e）—“O”形划痕.

Fig.7 RBA fluorescence switching mechanism and coating corrosion detection performance[30]

图8 负载CDs-APhen的Q235钢在HCl溶液中浸泡后的光学与紫外线图像[37]（a）—光学图像；（b）—紫外图像.

Fig.8 Optical and UV images of Q235 steel loaded with CDs-APhen after immersion in HCl solution [37]

图9 8-HQ与铝离子的络合及含有不同浓度探针的涂层荧光预警性能[42]（a）—荧光图像；（b）—络合机理；（c）—探针质量分数为0；（b）—探针质量分数为7.5%.

Fig.9 Complexation of 8-HQ with aluminum ions and fluorescence early-warning properties of coatings containing probes of different concentrations [42]

图10 环氧树脂/PAN@(HDI+TPE)纤维涂层的自预警与自修复机制及涂层在质量分数为3.5%的NaCl溶液中浸泡不同时间后的图像[46]（a）—纤维涂层示意图；（b）—自预警机制；（c）—自修复机制；（d）—1 h；（e）—5 h；（f）—30 h；（g）—120 h.

Fig.10 Mechanism of self-warning and self-repair of epoxy/PAN@(HDI+TPE) fiber coatings and images of coatings after immersion in 3.5 wt% NaCl solution for different duration[46]

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