微胶囊型自预警自修复环氧涂层制备及其防腐性能研究OA
Preparation and Corrosion Resistance of Microcapsule-based Self-reporting and Self-healing Epoxy Coating
目的 制备微胶囊型自预警自修复环氧涂层,研究其在海水环境中的腐蚀失效行为并揭示自预警自修复机理.方法 筛选最佳工艺参数制备以 2′,7′-二氯荧光素(DCF)为预警剂,桐油(TO)为修复剂,聚氨酯/脲醛(PU/UF)为壳材的DT@PU/UF微胶囊,将其掺入环氧涂层中制备DP涂层并开展海水浸泡实验.通过超景深显微镜、红外光谱、电化学阻抗谱、附着力等测试手段进行涂层失效行为对比分析.结果 以最佳工艺参数制备了DT@PU/UF微胶囊,DCF和TO的负载率分别为 1.3%和 35.82%;随着微胶囊添加量增多至 9%(质量分数),自预警效果逐渐显著,且 DP9wt.%与 DP12wt.%涂层自预警效果差别不大,说明 DP9wt.%涂层表现出良好的自预警性能;在浸泡240 h后,DP9wt.%涂层阻抗值为2.88×105 Ω·cm2,比EP涂层高出一个数量级,并且具有更高的附着力,说明DP9wt.%涂层表现出良好的自修复性能.结论 DP9wt.%涂层具有最佳的自预警与自修复性能.当涂层破损时,微胶囊破裂释放出DCF和TO,DCF与涂层中残留的胺基发生反应产生 DCF 离子沉淀物,在自然光下呈现明显的红色,在紫外光下呈现醒目的黄色荧光;TO 与氧气发生交联聚合反应以修复损伤区域,从而实现涂层自预警与自修复性能.
The organic coating is one of the most widely used anti-corrosion methods,it acts as a physical barrier to isolate the penetration of corrosive medium.However,it is easy to deteriorate and fail under the synergistic effect of complex marine environmental corrosion factors.The self-reporting and self-healing coating can not only report the damaged area of the coating,but also repair the damaged area,thus effectively delaying the process of metal corrosion.In this paper,2′,7′-dichlorofluorescein(DCF)as the reporting agent and tung oil(TO)as the healing agent are used to prepare DT@PU/UF microcapsules by one-step synthesis.A self-reporting and self-healing system with dual signal response of color and fluorescence and self-healing function is developed.The effect of process parameters such as stirring speed,reaction time and the addition amount of emulsifier on the performance of the microcapsules is investigated.By controlling the single variable experiment,the optimal process parameters for preparing microcapsules are determined.The DT@PU/UF microcapsules are prepared by the optimal process parameters and characterized.The DP coating is prepared by incorporating microcapsules into the epoxy coating and a seawater immersion experiment is carried out.The failure behavior of the coating is compared and analyzed by means of super depth of field microscope,infrared spectroscopy,electrochemical impedance spectroscopy and adhesion test.The results show that the loading percentage of DCF and TO in DT@PU/UF microcapsules is 1.3%and 35.82%,respectively.As the microcapsule content increased to 9wt.%,the self-reporting effect is gradually observed to become significant,which indicates that good self-reporting performance can be exhibited by the DP9wt.%coating.With the increase of microcapsule content,the impedance value of the DP coating increases first and then decreases.After 240 h of immersion,the impedance value of the DP9wt.%coating is 2.88×105 Ω·cm2,while the impedance value of the EP coating is only 2.16×104 Ω·cm2,indicating that good self-healing performance is exhibited by the DP9wt.%coating.In the test of adhesion,after being immersed for 240 h,the adhesion of the EP coating and the DP9wt.%coating was decreased from 7.28 MPa and 7.17 MPa to 3.42 MPa and 4.47 MPa,respectively,and the adhesion loss is calculated as 53.0%and 37.7%,respectively.It is considered that the DP9wt.%coating is found to have the best self-reporting and self-healing properties.When the coating is damaged,the microcapsules are ruptured,DCF and TO are subsequently released.The hydrogen on the hydroxyl group of DCF is quickly captured by the residual amine group in the coating,causing DCF to undergo the isomerization reactions.The damaged area of the coating shows red under natural light and yellow fluorescence under ultraviolet light,which plays a role in self-reporting.At the same time,TO is slowly released and the cracks are filled.Under the action of oxygen,cross-linking polymerization is carried out,and a new protective film is formed.The metal is prevented from contacting the corrosive medium,and the self-healing function of the coating is realized.
郭赞洪;曾晓彤;张凯;陆庆红;杨小奎;刘杰
西南技术工程研究所,重庆 400039烟台大学 化学化工学院,山东 烟台 264005西南技术工程研究所,重庆 400039烟台大学 化学化工学院,山东 烟台 264005西南技术工程研究所,重庆 400039烟台大学 化学化工学院,山东 烟台 264005
矿业与冶金
2′,7′-二氯荧光素桐油微胶囊自预警自修复涂层电化学阻抗谱
2′,7′-dichlorofluoresceintung oilmicrocapsuleself-reporting and self-healing coatingelectrochemical impedance spectroscopy
《表面技术》 2026 (8)
54-66,13
山东省泰山学者工程(tsqn202306160)西南技术工程研究所合作基金项目(HDHDW59C020102)烟台先进材料与绿色制造山东省实验室开放课题(AMGM2024F03) Scholar Project of Shandong Province(tsqn202306160)Open Research Foundation of Southwest Technology and Engineering Research Institute(HDHDW59C020102)Science Fund of Shandong Laboratory of Advance Materials and Green Manufacturing at Yantai(AMGM2024F03)
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