Prepared of Self-Healing and Anti-Corrosion Dual-Function Microcapsules via Emulsion Template Method
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摘要: 首先以木质素磺酸钙作为乳化剂稳定含有桐油（Tung oil）、甲基丙烯酸缩水甘油酯（GMA）和1,6-己二醇二丙烯酸酯（HDDA）的油相，通过紫外辐照引发油相中GMA和HDDA的聚合形成交联聚丙烯酸酯微胶囊壳层；然后向水相中加入苯胺单体，通过木质素磺酸钙和苯胺之间的静电作用将苯胺吸附于微胶囊外表面，以过硫酸铵引发氧化聚合反应形成聚苯胺（PANI）壳层，成功制备得到负载桐油的聚苯胺（Tung oil-PGMA@PANI）微胶囊。该微胶囊为复合壳层结构，其中交联聚丙烯酸酯壳层可以稳定乳液滴形貌并提高微胶囊韧性，PANI壳层赋予微胶囊防腐性能，并且微胶囊内部负载的桐油可以赋予微胶囊自修复性能。添加Tung oil-PGMA@PANI微胶囊的水性环氧涂层表现出优异的自修复性能和防腐蚀性能。Abstract: A new type of microcapsule with self-healing and anti-corrosion function was prepared by emulsion template combined with photopolymerization and in-situ polymerization. Then the dual-functional microcapsules were dispersed in water-based epoxy resin to fabricate smart anti-corrosion coatings. In our strategy, lignosulfonate was used as an emulsifier to stabilize the oil phase composed of tung oil, glycidyl methacrylate (GMA) and 1, 6-hexanediol diacrylate (HDDA). GMA and HDDA underwent crosslinking and formed the shell of microcapsule initiated by UV light. Aniline monomer was added to the water phase subsequently and adsorbed on the outer surface of the microcapsules through the electrostatic interaction between lignosulfonate and aniline. Then the polyaniline (PANI) shell was synthesized subsequently via chemical oxidative polymerization of aniline initiated by ammonium persulfate in the water phase. The polyaniline microcapsules (Tung oil-PGMA@PANI) loaded with tung oil were prepared. The microcapsule has a composite shell structure, in which the PGMA shell layer can stabilize the emulsion droplet and improve the toughness of the microcapsule, the PANI shell layer gives the microcapsule anti-corrosion performance, and the loaded tung oil can give the microcapsule self-healing performance.The FT-IR, TGA and SEM tests proved the successful preparation of the microcapsules, and the tung oil loading in the microcapsules reached 55.1% (mass fraction). The solvent resistance result showed that the microcapsules had strong resistance to water and common non-polar solvents. The self-healing and corrosion inhibition properties of coatings were tested by microscope and salt spray test. As the mass fraction of microcapsules were 7.5%, the defects of coating could be completely repaired after 3 days, and the salt spray test results proved that the microcapsules could significantly improve the anti-corrosion performance of the smart coatings.
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Key words:
- Microcapsule /
- Polyaniline /
- Tung oil /
- Self-healing /
- Anti-corrosion
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图 1 Tung oli-PGMA@PANI微胶囊的制备示意图
Figure 1. Schematic illustration of preparation of the Tung oil-PGMA@PANI microcapsules
图 2 不同质量分数的木质素磺酸钙稳定的乳液静置24 h后的显微镜照片及数码照片（a～e）；乳液液滴的平均粒径（f）
Figure 2. Microscope images and digital photos of emulsion stabilized by different mass fraction of lignosulfonate after 24 h stationary（a−e）; Average particle size of emulsion droplets（f）
图 3 乳液静置24 h后的显微镜照片及数码照片（a～d）；各组乳液液滴的平均粒径（e）
Figure 3. Microscope images and digital photos of emulsions after 24 h stationary（a— d）; Average particle size of each emulsion droplets（e）
图 4 Tung oil-PGMA@PANI微胶囊的光学显微镜照片（a）、SEM照片（b）、局部放大照片（c）和壳层横截面的SEM照片（d）
Figure 4. Optical microscope（a）、SEM image （b）、 magnified image（c） and SEM image of cross section of shell （d） of Tung oil-PGMA@PANI microcapsules
图 5 桐油、PGMA@PANI微胶囊和Tung oli-PGMA@PANI微胶囊的FT-IR光谱（a）和TGA曲线（b）
Figure 5. FT-IR spectra（a） and TGA curves（b） of Tung oil, PGMA@PANI and Tung oil-PGMA@PANI microcapsules
图 6 微胶囊在不同溶剂中桐油随时间的质量损失曲线
Figure 6. Residual of Tung oil mass from microcapsules in different solutions
图 7 涂层截面的扫描电镜图像
w（Tung oil-PGMA@PANI）/%：a−0；b−5；c−7.5；d−10
Figure 7. SEM images of coating fracture surfaces
图 8 Tung oil-PGMA@PANI微胶囊涂层自修复前（a）和自修复3 d后（b）的超景深显微镜图像及愈合划痕的SEM图像（c）
Figure 8. Super depth microscope image of coatings with Tung oil-PGMA @PANI microcapsules before（a） and after self-healing for 3 d（b）;（c）SEM image of healed scratch
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