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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[1] DUTTA D, GAND A N F, CHIH J K, et al. Revisiting graphene-polymer nanocomposite for enhancing anticorrosion performance: A new insight into interface chemistry and diffusion model [J]. Nanoscale,2018,10(26):12612-12624. doi: 10.1039/C8NR03261K [2] MONTEMOR M F. Functional and smart coatings for corrosion protection: A review of recent advances [J]. Surface & Coatings Technology,2014,258:17-37. [3] WHITE S R, SOTTOS N R, GEUBELLE P H, et al. Autonomic healing of polymer composites [J]. Nature,2002,415(6873):817-817. doi: 10.1038/415817a [4] KIM S R, GETACHEW B A, KIM J H. Toward microvascular network-embedded self-healing membranes [J]. Journal of Membrane Science,2017,531:94-102. doi: 10.1016/j.memsci.2017.02.038 [5] HAN S, ZHANG X, GUO Y, et al. Research progress of self-healing material using hollow fiber [J]. New Chemical Materials,2018,46(10):36-39. [6] ZHU D Y, RONG M Z, ZHANG M Q. Self-healing polymeric materials based on microencapsulated healing agents: From design to preparation [J]. Progress in Polymer Science,2015(49-50):175-220. [7] HAFEEZ U, KHAIRUN A M A, ZAKARIA B M, et al. The potential of microencapsulated self-healing materials for microcracks recovery in self-healing composite systems: A review [J]. Polymer Reviews,2016(56):429-485. [8] 杜逸纯, 刘治华. 微胶囊型自修复高分子材料的研究进展 [J]. 皮革与化工,2020,37(4):24-28. doi: 10.3969/j.issn.1674-0939.2020.04.006DU Y C, LIU Z H. Research progress of microcapsule self-healing polymer materials [J]. Leather and Chemicals,2020,37(4):24-28. doi: 10.3969/j.issn.1674-0939.2020.04.006 [9] QIAO L, XUE Y, ZHANG Q Y. Synthesis and characterization of phenol–formaldehyde microcapsules for self-healing coatings [J]. Journal of Materials Science,2017,53:1035-1048. [10] LI H Y, CUI Y X, LI Z K, et al. Fabrication of microcapsules containing dual-functional tung oil and properties suitable for self-healing and self-lubricating coatings [J]. Progress in Organic Coatings,2017,115:164-171. [11] KIM D M, SONG I H, CHOI J Y, et al. Self-healing coatings based on linseed-oil-loaded microcapsules for protection of cementitious materials [J]. Coatings,2018,8(11):404. doi: 10.3390/coatings8110404 [12] 张微, 张志刚, 付广艳, 等. 基于自修复涂料的脲醛树脂微胶囊的制备及其表征 [J]. 材料保护,2017,50(4):64-68.ZHANG W, ZHANG Z G, FU G Y, et al. Preparation and characterization of urea-formaldehyde resin microcapsules based on self - repairing coatings [J]. Materials Protection,2017,50(4):64-68. [13] LI K K, LIU Z J, WANG C J, et al. Preparation of smart coatings with self-healing and anti-wear properties by embedding PU-fly ash absorbing linseed oil microcapsules [J]. Progress in Organic Coatings,2020,145:105668. doi: 10.1016/j.porgcoat.2020.105668 [14] 刘文俊, 程原, 赵本波, 等. 异氰酸酯型微胶囊自修复涂料的研究进展 [J]. 聚氨酯工业,2020,35(2):8-10. doi: 10.3969/j.issn.1005-1902.2020.02.003LIU W J, CHENG Y, ZHAO B B, et al. Research progress of isocyanate microcapsule self-healing coatings [J]. Polyurethane Industry,2020,35(2):8-10. doi: 10.3969/j.issn.1005-1902.2020.02.003 [15] YI H, YANG Y, GU X Y, et al. Multilayer composite microcapsules synthesized by Pickering emulsion templates and their application in self-healing coating [J]. Journal of Materials Chemistry A,2015,3:13749. doi: 10.1039/C5TA02288F [16] YAO J L, YANG C P, ZHU C F, et al. Preparation process of epoxy resin microcapsules for self-healing coatings [J]. Progress in Organic Coatings,2019,132:440-444. doi: 10.1016/j.porgcoat.2019.04.015 [17] 孙金成, 赖俊英, 李婉文, 等. 环氧微胶囊对不同龄期砂浆自修复性能研究 [J]. 混凝土,2020,6:126-129. doi: 10.3969/j.issn.1002-3550.2020.10.030SUN J C, LAI J Y, LI W W, et al. Study on self-repair performance of epoxy microcapsules for mortar at different ages [J]. Concrete,2020,6:126-129. doi: 10.3969/j.issn.1002-3550.2020.10.030 [18] GUO W C, JIA Y, TIAN K S, et al. UV-triggered self-healing of a single robust sio2 microcapsule based on cationic polymerization for potential application in aerospace coatings [J]. ACS Applied Materials & Interfaces,2016,8(32):21046-21054. [19] SHI S E, ZHAO Y Y, ZHANG Z M, et al. Corrosion protection of a novel SiO2@PANI coating for Q235 carbon steel [J]. Progress in Organic Coatings,2019,132:227-234. doi: 10.1016/j.porgcoat.2019.03.040 [20] 董佳豪, 潘威豪, 罗静, 等. Pickering 乳液模板法制备pH 响应型双重防腐蚀功能微胶囊 [J]. 功能高分子学报,2020,33(4):357-364.DONG J H, PAN W H, LUO J, et al. Preparation of pH-responsive dual anticorrosion microcapsules by pickering emulsion template method [J]. Journal of Functional Polymers,2020,33(4):357-364. [21] ZHANG Y J, SHAO Y W, LIU X L, et al. A study on corrosion protection of different polyaniline coatings for mild steel [J]. Progress in Organic Coatings,2017,111:240-247. doi: 10.1016/j.porgcoat.2017.06.015 [22] RAJA P B, SETHURAMAN M G. Natural products as corrosion inhibitor for metals in corrosive media: A review [J]. Materials Letter,2007,62(1):113-116. [23] 孙杨, 张红明, 王献红, 等. 基于可分散聚苯胺的紫外光固化防腐涂料的研究 [J]. 高分子学报,2016(1):105-110. doi: 10.11777/j.issn1000-3304.2016.15156SUN Y, ZHANG H M, WANG X H, et al. Study on UV-curable anticorrosive coatings based on disperse polyaniline [J]. Acta Polymerica Sinica,2016(1):105-110. doi: 10.11777/j.issn1000-3304.2016.15156 [24] 张金勇, 李季, 王献红, 等. 聚苯胺在防腐领域的应用 [J]. 功能高分子学报,1999,12(3):350-356.ZHANG J Y, LI J, WANG X H, et al. Application of polyaniline in anticorrosion field [J]. Journal of Functional Polymers,1999,12(3):350-356. [25] OGURTSOV N A, PUD A A, KAMARCHIK P, et al. Corrosion inhibition of aluminum alloy in chloride mediums by undoped and doped forms of polyaniline [J]. Synthetic Metals,2004,143(1):43-47. doi: 10.1016/j.synthmet.2003.10.015 -
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