镁合金表面自清洁、自修复防护膜研究
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摘要
目的在镁合金表面制备具有自清洁、自修复功能的防护膜,实现镁合金的智能防护。方法采用提拉法在AZ61镁合金表面制备含有pH敏感型"核/壳"纳米结构缓蚀剂的无机-有机杂化硅膜,该膜层具有自清洁、自修复功能。利用扫描电子显微镜(SEM)表征膜层表面形貌,利用接触角测量仪(CA)表征膜层的润湿性和粘附性,利用粉笔灰模拟测试膜层的自清洁功能,利用电化学工作站测试膜层的防护性能,并结合分光光度计对缓蚀剂释放浓度的检测来评价膜层的自修复功能。结果制备的膜层中含有大量pH敏感型"核/壳"纳米结构缓蚀剂,且表面粗糙。水在膜层表面的静态接触角高达156.7°,而滚动角只有5°,表明膜层具有超疏水、低粘附特性,这样水滴滚落到膜层表面时,能够带走膜层表面的污染物,从而实现自清洁功能。开路电位及分光光度计测试表明,溶液pH的变化引起膜层中缓蚀剂释放,从而使膜层实现自修复。极化曲线测试结果表明,含有"核/壳"纳米结构缓蚀剂的膜层样品的腐蚀电流密度比镁合金基底样品小了接近2个数量级,其缓蚀效率可达99.36%。电化学阻抗谱(EIS)测试结果显示,含有"核/壳"纳米结构缓蚀剂的膜层阻值高达85105Ω·cm~2,且具有较持久的自修复防护能力。结论成功制备了含有pH敏感型"核/壳"纳米结构缓蚀剂的无机-有机杂化硅膜,该膜层具有自清洁、自修复功能以及优异的防护性能。
The work aims to realize the intelligent protection for magnesium alloy by preparing the coating with the self-cleaning and self-healing properties on the surface. The inorganic-organic hybrid silicon coating containing pH-sensitive "core/shell" nanostructure inhibitors was prepared on the AZ61 magnesium alloy surface by dip-coating method. The obtained coating had self-cleaning and self-healing properties. The surface morphology of the coating was observed by scanning electron microscopy(SEM). The wettability and adhesion to water were evaluated by contact angle measuring instrument(CA). The chalk ashes were used to simulate the self-cleaning property of the coating. The corrosion protection performance of the coating was analyzed by the electrochemical workstation, and the spectrophotometer was used to evaluate the self-healing property of the coating by measuring the release concentration of the inhibitors. The as-prepared coating had the rough surface, which contained a large number of pH-sensitive "core/shell" nanostructure corrosion inhibitors. The coating surface had a high static water contact angle of 156.7° and low roll-off angle of 5°, which indicated that the coating had superhydrophobic and low adhesive characteristics, so that water droplets could take away the pollutants when rolling down to the surface, thus realizing the self-cleaning property. Open-circuit potential tests and spectrophotometer measurements showed that the change of solution pH led to the release of corrosion inhibitors, thus the coating could heal. From the results of polarization curves, the corrosion current density of the coating containing "core/shell" nanostructure inhibitors was nearly two orders of magnitude smaller than that of the substrate, and the corrosion inhibition efficiency could reach 99.36%. From the electrochemical impedance spectroscopy(EIS), the resistance of the coating containing "core/shell" nanostructure inhibitors was as high as 85 105 Ω·cm~2, which had long-term self-healing protection ability. The inorganic-organic hybrid silicon coating containing p H-sensitive "core/shell" nanostructure inhibitors has been successfully prepared and has self-cleaning, self-healing and excellent protective properties.
The work aims to realize the intelligent protection for magnesium alloy by preparing the coating with the self-cleaning and self-healing properties on the surface. The inorganic-organic hybrid silicon coating containing pH-sensitive "core/shell" nanostructure inhibitors was prepared on the AZ61 magnesium alloy surface by dip-coating method. The obtained coating had self-cleaning and self-healing properties. The surface morphology of the coating was observed by scanning electron microscopy(SEM). The wettability and adhesion to water were evaluated by contact angle measuring instrument(CA). The chalk ashes were used to simulate the self-cleaning property of the coating. The corrosion protection performance of the coating was analyzed by the electrochemical workstation, and the spectrophotometer was used to evaluate the self-healing property of the coating by measuring the release concentration of the inhibitors. The as-prepared coating had the rough surface, which contained a large number of pH-sensitive "core/shell" nanostructure corrosion inhibitors. The coating surface had a high static water contact angle of 156.7° and low roll-off angle of 5°, which indicated that the coating had superhydrophobic and low adhesive characteristics, so that water droplets could take away the pollutants when rolling down to the surface, thus realizing the self-cleaning property. Open-circuit potential tests and spectrophotometer measurements showed that the change of solution pH led to the release of corrosion inhibitors, thus the coating could heal. From the results of polarization curves, the corrosion current density of the coating containing "core/shell" nanostructure inhibitors was nearly two orders of magnitude smaller than that of the substrate, and the corrosion inhibition efficiency could reach 99.36%. From the electrochemical impedance spectroscopy(EIS), the resistance of the coating containing "core/shell" nanostructure inhibitors was as high as 85 105 Ω·cm~2, which had long-term self-healing protection ability. The inorganic-organic hybrid silicon coating containing p H-sensitive "core/shell" nanostructure inhibitors has been successfully prepared and has self-cleaning, self-healing and excellent protective properties.
引文
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[17]LIU Lei,LEI Jing-lei,LI Ling-jie,et al.Robust rareearth-containing superhydrophobic coatings for strong protection of magnesium and aluminum alloys[J].Advanced materials interfaces,2018,5(16):1800213.
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[20]LI Wei,KANG Zhi-xin.Fabrication of corrosion resistant superhydrophobic surface with self-cleaning property on magnesium alloy and its mechanical stability[J].Surface and coatings technology,2014,253:205-213.
[21]SHE Zu-xin,LI Qing,WANG Zhong-wei.Researching the fabrication of anticorrosion superhydrophobic surface on magnesium alloy and its mechanical stability and durability[J].Chemical engineering journal,2013,228:415-424.
[22]LI Ling-xiao,LI Bu-cheng,DONG Jie,et al.Roles of silanes and silicones in forming superhydrophobic and superoleophobic materials[J].Journal of materials chemistry,2016,4:13677-13725.
[23]XU Chun-ling,FANG Liang,HUANG Qiu-liu,et al.Preparation and surface wettability of TiO2 nanorod films modified with triethoxyoctylsilane[J].Thin solid films,2013,531:255-260.
[24]LI Ling-jie,ZHANG Yue-zhong,LEI Jing-lei,et al.Afacile approach to fabricate superhydrophobic Zn surface and its effect on corrosion resistance[J].Corrosion science,2014,85:174-182.
[25]郑兴睿,刘成,于晓华,等.无铬复合钝化膜的微观组织结构及耐腐蚀性能[J].表面技术,2018,47(8):197-203.ZHENG Xing-rui,LIU Cheng,YU Xiao-hua,et al.Microstructure and corrosion resistance of chromium-free composite passive film[J].Surface technology,2018,47(8):197-203.
[26]MICHAILIDIS N,STERGIOUDI F,MALIARIS G,et al.Influence of galvanization on the corrosion fatigue performance of high-strength steel[J].Surface and coatings technology,2014,259:456-464.
[2]孟树昆.中国镁工业进展[M].北京:冶金工业出版社,2012.MENG Shu-kun.Progress of magnesium industry in China[M].Beijing:Metallurgical Industry Press,2012.
[3]宋光铃.镁合金腐蚀与防护[M].北京:化学工业出版社,2006.SONG Guang-ling.Corrosion and protection of magnesium alloys[M].Beijing:Chemical Industry Press,2006.
[4]李玲莉,杨雨云,赵刚,等.镁合金表面钇盐化学转化膜的制备与表征[J].哈尔滨工程大学学报,2012,33(12):1553-1558.LI Ling-li,YANG Yu-yun,ZHAO Gang,et al.Preparation and characterization of yttrium-based chemical conversion coating for magnesium alloys[J].Journal of Harbin Engineering University,2012,33(12):1553-1558.
[5]WANG Xi-mei,ZHU Li-qun,LI Wei-ping,et al.Effects of half-wave and full-wave power source on the anodic oxidation process on AZ91D magnesium alloy[J].Applied surface science,2009,255(11):5721-5728.
[6]TRUONG V T,LAI P K,MOORE B T,et al.Corrosion protection of magnesium by electroactive polypyrrole/paint coatings[J].Synthetic metals,2000,110(1):7-15.
[7]GHALI E,DIETZEL W,KAINER K U.General and cocalized corrosion of magnesium alloys:A critical review[J].Journal of materials engineering and performance,2013,22(10):2875-2891.
[8]KESSLER M R,SOTTOS N R,WHITE S R.Self-healing structural composite materials[J].Composites part A:Applied science and manufacturing,2003,34(8):743-753.
[9]ZHANG X,VANDENBOS C,SLOOF W G,et al.Comparison of the morphology and corrosion performance of Cr(VI)-and Cr(III)-based conversion coatings on zinc[J].Surface&coatings technology,2005,199(1):92-104.
[10]LIN X,EJII A,GENRALD F,et al.Storage and release of soluble hexavalent chromium from chromate conversion coatings equilibrium aspects of Cr[J].Journal of the electrochemical society,2000,147:2556-2562.
[11]SHARMA A K.Chromate conversion coatings for magnesium lithium alloys[J].Metal finishing,1989,87(2):72-74.
[12]OBRIEN P,KORTENKAMP A.The chemistry underlying chromate toxicity[J].Transition metal chemistry,1995,20(6):636-642.
[13]SINKO J.Challenges of chromate inhibitor pigments replacement in organic coatings[J].Progress in organic coatings,2001,42(3-4):267-282.
[14]LI Ling-jie,HE Jian-xin,LEI Jing-lei,et al.Anticorrosive superhydrophobic AZ61 Mg surface with peony-like microstructures[J].Journal of the Taiwan Institute of Chemical Engineers,2017,75:240-247.
[15]LIU Qin,CHEN De-xin,KANG Zhi-xin.One-step electrodeposition process to fabricate corrosion-resistant superhydrophobic surface on magnesium alloy[J].ACS applied materials&interfaces,2015,7(3):1859-1867.
[16]JIA Jing,FAN Jian-feng,XU Bing-she,et al.Microstructure and properties of the super-hydrophobic films fabricated on magnesium alloys[J].Journal of alloys and compounds,2013,554:142-146.
[17]LIU Lei,LEI Jing-lei,LI Ling-jie,et al.Robust rareearth-containing superhydrophobic coatings for strong protection of magnesium and aluminum alloys[J].Advanced materials interfaces,2018,5(16):1800213.
[18]ZHANG Jun-yi,KANG Zhi-xin.Effect of different liquid-solid contact models on the corrosion resistance of superhydrophobic magnesium surfaces[J].Corrosion science,2014,87:452-459.
[19]FENG Li-bang,ZHU Ya-li,WANG Jing,et al.One-step hydrothermal process to fabricate superhydrophobic surface on magnesium alloy with enhanced corrosion resistance and self-cleaning performance[J].Applied surface science,2017,422:566-573.
[20]LI Wei,KANG Zhi-xin.Fabrication of corrosion resistant superhydrophobic surface with self-cleaning property on magnesium alloy and its mechanical stability[J].Surface and coatings technology,2014,253:205-213.
[21]SHE Zu-xin,LI Qing,WANG Zhong-wei.Researching the fabrication of anticorrosion superhydrophobic surface on magnesium alloy and its mechanical stability and durability[J].Chemical engineering journal,2013,228:415-424.
[22]LI Ling-xiao,LI Bu-cheng,DONG Jie,et al.Roles of silanes and silicones in forming superhydrophobic and superoleophobic materials[J].Journal of materials chemistry,2016,4:13677-13725.
[23]XU Chun-ling,FANG Liang,HUANG Qiu-liu,et al.Preparation and surface wettability of TiO2 nanorod films modified with triethoxyoctylsilane[J].Thin solid films,2013,531:255-260.
[24]LI Ling-jie,ZHANG Yue-zhong,LEI Jing-lei,et al.Afacile approach to fabricate superhydrophobic Zn surface and its effect on corrosion resistance[J].Corrosion science,2014,85:174-182.
[25]郑兴睿,刘成,于晓华,等.无铬复合钝化膜的微观组织结构及耐腐蚀性能[J].表面技术,2018,47(8):197-203.ZHENG Xing-rui,LIU Cheng,YU Xiao-hua,et al.Microstructure and corrosion resistance of chromium-free composite passive film[J].Surface technology,2018,47(8):197-203.
[26]MICHAILIDIS N,STERGIOUDI F,MALIARIS G,et al.Influence of galvanization on the corrosion fatigue performance of high-strength steel[J].Surface and coatings technology,2014,259:456-464.