Article(id=1195733615666578374, tenantId=1146029695717560320, journalId=1189873562199433220, issueId=1195733614798357446, articleNumber=null, orderNo=null, doi=10.19710/J.cnki.1003-8817.20250015, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=null, receivedDateStr=null, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1763014709631, onlineDateStr=2025-11-13, pubDate=1745078400000, pubDateStr=2025-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763014709631, onlineIssueDateStr=2025-11-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763014709631, creator=13701087609, updateTime=1763014709631, updator=13701087609, issue=Issue{id=1195733614798357446, tenantId=1146029695717560320, journalId=1189873562199433220, year='2025', volume='', issue='4', pageStart='1', pageEnd='72', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763014709424, creator=13701087609, updateTime=1763015213929, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1195735730925388785, tenantId=1146029695717560320, journalId=1189873562199433220, issueId=1195733614798357446, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1195735730925388786, tenantId=1146029695717560320, journalId=1189873562199433220, issueId=1195733614798357446, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=13, endPage=24, ext={EN=ArticleExt(id=1195733615901459402, articleId=1195733615666578374, tenantId=1146029695717560320, journalId=1189873562199433220, language=EN, title=Progress of Research on Bionic Corrosion Resistant Surface of Magnesium Alloy, columnId=1190284220686766583, journalTitle=Automobile Technology & Material, columnName=Original article, runingTitle=null, highlight=null, articleAbstract=

To explore the surface technology for corrosion protection of magnesium alloys, biomimetic anticorrosion surfaces such as superhydrophobic and slippery surfaces have received extensive attention in the past decade. This paper summarizes typical bionic superhydrophobic anticorrosion methods for preparing magnesium alloy surface, including electrochemical deposition, chemical etching, anodic oxidation, laser etching, spraying and so on, and discusses the characteristics of each preparation method and the research progress of bioinspired surface anticorrosion of magnesium alloy. In addition, the paper also summarizes the commonly used methods for preparing anticorrosion slippery surface of magnesium alloy, which means constructing structured substrate first and then injecting lubricant, and one-step spraying method. The research progress of slippery anticorrosion surface of magnesium alloy is discussed. Finally, the challenges and future development directions of superhydrophobic and slippery surfaces of magnesium alloys are summarized.

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为探索镁合金腐蚀保护的表面技术,仿生耐腐蚀如超疏水、超滑表面在过去十年中受到广泛关注。总结了制备镁合金表面的典型仿生超疏水防腐蚀方法,包括电化学沉积、化学刻蚀、阳极氧化、激光刻蚀、喷涂法等,并探讨了各制备方法的特点和镁合金仿生表面防腐蚀的研究进展。此外,总结了制备镁合金防腐蚀超滑表面的常用方法,即先构建结构化基底再注入润滑剂,以及一步喷涂法,并探讨了镁合金超滑防腐蚀表面的研究进展。最后,总结了镁合金超疏水、超滑表面面临的挑战和未来发展方向。

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刘燕(1974—),女,教授,研究方向为材料仿生科学与工程;
田勇(1974—),男,教授,研究方向为机电装备制造。
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=TPPHCCPFCwSRf3LkkixX5A==, magXml=CoQ9lOFId2xpQ7ZILrNIeA==, pdfUrl=null, pdf=eV5KLJQtqNKocEmNvGrCAQ==, pdfFileSize=6903972, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=9PlQ0Xi+nsAGR/nYqLsSIQ==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=//5IT73AqeUErmbE18cFMA==, mapNumber=null, authorCompany=null, fund=null, authors=

张文良(1991—),男,博士学位,研究方向为材料仿生科学与工程。

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张文良(1991—),男,博士学位,研究方向为材料仿生科学与工程。

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张文良(1991—),男,博士学位,研究方向为材料仿生科学与工程。

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镁合金仿生耐腐蚀表面的研究进展
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张文良 , 魏冬松 , 刘燕 , 史亚菲 , 王元鹏 , 田勇
汽车工艺与材料 | 镁合金汽车产业创新论坛优秀论文 2025,(4): 13-24
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汽车工艺与材料 | 镁合金汽车产业创新论坛优秀论文 2025, (4): 13-24
镁合金仿生耐腐蚀表面的研究进展
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张文良, 魏冬松, 刘燕, 史亚菲, 王元鹏, 田勇
作者信息
  • 吉林大学仿生工程教育部重点实验室, 长春 130022
  • 张文良(1991—),男,博士学位,研究方向为材料仿生科学与工程。

通讯作者:

刘燕(1974—),女,教授,研究方向为材料仿生科学与工程;
田勇(1974—),男,教授,研究方向为机电装备制造。
Progress of Research on Bionic Corrosion Resistant Surface of Magnesium Alloy
Wenliang Zhang, Dongsong Wei, Yan Liu, Yafei Shi, Yuanpeng Wang, Yong Tian
Affiliations
  • Key Laboratory of Bionic Engineering (Ministry of Education), Jilin University, Changchun 130022
出版时间: 2025-04-20 doi: 10.19710/J.cnki.1003-8817.20250015
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为探索镁合金腐蚀保护的表面技术,仿生耐腐蚀如超疏水、超滑表面在过去十年中受到广泛关注。总结了制备镁合金表面的典型仿生超疏水防腐蚀方法,包括电化学沉积、化学刻蚀、阳极氧化、激光刻蚀、喷涂法等,并探讨了各制备方法的特点和镁合金仿生表面防腐蚀的研究进展。此外,总结了制备镁合金防腐蚀超滑表面的常用方法,即先构建结构化基底再注入润滑剂,以及一步喷涂法,并探讨了镁合金超滑防腐蚀表面的研究进展。最后,总结了镁合金超疏水、超滑表面面临的挑战和未来发展方向。

镁合金  /  超疏水  /  超滑  /  防腐方法  /  仿生

To explore the surface technology for corrosion protection of magnesium alloys, biomimetic anticorrosion surfaces such as superhydrophobic and slippery surfaces have received extensive attention in the past decade. This paper summarizes typical bionic superhydrophobic anticorrosion methods for preparing magnesium alloy surface, including electrochemical deposition, chemical etching, anodic oxidation, laser etching, spraying and so on, and discusses the characteristics of each preparation method and the research progress of bioinspired surface anticorrosion of magnesium alloy. In addition, the paper also summarizes the commonly used methods for preparing anticorrosion slippery surface of magnesium alloy, which means constructing structured substrate first and then injecting lubricant, and one-step spraying method. The research progress of slippery anticorrosion surface of magnesium alloy is discussed. Finally, the challenges and future development directions of superhydrophobic and slippery surfaces of magnesium alloys are summarized.

Magnesium alloy  /  Superhydrophobic  /  Super-slippery  /  Anticorrosion methods  /  Bionic
张文良, 魏冬松, 刘燕, 史亚菲, 王元鹏, 田勇. 镁合金仿生耐腐蚀表面的研究进展. 汽车工艺与材料, 2025 , (4) : 13 -24 . DOI: 10.19710/J.cnki.1003-8817.20250015
Wenliang Zhang, Dongsong Wei, Yan Liu, Yafei Shi, Yuanpeng Wang, Yong Tian. Progress of Research on Bionic Corrosion Resistant Surface of Magnesium Alloy[J]. Automobile Technology & Material, 2025 , (4) : 13 -24 . DOI: 10.19710/J.cnki.1003-8817.20250015
镁合金是最轻的金属结构材料,具有特殊的性能,包括高比强度、低密度、高导热性、优异的机加工性能、良好的电磁干扰屏蔽性能、可控环境下良好的焊接性和可回收性,其在汽车工业、航空航天、生物医用材料和电子设备等领域有着广阔的应用前景[1-6]。然而,在日常生活和工业生产中,镁合金经常暴露在潮湿或液体环境中,与其他金属合金相比,镁合金的化学性质活泼,更易被腐蚀,从而在短时间内失去机械性能[7-9]。因此,解决镁合金的耐腐蚀问题具有重要意义[10-13]
在自然界中,许多生物,如荷叶、玫瑰、仙人掌刺、猪笼草等,经过长期进化,形成了具有超润湿性的复杂、精致表面[14-17]。这些生物在其生活环境中表现出很高的拒液性。受荷叶超疏水性的启发,研究人员通过制备接触角大于150°和滚动角小于10°的超疏水表面用于镁合金的腐蚀保护。超疏水表面之所以具有较强的拒液性,是由于表面微纳纹理和低表面能的协同作用[18-19]。空气层可存储在微纳纹理中,形成固-液-气三相界面,即Cassie-Baxter态[20-22]。储存在超疏水表面纹理上的空气层可避免腐蚀介质与金属基体接触,对镁合金具有良好的腐蚀保护作用[23-26]。受猪笼草启发的超滑表面一般具有极高的液体排斥性和极低的滑动角,液体运动滑动角小于10°。拒液性的光滑液体注入多孔表面,通过油相和水相之间的排斥性使镁合金避免接触腐蚀物质,起到优异的防腐蚀效果。
本文综述了近年来镁合金超疏水、超滑防腐2种典型仿生表面的常见制备方法及耐腐蚀性研究进展,并分析总结了超疏水、超滑表面的制备方法在镁合金防腐蚀应用中存在的问题及发展方向。
随着表面改性技术的发展,镁合金超疏水表面的制备方法越来越多。超疏水表面的构建通常需满足2个条件,一是需要构造微观结构来增加表面的粗糙度,二是需要使用低表面能试剂修饰表面。当水接触角大于150°且滚动角小于10°时,可获得超疏水表面。在镁合金上制备超疏水表面的常用方法有电化学沉积法、化学刻蚀法、阳极氧化法、激光刻蚀法和喷涂法等。
电化学沉积是指以镁合金作为阴极,惰性金属作为阳极,浸入电解液中,电解液中的离子在外电场作用下迁移的过程,并在电极上发生氧化还原反应从而在镁合金表面沉积形成电镀层。同时,结合低表面能物质修饰后获得超疏水表面。
Liu[27]等通过一种简便、快速的电沉积工艺,在Mg-Sn-Zn(TZ51)镁合金上构建了具有微/纳米级结构的超疏水表面。超疏水微纳结构所捕获的空气层可避免腐蚀性物质与基底的接触,从而有效保护镁合金[23-24]。随着电沉积时间增加,表面粗糙度明显增大。通过调整电沉积时间(10 min),接触角可达到160.4°±0.7°,具有优异的超疏水性能。电化学测试表明,涂层的耐腐蚀性大幅提高,腐蚀电流密度降低2个数量级,如图1a图1b所示。Wang[28]等通过电化学沉积在AZ41镁合金上制备了防腐CaCO3/MgO涂层。与未进行预处理的涂层相比,电化学沉积的CaCO3/MgO涂层具有更好的防腐性能,腐蚀电流密度降低了3个数量级,这归功于外CaCO3层和致密的内层MgO。Liu[29]等通过合镀镍工艺和全氟丙烯酸改性,成功制备了超疏水表面。随着电解液浓度的增加,表面沉积的结构越发致密,NiCl2·6H2O的最佳电解液浓度为1.0 mol/L。分层微纳结构与低表面能的全氟丙烯酸的协同作用对超疏水表面的形成起到了重要作用,水接触角达到160.2°±1°。超疏水表面的电化学测量表明,与裸基底相比,超疏水表面的缓蚀性能改善显著,腐蚀电流密度降低1个数量级,如图1c图1d所示。电化学沉积法制备的超疏水表面具有优异防腐蚀性能的原因主要有:超疏水微纳结构中稳定捕获空气层[20-21]与电沉积所形成的致密粗糙微纳结构可阻挡腐蚀性物质的渗透。
电化学沉积法工艺简单、表面微结构可塑性强,但仅能针对导电界面构建微纳复合结构,应用范围受限。
化学刻蚀法是指对镁合金表面进行刻蚀,再以低表面能物质加以修饰或结合其他技术从而获得超疏水表面。
Liu[30]等受具有超疏水特性的荷叶和红玫瑰花瓣等植物表面的启发,通过激光对样品进行处理,然后将其浸入不同浓度(浓度分别为0.1 mol/L、0.3 mol/L和0.5 mol/L,刻蚀时间分别为15 s、40 s和60 s)的AgNO3水溶液中化学刻蚀,最后用硅烷进行改性,制备了具有微米级火山口状和纳米级花朵状二元结构的疏水表面[14,16]。与裸镁合金相比,所制备镁合金疏水表面的耐腐蚀性能更高,腐蚀电流密度降低了2个数量级。Shi[31]等通过连续抛光、4M盐酸溶液蚀刻(18 min)、沸腾处理(60 s)和氟烷基硅烷改性制备了具有接触角为160.5°的迷宫状凹凸微结构和扭曲纳米片组成的多功能分层二元结构超疏水表面。电化学测试表明,超疏水样品在海水中具有优异的防腐性能,腐蚀电流密度降低了3个数量级。Wei[32]等通过简单的化学蚀刻和表面改性,在AZ31和AZ91表面制备了超疏水表面,如图2所示。随着刻蚀时间的增加,表面粗糙度明显增加。与裸镁合金相比,所制备超疏水表面的耐腐蚀性能显著提高,腐蚀电流密度降低了1个数量级。此外,超疏水表面在较大的温度和pH值范围内分别表现出高温稳定性和化学稳定性。化学刻蚀法通过构建粗糙的微纳结构和低表面能改性来制备超疏水表面,粗糙微纳结构中捕获空气层可有效避免腐蚀性物质与基底的接触,从而保护镁合金免受腐蚀性物质的侵蚀[22,25]
化学蚀刻具有操作简单和成本低的特点,但均匀性和重复性较差。此外,化学蚀刻技术通常需要使用强酸、强碱或有害的蚀刻试剂,易造成二次污染。
激光刻蚀法通过激光对镁合金表面进行加工,然后再通过低表面能物质修饰或结合其他技术获得超疏水表面。
Li[33]等通过激光刻蚀技术在Mg-3Al-1Zn(AZ31)镁合金表面制备了具有不同中心距(80 μm、250 μm)的周期性微尺度乳头状凹坑微结构,经过化学蚀刻和硬脂酸改性后,其接触角达到158.2°,具有优异的超疏水性能。通过调整镁合金微观结构中心距,实现了从低粘附力(中心距为80 μm)到高粘附力(中心距为250 μm)的转变。与AZ31镁合金相比,所制备的超疏水表面的耐腐蚀性能显著提高,腐蚀电流密度降低了1个数量级。Wei[34]等通过简单的激光刻蚀和退火处理,在轧制的Mg-9Al-1Zn(AZ91)镁合金板材上制备了超亲水和超疏水表面,如图3所示。在160 ℃下退火60 min后,激光刻蚀的超亲水表面转变为超疏水表面,水接触角高达158.8°±2°。相较于裸镁合金,超疏水表面具有更高的耐腐蚀性,腐蚀电流密度降低了1个数量级。激光刻蚀和改性后的表面主要通过超疏水空气层阻止腐蚀性物质与基底的接触,从而保护镁合金免受腐蚀性物质的侵蚀。Zhang[35]等通过激光加工和喷涂涂层制备了一种无氟、坚固和自修复的超疏水涂层。所喷涂涂层中纳米颗粒的增加使所制备超疏水表面粗糙度也有所提高。超疏水空气层以及致密有机涂层的协同阻隔作用使其对镁合金具有>99%的缓蚀效率。在多次机械磨损后仍能表现出良好的防腐性能,腐蚀电流密度降低了2个数量级。
激光刻蚀具有高精度和可控性的特点,但也存在维护和操作成本高、不适合大规模生产且制备工艺复杂等缺陷。
微弧氧化法又称微等离子体氧化,依靠电弧发射引起的瞬时高温、高压在合金表面形成金属氧化膜,然后再通过低表面能物质修饰或结合其他技术获得超疏水表面。
Cui[36]等通过对AZ31镁合金进行微弧氧化和硬脂酸表面改性,制备了超疏水涂层。随着硬脂酸改性时间的增加,涂层疏水性逐渐提高,当改性时间达到10 h时,涂层的接触角达到151.5°。涂层超疏水涂层所捕获的空气层有效抑制了镁合金的腐蚀,尤其是点腐蚀,腐蚀电流密度降低了4个数量级。Jiang[37]等通过在植酸和Ce(NO3)3溶液中进行微弧氧化和循环组装,在AZ91镁合金上制备了超疏水表面,如图4所示。组装周期对复合涂层的表面形貌、润湿性和抗腐蚀能力有显著影响。随着组装周期的增加,超疏水表面粗糙度有所提高,经过3次循环组装后,可获得接触角为159°的超疏水表面。电化学测试表明,超疏水复合涂层将镁合金的耐腐蚀性提高了3个数量级。此外,72 h的电化学测试表明,复合涂层可为镁合金提供长期防腐保护。Wang[38]等通过在等离子电解氧化陶瓷底层上组装改性二氧化硅基有机-无机混合薄膜,在AZ31镁合金上实现了具有优异防腐性能的超疏水双层涂层,腐蚀电流密度降低了5个数量级。所制备涂层具有优异的拒液性,其隔离层将底层基材与外部环境隔离,为多层覆盖的镁合金提供了长期的活性腐蚀保护。微弧氧化法通过构建致密的金属氧化膜或陶瓷氧化层,并使用低表面能改性实现对镁合金的高效防腐。空气层和致密氧化膜可有效避免腐蚀性物质与基底的接触,从而保护镁合金。
微弧氧化可通过特殊溶液或颗粒构建特定的表面微结构,具有表面粗糙度可控的特性,但存在稳定性较差、适用范围有限的缺陷。
喷涂法通常是将均匀的涂料喷涂在各种基体表面,从而制备超疏水表面。喷涂法适用于大规模制备超疏水表面,适合实际生产需求。但其喷涂过程中也存在表面粗糙度不可控等问题。
Zhang[39]等通过简单喷涂由疏水改性环氧树脂和2种改性纳米填料(碳纳米管和二氧化硅)组成的混合物,制备了一种耐腐蚀的光热自修复超疏水涂层。随着碳纳米管和二氧化硅含量的增加,涂层的超疏水性能有所提高。过量添加的碳纳米管和二氧化硅会降低涂层的附着力。环氧树脂质量分数为10%的碳纳米管和环氧树脂质量分数为20%的二氧化硅被认为是最佳添加量,腐蚀电流密度降低了5个数量级。在经过20 m的磨损后,涂层仍表现出了优异的防腐能力。Wei[40]等通过喷涂法在镁合金上制备了一种由底部绝缘膜和顶部超疏水膜组成的无氟电热/超疏水涂层。随着石墨烯含量的增加,颗粒发生团聚,粗糙度增大,涂层超疏水性提高。由于超疏水性涂层具有持久的空气层和有机涂层,因而具有长期防腐蚀效果,腐蚀电流密度降低了6个数量级,此外,超疏水涂层在受到化学侵蚀后能通过修复超疏水性恢复涂层的防腐蚀性能。Li[41]等通过在镁合金基底上喷涂由环氧树脂、聚二甲基硅氧烷和改性二氧化硅组成的无氟悬浮液,制造出具有接触角为159.5°、滑动角为3.8°的超疏水涂层。所制备的涂层具有出色的长期防腐蚀性能,腐蚀电流密度降低了2个数量级,如图5所示。喷涂法通过构建致密的超疏水涂层、微纳结构所捕获的空气层以及致密涂层中所添加颗粒的阻隔效应有效抑制了腐蚀性物质与基底的接触,从而保护镁合金免受侵蚀。
除上述方法外,为提升镁合金耐腐蚀性能,还有一些其他的超疏水表面制备方法。
Liu[42]等通过对TZ51镁合金进行不同加工电流密度下的阳极氧化处理,并在室温下进行硬脂酸改性后,制备了具有水接触角高达163°的超疏水表面。与裸镁合金基底相比,超疏水样品具有良好的耐腐蚀性能,腐蚀电流密度降低了1个数量级,如图6所示。Wang[43]等通过水热法在Mg-9Li合金上实现了涂层超疏水和防腐蚀性能的增强。由于微纳米粗糙结构和低表面能,涂层接触角达到154°,可有效延缓腐蚀破坏,腐蚀电流密度降低了2个数量级。Xi[44]等通过浸涂法和加热工艺制备了可降解的复合材料,用于提高AZ91D镁合金的耐腐蚀性。在50 ℃下加热30 min使分子重排,从而获得疏水和超疏水特性。所制备的复合材料具有高效的自清洁性能、良好的粘合强度和在潮湿环境中的稳定性。电化学测量结果显示,复合材料显著提高了镁合金在NaCl溶液中的耐腐蚀性,腐蚀电流密度降低了5个数量级。Jin[45]等通过水热处理在镁合金基底上形成了氢氧化镁层,在氢氧化镁层上接枝硬脂酸制备了水接触角为159°的超疏水表面,提高了镁合金的耐腐蚀性。水热处理2 h后,样品表面布满了与基底平行或相交的片状氢氧化镁层。随着水热处理时间的延长,相交片层结构更加致密,片层也越来越大,片层之间的空间越来越小,形成了更加均匀的微纳米结构。盐水浸泡10天后,相较于镁合金,涂层的腐蚀电流密度降低了1个数量级。
注入滑液的多孔表面一般由具有适当表面张力的结构基底和低表面张力流体组成,低表面张力流体通常称为润滑剂。结构化基底提供毛细吸附孔或凹坑以保留流体。大多数报道的基底均为疏水或超疏水基底,因为其对低表面张力流体有很高的亲和力,能够保持润滑液的稳定,防止液滴进入。超滑表面一般具有极高的液体排斥性和极低的滑动角,液体运动所需的表面倾角小于10°。
制备镁合金超滑表面通常需要构建结构化表面,其可提供很好的平台用于容纳润滑液体,形成低摩擦的界面,从而排斥各种材料。近年来,构建结构化表面后注入润滑剂的研究较多。Wei[46]等通过激光刻蚀聚二甲基硅氧烷@Al2O3@Fe2O3涂层(PAFC)薄膜,刻蚀后的PAFC由微/纳米结构纹理组成,呈现超疏水性能。超滑表面通过将润滑剂(氟硅油)注入PAFC微/纳米结构纹理中获得。在质量分数为3.5%的NaCl水溶液中浸泡60天后,涂层超滑表面的润滑层仍然存在,且涂层的防腐蚀能力未明显变化,硅油对水基溶液的排斥性使其有效阻隔了腐蚀性物质。此外,由于硅油具有流动性,可及时流动至受损区域,因此,可延缓划痕缺陷区域的腐蚀,如图7所示。Tian[47]等通过阳极氧化和水热处理相结合的原位生长,在镁-锂合金上制备了陶瓷状层状氢氧化物(Ceramic-like Layered Hydroxide,CLH)涂层,然后用1H、1H、2H、2H-全氟癸基三乙氧基硅烷进行化学改性并注入润滑剂,获得光滑液体注入的多孔表面(Smooth Liquid Injected Porous Surface,SLIPS)。润滑剂的注入显著改善了涂层的防腐蚀性能,相较于裸镁合金,涂层的腐蚀电流密度仍降低了2个数量级,且SLIPS表润滑剂的流动性使其具有自愈能力,可为镁合金提供更持久的防腐能力。Wei[48]等通过一步电沉积在高活性镁锂合金上构建了微结构,随后使用食用蜂蜡-葵花籽油形成复合油凝胶浸泡超滑表面,所制备的超滑表面表现出99.99%的高腐蚀抑制效率,远超疏水表面。超滑表面具有自修复能力,高温时蜂蜡-葵花籽油变为液相可流动至受损区域,在经历相变后可修复表面损伤,从而保持防腐能力。
与超疏水空气层不同,润滑剂通过与水不混溶来实现对腐蚀性物质的有效阻隔。微/纳米结构表面的锁定作用可使润滑剂均匀分散在表面上。微纳米结构可实现稳定的框架作用,具有高毛细管力,在水中仍可保留润滑剂。润滑剂的表面能较低,不会被水取代。当表面受到损伤时,超滑表面润滑剂的流动性使其可及时填补受损区域,具有自愈能力。
此外,研究人员通过一步喷涂制备超滑表面。Zhang[49]等受青蛙皮肤的启发,通过一步喷涂由环氧树脂、硅油、改性纳米TiO2和改性微米云母粉的混合物,制备了一种仿生无氟多功能超滑涂层(Multifunctional Slippery Coating,MSC)。与超疏水涂层和传统SLIPS的特殊界面防腐机理不同,MSC将硅油储存在涂层表面和内部,使涂层整体具有出色的阻隔效果,对镁合金表现出超长效的防腐能力。在经过中性盐雾试验60天和质量分数为3.5%的NaCl溶液浸泡60天后,涂层仍展现出优异的腐蚀保护能力,且MSC的划痕缺陷区域在盐雾试验14天后仅在划痕区域出现轻微点蚀,如图8所示。MSC优异的防腐性能促进了镁合金在更广泛的领域的应用。
一步喷涂制备的超滑涂层具有优异的超长效防腐能力,可能原因为存储于MSC内部的硅油可填充涂层内部孔隙,储存在涂层内的硅油与水介质具有排斥性,能有效阻止腐蚀离子和水的渗透。此外,添加的TiO2或片状云母粉可进一步阻塞涂层内部的孔隙,并阻碍腐蚀性物质的渗透路径,进一步增强MSC的防腐能力。因纳米TiO2固有的纳米结构和较大的比表面积为硅油分子提供了足够的附着空间,有利于硅油在涂层内部的储存。MSC缺陷区长期延迟腐蚀效应的原因推测为涂层内部紧密排列的TiO2或片状云母粉之间存在细小的通道,硅油可从这些通道缓慢释放至划痕处,从而长时间阻止腐蚀性物质的侵入。
镁合金的耐腐蚀性能差,限制了其在不同领域的应用,提高镁合金的耐腐蚀性已成为亟待解决的问题。基于仿生原理,在镁合金表面制备了超疏水、超滑表面,以提高镁合金的耐腐蚀性能。超疏水表面的制备基于2个原则:粗糙微观结构和低表面能。超滑表面的制备通常基于结构化基底和低表面张力流体。本文总结了制备镁合金超疏水表面的典型方法,包括电化学沉积、化学刻蚀、阳极氧化、激光刻蚀、喷涂法等,并总结了制备镁合金超滑表面的制备方法,即先构建结构化基底再注入润滑剂,以及镁合金防腐超滑表面的一步喷涂。此外,对近年来镁合金超疏水表面和超滑表面的研究进展进行了分析。目前已提出了多种在镁合金表面构建超疏水、超滑表面的加工技术,但在工业应用之前还需解决以下难题:
a.超疏水、超滑表面的机械耐久性。目前已设计出了具有优异机械耐久性的超疏水、超滑表面,但仅在实验室中完成测试。如机械稳定性的测试方法为在砂纸上摩擦一定距离,不足以代表实际应用情况,应在更严格的实际应用环境中检测超疏水、超滑表面对镁合金的长期稳定性能。
b.超疏水、超滑表面的稳定性。在运输过程中,灰尘、颗粒物和其他污染物可能会粘附在涂层表面,影响表面的超疏水、超滑性能。因此,可能需要额外的清洁和维护程序来确保涂层的功能。此外,超疏水表面在潮湿环境中的不稳定性以及超滑表面润滑剂的流失均会降低涂层的使用寿命和整体效率。
c.超疏水、超滑表面存在制造成本高、大规模生产受限、有毒氟烷基硅烷和含氟硅油等含氟物质的问题。因此,需要开发环境友好、低成本且设计简单有效的生产工艺。
d.虽然其他基材上的超疏水、超滑表面在海洋环境中的应用已被广泛研究,但镁合金超疏水、超滑表面在海洋环境中的应用研究较少。为拓宽镁合金的应用领域,应开展镁合金超疏水、超滑表面在高盐、高湿、高溶氧、微生物和冲击腐蚀等海洋环境中的腐蚀行为的研究。
  • 国家自然科学基金(U2106226)
参考文献 引证文献
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2025年第卷第4期
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doi: 10.19710/J.cnki.1003-8817.20250015
  • 首发时间:2025-11-13
  • 出版时间:2025-04-20
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国家自然科学基金(U2106226)
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    吉林大学仿生工程教育部重点实验室, 长春 130022

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刘燕(1974—),女,教授,研究方向为材料仿生科学与工程;
田勇(1974—),男,教授,研究方向为机电装备制造。
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2种不同金属材料的力学参数

Family
属数
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genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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