超疏水表面研究进展

超疏水表面由于其独特的润湿性,在自清洁等领域具有非常重要的作用。本文阐述了超疏水表面的研究背景、制备超疏水表面的基本方法和含氟及无氟超疏水表面的最新研究进展,总结了当前超疏水表面仍需解决的问题并提出了建议,最后对未来绿色环保的超疏水表面进行了展望。     

树莓状结构纳米复合粒子超疏水表面的研究进展

综述了制备树莓状结构纳米复合粒子的方法,包括化学键接方法和物理吸附方法,以及树莓状结构纳米复合粒子构建超疏水表面的流程,最后指出了目前该领域的应用前景及以后的研究发展方向。     

纤维素基超疏水纸的研究进展

从制备方法角度概述了纤维素基超疏水纸的研究现状,重点介绍了化学改性法、物理化学改性法、表面涂布法和纳米粒子改性法,同时介绍了超疏水纸在油水分离和微流体装置中的最新应用,对pH、温度和光照具有智能响应性超疏水表面的开发,以及超疏水纸表面力学性能和耐酸碱腐蚀性能的改善。使用廉价、绿色生物聚合物研制多功能、性能优异的超疏水纸产品是未来的发展方向,材料学、聚合物化学、纳米技术和机械学多学科理论知识的综合运用,是实现超疏水表面突破性发展的关键,也是满足工业化生产要求迫切需要解决的难题。     

超疏水表面的研究进展

综述了超疏水的研究进展,在以荷叶和水黾为例介绍湿润现象的基础上,讨论了超疏水结构在自然界中的真实存在。还介绍了接触角的原理和接触角与粗糙表面的联系,探究了湿润的微观现象以及接触角的影响因素。不仅介绍了超亲水表面的主要制备方法及其相关的理论研究,还综述了超疏水材料在耐腐蚀、自清洁、织物中的应用。目前超疏水材料研究如火如荼,超疏水表面具有非常广阔的发展前景。超亲水表面材料目前还是处于大规模工业化应用之前的研究阶段,成本较高、耐久性差都是这种材料的不足之处,因此还有极大的空间有待后人去探究发掘。     

超疏水表面的研究进展

综述了超疏水的研究进展,在以荷叶和水黾为例介绍湿润现象的基础上,讨论了超疏水结构在自然界中的真实存在。还介绍了接触角的原理和接触角与粗糙表面的联系,探究了湿润的微观现象以及接触角的影响因素。不仅介绍了超亲水表面的主要制备方法及其相关的理论研究,还综述了超疏水材料在耐腐蚀、自清洁、织物中的应用。目前超疏水材料研究如火如荼,超疏水表面具有非常广阔的发展前景。超亲水表面材料目前还是处于大规模工业化应用之前的研究阶段,成本较高、耐久性差都是这种材料的不足之处,因此还有极大的空间有待后人去探究发掘。     

超疏水表面润湿性能研究

润湿性能是固体表面的重要特征之一,具有特殊润湿性和可控润湿性材料因其巨大的应用潜力而成为人们关注的热点。介绍超疏水状态下Wenzel和Cassie-Baxter两种接触角模型及其相互关系,讨论了微纳米结构对疏水表面接触角的影响,总结了近年来超疏水表面制备技术的研究进展,并展望了超疏水表面润湿理论研究前景。     

超疏水表面制备技术的研究进展

对固体表面浸润性的基本理论及超疏水表面制备技术进行了概括,简单介绍了本研究小组最新研制的一种超疏水涂层材料制备技术。     

羧基化纳米纤维素乳化马来松香甘油酯乳液稳定性及超疏水纸制备

采用溶剂助溶法制备马来松香酯乳液,确定了最佳的工艺合成条件。比较分析了十二烷基硫酸钠（SDS）、烷基酚聚氧乙烯醚（OP-10）和羧基化纳米纤维素（CNF-C）马来松香酯乳液粒径和稳定性的影响。采用双层涂布的方式,机械浆纳米纤维素和沉淀碳酸钙PCC作为第一道涂布,马来松香酯乳液作为第二道涂布,构建了超疏水性纸张的工艺策略。研究发现：马来松香酯的最佳合成工艺条件为马来松香和甘油的配比为1:3;引发剂（偶氮二异丁腈）用量为0.4%;催化剂（纳米ZnO2）用量为2%;在250℃条件下反应5小时。羧基化纳米纤维素作为乳化剂,制备的马来松香乳液粒径达到527 nm,在室温下静置90天不破乳分层,具有较强的稳定性。双层涂布制备的PCC-CNF-MAP-DG涂布纸与水的接触角159.1°,cobb值为2.4 g/m2,且经过200次折叠后仍具有超强的疏水性能,并且耐酸碱,具有良好的化学稳定性。纸张的超疏水性源于双级结构间滞留的空气对水滴的托举,在纸张纤维表面形成致密的疏水层。     

纤维基改性SiO2柔性超疏水表面构建研究

采用溶胶-凝胶法以正硅酸四乙酯(TEOS)、3-氨基丙基三甲氧基硅烷(APTMS)和十六烷基三甲氧基硅烷(HDTMS)为原料,制得改性SiO2溶胶,将其应用于柠檬酸预先处理的棉织物,构建棉纤维基柔性超疏水表面.采用场发射扫描电镜(FE-SEM)观察得到改性SiO2溶胶干燥后形成有球形颗粒的致密粗糙膜,改性SiO2红外谱图(FT-IR)显示氨丙基和十六烷基在SiO2表面接枝.当HDTMS浓度为2％时,整理的棉织物静态接触角为155.3°,动态滚动角是8°,达到优异的超疏水效果,经洗涤20次后接触角仍为143.4°,具有疏水耐久性.扫描电子显微镜(SEM)观察得知整理棉纤维洗涤前后表面均具有较好的粗糙结构,整理棉纤维表面形成了牢固的改性SiO2疏水膜.     

由无机特殊表面结构构造的超疏水材料

超疏水材料因在自清洁、防腐蚀、防冰附以及减阻等功能上具有广泛的应用,吸引了越来越多的关注。近年来,无机材料因易于构造具有特殊形貌的高比表面结构,在超疏水领域中显示出独特的优势。本文在简要介绍超疏水现象的定义、发展与应用的基础上,综述了超疏水理论的三个经典模型,并对国内外部分已商业化的超疏水材料进行了分析和总结。重点概括了不同种类无机材料构建的超疏水表面的研究进展。最后,本文总结了目前超疏水材料在制备过程中存在的一些问题,针对性地提出该领域未来研究的两个主要趋势：从仿生角度改进材料设计,制备集强附着力与耐久性于一体的多功能复合涂层;降低制备成本以推动产品的规模化和实用化。     

Fabrication of flower clusters-like superhydrophobic surface via a UV curable coating of ODA and V-PDMS

In this work, a flower clusters-like superhydrophobic surface was fabricated via an ultraviolet (UV) curable coating of octadecylamine (ODA) and vinyl-terminated polydimethylsiloxane (V-PDMS). ODA self-assembled into many flower clusters-like structures on the surface of the coating, increasing the roughness of the coating surface without additional nanoparticles. V-PDMS formed a highly crosslinked network under a UV lamp, which would be helpful for a robust superhydrophobic surface. The obtained PDMS/ODA fabric showed water contact angle of 161° and sliding angle of 5°. The durability of the superhydrophobic surface was tested by water impacting, tube brush scrubbing, knife scratching, hand twisting, finger pressing, tape adhesion, abrasion, continuous rinsing, and chemical conditions. The experimental results indicated that the superhydrophobic surface have good durability for long service life. Moreover, the PDMS/ODA fabric could selectively absorb oils from water with good separation performance. This work will provide a facile, low cost, and versatile method to prepare superhydrophobic surfaces, and enhance their efficiency of oil–water separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48210.     

生物基聚苯并嗪/纤维素纳米晶超疏水防腐蚀涂层的制备及性能

以腰果酚、十八胺和多聚甲醛为原料合成出生物基苯并嗪单体,以单宁酸为固化剂,采用差示扫描量热分析技术和红外光谱考察了苯并嗪单体的热固化行为,结果表明单宁酸可以有效降低苯并嗪的开环固化温度。在钢片表面首先制备聚苯并嗪涂层作为底漆,再通过在涂层中掺杂氨基修饰纤维素纳米晶制备面漆,构建出静态水接触角为161.1°±2.9°的生物基超疏水防腐蚀涂层（PBTC）。该超疏水涂层表现出良好的耐高低温性能和耐刮擦性。电化学测试结果表明PBTC涂层在NaCl水溶液中浸泡30天后仍然具有良好的防腐蚀性能。     

Facile preparation of robust superhydrophobic surface based on multi-scales nanoparticle

A new superhydrophobic surface based on multi-scales nanoparticle was designed and prepared to enhance the robustness and reproducibility. The influence of multi-scale nanoparticles on the structure and property of the superhydrophobic surface was further investigated. The superhydrophobic surface with optimized composition did not only show high contact angle of 160°-166.3° but also exhibited good durability to the mechanical, chemical, and thermal environments. Furthermore, the superhydrophobic surface was evaluated for application in anticorrosion, anti-icing, and self-cleaning. This study provides a new method to prepare robust superhydrophobic surface based on polymer nanocomposite coating for various potential applications.     

Fabrication of superhydrophobic titanium surfaces by anodization and surface mechanical attrition treatment

A superhydrophobic surface of titanium was fabricated by anodization in sodium chloride solution followed by immersion in perfluorodecyltriethoxysilane. The surface characteristics of the anodic film (morphology, composition, microstructure, and adhesion) were investigated by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and scratch testing. The anodic film was comprised of TiO₂ and TiCl₃ with a thickness of 50 nm. The anodized titanium surface exhibited a hierarchical structure, which consisted of a microscale horn structure with a nanoscale strip-overlay. This structure provided superhydrophobicity (water contact angle: 151.9° and sliding angle: 3°) following the immersion process. Furthermore, coverage of the hierarchical structure on the anodized titanium surface was improved by performing surface mechanical attrition treatment (SMAT) to grain-refine titanium surface which was then anodized and it enhanced a slightly increased water contact angle. The thickness (200 nm) of the anodic film on the SMAT-pretreated titanium surface was much higher than that on the titanium surface (50 nm). This resulted from a large number of grain boundaries on the surface serving as a fast diffusion path during anodization. However, the adhesion of the SMAT-and-anodized film was worse than that formed by anodization only. This is due to a large number of pores within the SMAT-and-anodized film.     

一种防渗透硅烷纳米粒子/聚乳酸复合超疏水涂料

以十六烷基三甲氧基硅烷与原硅酸四乙酯为原料,经溶胶-凝胶反应得到疏水硅烷纳米粒子,再将其加入到聚乳酸的二氯甲烷溶液中与硅烷偶联剂正丙氨基三乙氧基硅烷反应,得到一种具有优异防渗透性能的超疏水涂料。采用FTIR和SEM对涂料结构和形貌进行了表征。红外分析表明,硅烷偶联剂不参与化学反应。SEM表明,涂料的超疏水性源自表面多级拓扑结构。接触角测试表明,硅烷纳米粒子极大地提高了涂料的防水性,当硅烷纳米粒子用量为4%(以聚乳酸/二氯甲烷溶液总质量计)时,超疏水涂料的水接触角达到150°以上;在10～20min测试时间内,相对于单一疏水硅烷纳米粒子〔接触角降速150(°)/min〕和单一聚乳酸溶液〔接触角降速9.5(°)/min〕涂覆,疏水硅烷纳米粒子/聚乳酸复合防水涂料的涂覆大幅度提高了样品的防渗透性,接触角降速仅为0.8(°)/min,这是疏水硅烷纳米粒子的多级结构与聚乳酸优异的成膜性相结合的结果。     

Fabrication of robust self-cleaning superhydrophobic coating by deposition of polymer layer on candle soot surface

A facile and inexpensive way have been developed to fabricate robust self-cleaning superhydrophobic coating by depositing polymer layer on candle soot (CS) surface using dip coating method. The stability and robustness of the CS deposited superhydrophobic surface is much weaker due to weak interaction and nonchemical bonding with the substrate. We introduced a thin layer of polystyrene, polyethylene, polypropylene (PP), and polyvinylidene fluoride on CS surface in order to improve its mechanical properties. The fabricated surfaces with the use of respective polymers exhibited water contact angles of nearly 170, 174, 175, and 171° with sliding angles of 2, 1, 1, and 3°, respectively. Although, all the polymers used in this work exhibited excellent superhydrophobic and self-cleaning surface property, we found that the PP deposited CS surface exhibit better stability against water jet hitting and water drop impact tests. The PP deposited CS surface almost maintained their surface properties even after 50 cycles of sandpaper abrasion and 20 cycles of adhesive tape peeling tests. The mechanical durability tests confirmed that PP is a better polymer to improve the long-term durability of CS surface. Therefore, this simple, time saving, and inexpensive method for fabricating superhydrophobic coating can be used for potential industrial application.     

纳米二氧化钛/氟树脂超疏水涂层的制备及性能

以金红石型纳米TiO2及自制的氟树脂制备了氟碳涂料,采用刷涂法于铁片表面构筑了超疏水涂层。考察了纳米TiO2与氟树脂用量、热处理温度等对涂层疏水性的影响,并分别用扫描电镜(SEM)、接触角测量仪观察和测试了涂层表面的微观结构及疏水性。结果表明,涂层表面的水接触角随着氟树脂用量的增加而增大,随纳米TiO2用量的增加呈先增后减的趋势。涂层的吸水率随着氟树脂用量的增加而减少,随纳米TiO2用量的增加呈先减后增的趋势。随着热处理温度的升高,涂层的水接触角先增后减,吸水率先减后增。最佳工艺条件是TiO2及氟树脂的质量分数分别为12%与40%,热处理温度170℃。此条件下得到的涂层表面具有微/纳二元粗糙结构,对水静态接触角达152°,为超疏水涂层,并具有优异的耐水、耐酸碱、耐洗刷、耐沾污及自清洁性能。     

纳米杂化耐磨超疏水环氧树脂涂层的构筑及性能

采用层层组装法通过十八烷基胺（C18-NH2）、正硅酸乙酯（TEOS）、γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）合成出长链烷基改性纳米粒C18-NH2/570@SiO2,将其引入有机硅改性环氧树脂,制备得到耐摩擦性能优异的超疏水环氧树脂涂层C18-NH2@SiO2/DE51。采用FT-IR、XRD、XPS、TEM、AFM等对纳米粒子的结构以及涂层的成膜形貌进行表征。结果表明,长链烷基纳米粒成功引入聚合物链段中,并且涂层表面喷涂C18-NH2/570@SiO2后表面粗糙度明显提高。通过接触角、透光率、自清洁、耐酸碱和耐摩擦测试表明,当喷涂质量分数为0.8%的纳米粒子时,改性后的环氧树脂涂层接触角可以达到150.6±0.6°,滚动角可达到7.8±0.4°,透光率可达到91.98%,拥有良好的自清洁、耐酸碱和耐摩擦性能并且摩擦次数可达到1500次以上。     

Novel superhydrophobic top coating on surface modified PVC-coated fabric

A superhydrophobic surface was created on poly(vinylchloride)-coated architectural fabric using spray coating method. Dispersions of nanoparticles and a flourochemical were prepared as top coating solutions. After spray-dry-cure process, contact angle, sliding (tilt) angle, 3 M water repellency test and surface morphology were compared between uncoated and top coated PVC surfaces. The results indicated that a specific nano-TiO₂ dispersion top coating produced a superhydrophobic layer on the top of the PVC surface with high contact angle (150°) and very low sliding angle (2°). Combination of two major requirements, the magnified of the degree of roughness and low surface energy, created self-cleaning effect on the PVC surface. Abrasion fastness of superhydrophobic top coating was improved by surface oxidation via UV–ozone surface treatments. Spectroscopic analysis demonstrated that formation of oxygenated functional groups has improved PVC wettability and adhesion. Results of artificial weathering test indicated no change in superhydrophobicity of top coated PVC.     

碳黑/PDMS超疏水涂层的制备及防冰性能 (急)

固体表面冰的形成和累积引起了一系列的安全问题同时造成了巨大的经济损失。因此，防冰对减少冰灾和经济损失具有重要意义。通过喷涂方法在基质上喷涂碳黑纳米粒子、聚二甲基硅氧烷 (PDMS)以及十七氟葵基三乙氧基硅烷 (PFDTES)的混合液制备了一种具有防冰性能的碳黑/PDMS超疏水涂层。碳黑使涂层具有微纳粗糙结构，PDMS作为粘合剂增加涂层的牢度，PFDTES赋予表面较低的表面能。所制备的涂层具有优异的超疏水性能，使水滴在表面结冰的时间延迟到160 s，是普通玻璃结冰时间的5倍多。同时，冰的粘附强度也大大的减小。此外，涂层还展现出优异的自清洁性能、耐酸、碱、盐腐蚀和耐紫外灯照射性能。