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基于坡缕石制备的稳定超双疏涂层

  • 高兴华1

    机 构：

    1. 中国矿业大学（北京）机械与电气工程学院 北京 100083

    ×
  • ， 黄啸1

    机 构：

    1. 中国矿业大学（北京）机械与电气工程学院 北京 100083

    ×
  • ， 张晓强1

    机 构：

    1. 中国矿业大学（北京）机械与电气工程学院 北京 100083

    ×
  • ， 王欣2

    机 构：

    2. 中国航发北京航空材料研究院 北京 100095

    ×
  • ， 许春玲2

    机 构：

    2. 中国航发北京航空材料研究院 北京 100095

    ×

1. 中国矿业大学（北京）机械与电气工程学院 北京 100083；
2. 中国航发北京航空材料研究院 北京 100095；

Preparation of Stable Superamphiphobic Coatings Based on Palygorskite

  • GAO Xinghua1

    Affiliation：

    1. School of Mechanical & Electronic Engineering, China University of Mining & Technology, Beijing 100083 , China

    ×
  • ， HUANG Xiao1

    Affiliation：

    1. School of Mechanical & Electronic Engineering, China University of Mining & Technology, Beijing 100083 , China

    ×
  • ， ZHANG Xiaoqiang1

    Affiliation：

    1. School of Mechanical & Electronic Engineering, China University of Mining & Technology, Beijing 100083 , China

    ×
  • ， WANG Xin2

    Affiliation：

    2. AECC Beijing Institute of Aeronautical Materials, Beijing 100095 , China

    ×
  • ， XU Chunling2

    Affiliation：

    2. AECC Beijing Institute of Aeronautical Materials, Beijing 100095 , China

    ×

1. School of Mechanical & Electronic Engineering, China University of Mining & Technology, Beijing 100083 , China；
2. AECC Beijing Institute of Aeronautical Materials, Beijing 100095 , China；

作者简介:

高兴华，男，1998年出生，硕士研究生。主要研究方向为超双疏涂层制备及应用E-mail: 17810286684@sina.cn;

王欣，男，1983年出生，博士，研究员。主要研究方向为金属零件抗疲劳表面强化技术与残余应力分析。E-mail: rasheed990918@163.com

通讯作者:

黄啸，男，1988年出生，博士，副教授。主要研究方向为材料表面工程E-mail: hx@cumtb.edu.cn

中图分类号:TB333；TB37

DOI:10.11933/j.issn.1007-9289.20230816001

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目录contents

    摘要

    水、油接触角大于 150°的超双疏表面，因其在防污、防粘、防腐、自清洁和管道运输等方面具有巨大的应用潜力而备受关注。但因为超双疏表面结构的脆弱性，目前制备出的超双疏涂层仍具有稳定性不足和价格高昂的问题。使用溶胶-凝胶法在坡缕石（palygorskite, pal）表面原位生长二氧化硅（SiO2）并进行氟化改性，制备高含氟量的 pal@SiO2-F 填料，利用分层喷涂的方法将 pal@SiO2-F 填料与聚二甲基硅氧烷（PDMS）结合，制备出具有超双疏性的 PDMS / pal@SiO2-F 涂层。pal@SiO2-F 填料中氟元素含量达到了 33.14%，涂层的水、白矿油接触角分别达到 160°和 158.2°。电镜观察发现，复合涂层表面的微米尺度 pal 颗粒与表面生长的 SiO2纳米突起堆积，共同构成双重粗糙结构。PDMS 作为粘结剂，为涂层与基底提供稳定的结合力， pal 颗粒为表面的纳米结构提供支撑，使涂层捕获的气膜能够稳定存在，涂层在经历白矿油浸泡和腐蚀测试后，仍表现出优异的拒液性，同时在自清洁测试中展现出优异的自清洁性和抗污性。PDMS / pal@SiO2-F 超双疏涂层凭借其独特的制备方法和性能及相对低廉的制造成本展示出广泛应用的潜力。

    Abstract

    The challenges posed by liquid–solid infiltration phenomena, such as icing on transmission lines, corrosion on ship surfaces, blockage in oil pipelines, and fogging on car windows, significantly impact both industrial productivity and daily life. Inspired by the natural world, including lotus leaves, pitcher plants, and water striders, researchers have sought to develop biomimetic anti-wetting surfaces to address these issues. Superamphiphobic surfaces, characterized by water and oil contact angles exceeding 150°, have drawn considerable attention for their potential in anti-fouling, anti-sticking, anti-corrosion, self-cleaning, and pipeline transportation applications. However, the inherent fragility of the superamphiphobic surfaces' dual rough structure poses a significant challenge in creating durable superamphiphobic coatings. In this study, micron-sized irregular pal particles were utilized as precursors to develop pal@SiO2-F fillers, with polydimethylsiloxane (PDMS) serving as the binder due to its outstanding bonding strength, corrosion resistance, and elasticity. A nano-scale SiO2 rough structure was in situ synthesized on the pal particles' surface through a modified sol-gel method. Subsequently, the pal@SiO2 particles underwent fluorination using 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTES) to create pal@SiO2-F fillers with a high surface fluorine conten. Layered spraying of the binder and filler yielded PDMS / pal@SiO2-F superamphiphobic coatings with exceptional stability. The surface morphology and chemical composition of the pal@SiO2-F fillers were characterized using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). The analyses showed that the originally smooth pal particles acquired notable nano-projections in the form of short rods, which interlocked to form numerous pores on the surface of the pal@SiO2-F. The nano-protrusions on the pal particles are composed of amorphous silica, confirming successful in-situ growth of silica on the pal particle surfaces. The fluorine content in the pal@SiO2-F filler reached 33.14%, illustrating effective grafting of high fluorine groups onto the pal@SiO2 particles. Surface structures of the PDMS / pal@SiO2-F coatings, observed via SEM, reveal that micron-scale pal particles and SiO2 nano-protrusions on the pal surface collaborate to create a dual rough structure. PDMS serves as the binder, ensuring stable adhesion between the coating and substrate while supporting the micron-sized pal particles. This support enables the surface nanostructure to stably capture a gas film attributing to the coating’ s adaptability across diverse environments. This adaptability is further bolstered by PDMS's chemical inertness and strong adhesion. In anti-wetting tests, the pal@SiO2-F coating demonstrated remarkable repellency towards various liquids with surface tensions (γ ≥ 30.7 mN / m) and maintained its superamphiphobicity through 50 cycles of white mineral oil immersion. After 12h immersion in NaOH, HCl, and NaCl solutions, the coatings displayed oil contact angles (OCA) greater than 130° and water contact angles (WCA) greater than 150°, retaining their superhydrophobicity and oleophobicity under corrosive conditions and effectively shielding the substrate from infiltration and corrosion. Self-cleaning tests further showcased the coatings' ability to shed water droplets, which removed sand from the surface without leaving residues, even at low inclination angles, highlighting the coatings' superior self-cleaning and anti-fouling properties. Consequently, the superamphiphobic coating, with its distinct features and cost-effective production method, holds potential for broad application in various fields.

  • 0 前言

  • 水 / 油接触角大于 150°的超双疏表面，因其在防污[1]、防粘[2]、防腐蚀[3-5]、自清洁[6-7]和油气运输[8]等方面广阔的应用前景而备受关注。受自然界中如荷叶、猪笼草[6]和水黾腿[9]等动植物的启发，人们通过构造具有低表面能和微 / 纳二元结构的表面来实现超疏水。然而油的表面能远低于水，具有普通微 / 纳结构的表面难以实现超疏油。因此，在构造超疏油表面时，须要保证表面材料具有极低的表面能和特殊的粗糙结构，如重入式内凹结构[10]和内凹悬臂结构等 [11]，以保证涂层表面处于 Cassie-Baxter 状态[12]。构造超双疏表面需要严格精确的表面结构控制并使用具有足够低表面能的材料。目前利用光刻、化学气相沉积和反应离子刻蚀[13]等技术组合制备出的超双疏涂层较为昂贵，且通常缺乏较强的机械坚固性[14]。为了解决上述问题，DONG 等[9]尝试引入纳米黏土来增强涂层的化学和机械稳定性，并降低涂层制造成本。同时，涂料与基底结合力的强弱也会影响涂层的坚固性，为了让涂层能适应较为严苛的环境，许多人尝试引入不同种类的高分子粘结剂，以加强涂层与基底的结合力。ZHOU 等[15]引入聚二甲基硅氧烷（PDMS） 作为粘结剂，将硅纳米丝喷涂到预拉伸基底，成功制备了在高拉伸状态下仍能保持超拒液性的涂层。 PENG 等 [8] 将聚偏氟乙烯-六氟丙烯 / 聚醚砜 （PVDF-HFP / PES）与低表面能功能填料混合喷涂，制备出能应用于油气运输等极端环境的超双疏涂层。涂层的拒液性与鲁棒性的良好结合是涂层应用的先决条件。目前部分商用含氟低表面能有机涂层在应用中展现出了良好的稳定性，如特氟龙（PTFE） 涂层[16]和聚偏氟乙烯（PVDF）涂层等，但通常无法实现超双疏 [17]。而使用单一的无机材料，也存在基体与涂层粘附较弱、表面粗糙结构易被破坏等问题[11]。因此，尝试将有机与无机材料的优势结合，利用有机粘接剂提高涂层与基底的结合强度，以及各填料颗粒间的结合强度，同时，利用无机填料颗粒构造表面粗糙结构。这种方案能够使得涂层同时拥有较好稳定性与超双疏性。

  • 通常为了构造超双疏所需的微纳粗糙结构，会选用纳米颗粒作为前驱体。利用纳米颗粒的团聚效应，构造独特的微纳粗糙结构，在光滑板面上形成超双疏涂层。但纳米小颗粒堆积后颗粒间空隙很小，限制了粘结剂的进入，同时团聚的颗粒间结合力较弱，因此颗粒间可粘结性较差，经外力作用后，表面结构易被破坏，表现出较差的稳定性和坚固性。增加颗粒尺寸至微米级别，在微米颗粒表面构造纳米粗糙结构，则可以在构造微纳粗糙结构的同时，利用微米颗粒相对耐磨的特点，保护纳米粗糙结构不被外力破坏，以此提高整个涂层稳定捕获气膜的能力[18]。

  • 本文研究选择微米级的无规则 pal 颗粒作为 pal@SiO2-F 填料制备的前驱体，选用具有优异粘结强度、耐蚀性和弹性的 PDMS 作为粘结剂。为了获得具有低表面能、高纳米粗糙结构的功能填料，采用改性溶胶-凝胶法，在 pal 颗粒表面生长纳米级的 SiO2 粗糙结构，随后利用 1H，1H，2H，2H-全氟癸基三乙氧基硅烷（PFDTES）对 pal@SiO2 颗粒进行氟化改性，以获得表面具有高氟含量的 pal@SiO2-F 填料。通过粘结剂、填料分层喷涂制备了一种具有优异稳定性的 PDMS / pal@SiO2-F 超双疏涂层。涂层在浸泡、腐蚀和自清洁等测试中展现了优异的拒液性、耐腐蚀性、自清洁性和防污性，拥有在复杂油、污环境中应用的潜力。

  • 1 材料与方法

  • 1.1 试验材料

  • 坡缕石粉末（pal，无规则颗粒状，粒径 20～30 μm）；正硅酸乙酯（TEOS，AR，98%）；无水乙醇（EtOH，99.5%）；氨水（NH3· H2O，25%～28%）； 1H，1H，2H，2H-全氟癸基三乙氧基硅烷（PFDTES， 97%）；聚二甲基硅氧烷（PDMS，99%）；乙酸丁酯 （BA，AR，97%）盐酸溶液（HCl，AR，36%～38%）； 氢氧化钠（NaOH，ACS，97%）；氯化钠（NaCl， AR）

  • 1.2 pal@SiO2-F 填料制备

  • 采用改进的溶胶-凝胶法制备pal@SiO2-F填料，制备工艺如图1 所示。首先，将 2 g pal 粉末分散在 100 mL 无水乙醇与 12 mL 氨水的混合溶液中，形成均匀溶液 A，12 mL TEOS 与 20 mL 无水乙醇混合，得到溶液 B。其次，将 B 溶液加入到 A 溶液中，在室温下搅拌 10 h，确保水解完全。然后，向反应溶液中滴加 1.6 mL PFDTES，反应持续 8 h。最后，用无水乙醇离心清洗三次，在 80℃干燥 12 h，得到 pal@SiO2-F 填料。

  • 图1 pal@SiO2-F 填料和 PDMS / pal@SiO2-F 超双疏涂层制备示意图

  • Fig.1 Schematic illustration of the fabrication of composite filler pal@SiO2-F and superamphiphobic coatings.

  • 1.3 PDMS / pal@SiO2-F 涂层制备

  • 采用分层喷涂的方法制备 PDMS / pal@SiO2-F 涂层，制备工艺如图1 所示。首先，使用 600 目和 1200 目砂纸打磨铝板，确保氧化层去除，随后用去离子水和无水乙醇清洗铝板。其次，将 2 g PDMS 与 2 g 乙酸丁酯均匀混合，得到溶胶 A1；将 3 g pal@SiO2-F 填料分散在 10 mL 无水乙醇中，得到分散体 B1。然后，将溶胶 A1 与分散体 B1 依次喷涂到铝板表面，喷枪与铝板距离约为 20 cm，压力为 0.3 MPa。最后将涂层放置于烘箱内，80℃固化 8 h，得到具有超双疏性的 PDMS / pal@SiO2-F 涂层。

  • 1.4 表征及性能测试

  • 采用接触角测量仪（ZJ-6900）测试涂层表面液体接触角（CA）。用 X 射线衍射（X'Pert PRO MPD， XRD）测定pal 粉末和pal@SiO2-F填料的晶体结构。采用傅里叶变换红外吸收光谱仪（Nicolet iS 10， FT-IR）分析 pal 粉末和 pal@SiO2-F 填料的官能团。采用 X 射线光电子能谱仪（Thermo Scientific K-Alpha，XPS）分析 pal@SiO2-F 填料的表面化学成分，以 284.8 eV 下的 C1s 峰为参比标定所有结合能。采用扫描电子显微镜（Hitachi S3400N，SEM） 观测涂层表面形貌。

  • 涂层表面润湿性测试：使用接触角测量仪测量去离子水、牛奶、白矿油、食用油和机油等液体在 PDMS / pal@SiO2-F 涂层表面的接触角（在涂层表面随机选取 5 个点位测量，取平均值）。

  • 浸泡-提出循环测试：将 PDMS / pal@SiO2-F 涂层垂直浸入白矿油中，5 min 后垂直提出，30 s 后再次浸入，每循环 10 次测量一次浸泡部位涂层的水 / 油接触角。

  • 酸碱盐溶液浸泡腐蚀测试：将 PDMS / pal@ SiO2-F 涂层垂直浸入 HCl / NaOH / NaCl 标准溶液中，12 h 后取出，干燥完全，测量涂层浸泡部位水 / 油接触角。

  • 涂层自清洁性能测试：将砂土混合物（细砂石与自然黏土按质量比 1∶1 混合）铺在涂层表面，使用滴灌紧贴涂层表面滴加去离子水，观察去离子水滴滚落过程中能否去除涂层表面的砂土混合物，以及涂层表面是否会粘附污渍。

  • 2 结果与讨论

  • 2.1 pal@SiO2-F 填料分析

  • 正硅酸乙酯（TEOS）在氨水提供的碱性环境下，易发生水解反应产生-OH，经水解缩合后，在微米 pal 颗粒提供的生长点位上长出二氧化硅（SiO2）纳米颗粒，包覆在 pal 颗粒表面，得到疏水填料 pal@SiO2。该填料具有丰富的-OH 点位，能与 PFDTES 发生缩合反应，将高氟基团枝接到 pal@SiO2 填料表面[8]。

  • FT-IR 分析结果如图2a 所示，pal 粉末在 3 615 和 3 552 cm-1 处的特征峰属于-OH（Al）和-OH（Mg） 基团的伸缩振动，3 410 和 1 656 cm-1 特征峰对应配属和游离的水中的氢键[19]，1 027 cm-1 处的特征峰属于 Si-O-Si 的不对称拉伸模式，984 cm-1 处的特征峰对应-OH 弯曲带[20]。pal@SiO2-F 填料在 1 090 cm-1 处的特征峰属于 Si-O-Si 不对称拉伸振动，而 795 cm-1 处的特征峰则对应着 Si-O-Si 的对称拉伸振动[21]。这表明，在溶胶-凝胶反应过程中，成功实现了在微米 pal 颗粒表面生长 SiO2颗粒的目标。与 pal 相比，pal@SiO2-F 在 1 202 cm-1 处的新峰，对应着-CF2 基团的拉伸振动[22]。这表明，高氟基团成功枝接到了 pal@SiO2 填料表面，这也证实了 pal@SiO2-F 填料制备成功。

  • 图2 pal 粉末与 pal@SiO2-F 填料表征结果

  • Fig.2 Characterization results of pal powders and pal@SiO2-F fillers

  • XPS 试验结果可以进一步验证 pal@SiO2-F 的化学成分。如图2b 所示，在 668.4 eV 处检测到强 F1s 峰，高氟含量（氟原子百分比 33.14%）表明 pal@SiO2-F 表面含有丰富的含氟基团。此外，在高分辨率 C1s 光谱中，如图2c 所示，293.3、291、284.8 eV 处的峰，分别对应 PFDTES 的-CF3、-CF2、 C-C / C-H 基团[23-24]。上述结果表明，填料表面枝接了丰富的低表面能基团。

  • 通过 X 射线衍射（XRD）验证改性后的 pal 粉末晶体结构，如图2d 所示。与 pal 粉末相比，溶胶-凝胶反应后，pal@SiO2-F 填料特征峰变化不明显，在 2θ=20～30°处出现了一个较弱且较宽的特征峰，该峰属于无定形二氧化硅的特征峰[25-26]。这说明反应过程中，pal 颗粒表面成功生长出 SiO2 纳米结构，且并未改变填料的基础晶体结构。

  • 如图3a 所示，未经处理的原始 pal 颗粒边缘光滑平坦，无明显纳米突起，粒径为 20～30 μm。从图3b 可以看出，由于 SiO2 在 pal 颗粒表面原位生长，pal@SiO2-F 填料表面粗糙度明显增大，在颗粒表面能观察到明显的短棒状纳米突起，且突起相互交错，在填料表面构建了大量的孔洞，这为后续在涂层表面构建微 / 纳粗糙结构提供了必要条件。

  • 图3 pal 和 pal@SiO2-F 颗粒 SEM 图像

  • Fig.3 SEM images of pal and pal @ SiO2-F particles

  • 2.2 PDMS / pal@SiO2-F 涂层润湿性分析

  • 利用接触角测量仪测量不同液体在 PDMS-pal@SiO2-F 涂层表面的接触角。图4a 显示了去离子水（γ=72.8 mN / m）、牛奶（γ=51.3 mN / m）、食用油（γ=33.8 mN / m）、机油（γ=31.8mN / m）、白矿油（γ=30.7mN / m）[27]等液滴在涂层表面的接触角。可以发现，5 种液体在涂层表面的接触角均在 150°以上，这说明涂层能对表面张力（γ）大于 30.7 mN / m 的液体表现出超排斥作用。图4b 为 5 种液体滴加在涂层上 20 min 后拍摄的光学图片，展示了涂层对各种低表面能液体稳定的拒液性。

  • 图4 PDMS / pal@SiO2-F 涂层抗润湿性测试

  • Fig.4 Anti-wettability test of PDMS / pal@SiO2-F coatings

  • 2.3 PDMS / pal@SiO2-F 涂层表面形貌分析

  • PDMS / pal@SiO2-F 涂层表面形貌如图5 所示。从图中可以观察到，微米级无定形 pal 颗粒表面覆盖有纳米突起，提供了纳米级的二级结构，大量的填料在少量 PDMS 的粘结下，随机交错、叠加，形成发育良好的双重粗糙结构，依托丰富的乳突、微孔，以及其他微小空间，共同捕获稳定的气膜，使得涂层处于 Cassie-Baxter 状态，液滴容易悬浮在粗糙界面之上，获得超双疏性。

  • 图5 PDMS / pal@SiO2-F 涂层表面的 SEM 图像

  • Fig.5 SEM images of PDMS / pal@SiO2-F coatings surface

  • 2.4 PDMS / pal@SiO2-F 涂层稳定性测试

  • 对于超双疏涂层而言，表面结构的不稳定性是阻碍其大规模应用的重要原因，要使涂层能够广泛应用于各种环境，需要涂层具备较强的适应能力。因此，对 PDMS / pal@SiO2-F 涂层的稳定性进行了详细的测试。

  • 2.4.1 PDMS / pal@SiO2-F 涂层浸泡-提出循环测试

  • PDMS / pal@SiO2-F 涂层浸泡-提拉测试所得数据如图6a 所示。可以发现，在 50 次浸泡-提出循环过程中，涂层表面的水 / 油接触角呈缓慢下降的趋势，这可能是长时间浸泡，使得部分乳突结构与液体接触后，头部存留了微量油膜导致的。但经过 50 次循环后，水 / 油接触角仍能维持在 150°以上，这表明涂层表面双重粗糙结构捕获的气垫十分稳定，能使涂层在长时间浸泡的条件下仍能处于 Cassie-Baxter 状态，涂层表面乳突、微孔等构成的结构成功阻止了白矿油的渗透。图6b 显示了涂层浸入透明液体后显示出的“银镜现象”，这表明涂层表面结构捕获了稳定的气膜，将液体与涂层分隔开。试验结果表明，涂层具有优异的抗浸润性和抗粘附性能，具有在低表面能液体长期浸泡的环境中应用的潜力。

  • 图6 PDMS / pal@SiO2-F 涂层表面结构耐浸泡能力

  • Fig.6 Immersion resistance of PDMS / pal@SiO2-F coatings surface structure

  • 2.4.2 PDMS / pal@SiO2-F 涂层耐腐蚀性测试

  • 为了更好地了解涂层的稳定性，将 PDMS / pal@SiO2-F 涂层分别浸入 HCl 标准溶液、NaOH 标准溶液、NaCl 标准溶液中 12 h，验证其耐腐蚀性能。图7b 作为对照，涂层在水中浸泡 12 h 后，仍具有超双疏性能，证明了涂层在纯水浸泡工况下的优异性能。通过图7a 可知，涂层在 HCl 和 NaCl 溶液浸泡处理后，虽丧失了超疏油性，但其 CAoil＞130°，仍具备良好的疏油性和超疏水性，NaOH 溶液处理后的涂层，性能仍能接近超双疏，这显示出涂层具有抵抗恶劣环境下化学腐蚀的能力，能适应大部分工业环境。

  • 2.4.3 涂层自洁净性能测试

  • 从图8 可以观察到，水滴对涂层的粘附力很弱，在涂层表面滴加的水滴在能够在倾斜角大于 5°的状态下滚落，轻易浸润并带走涂层表面的砂粒；并且带走了涂层表面被水浸润的土浆，完全离开表面后，并未留下污渍与残留物。这证明了涂层具有优异的自清洁与防污性能。

  • 图7 PDMS / pal@SiO2-F 涂层耐腐蚀性测试

  • Fig.7 Corrosion resistance test of PDMS / pal@SiO2-F coatings

  • 图8 自清洁性能测试

  • Fig.8 Self-cleaning performance test

  • 2.5 气膜稳定性与超双疏机理

  • PDMS / pal@SiO2-F 涂层由 PDMS 高分子聚合物层和氟化微坡缕石层组成，具有优异的抗附着和抗腐蚀性能，为了阐明气垫对于涂层拒液性的影响，提出了涂层与水 / 油之间可能的相互作用机制。如图9 所示，涂层表面颗粒的堆积形成许多微乳头结构和内凹微孔结构，利用这种结构及填料本身具有的低表面能，可以在涂层表面捕获稳定的气垫，阻止水 / 油与涂层表面的接触。根据 Cassie-Baxter 方程[27]，cosθD =fs cosθY-fg，其中 θD 为表观接触角，θY 为液固本征接触角，理想 Cassie 状态下 fs 和 fg（液固 / 气固接触分数）之和为 1，由此可以得到 cosθD =fs（1+ cosθY）-1。因此，随着液固接触分数 fs 减小，表观接触角 θD 大大增加，实现了对低表面能液滴的排斥（γ＞ 30.7 mN / m）。

  • 图9 涂层表面超双疏机理示意图

  • Fig.9 Schematic diagram of the superamphiphobic mechanism of the PDMS / pal@SiO2-F coating

  • 3 结论

  • （1）选用成本较低的微米级无规则 pal 颗粒作为前驱体，使用溶胶-凝胶法，以微米级颗粒为基础，在其表面原位生长纳米二级结构，并进行氟化改性，制备了高含氟量 pal@SiO2-F 填料。

  • （2）引入 PDMS 作为粘结剂，增强 pal@SiO2-F 填料与基底结合力，通过简单的分层喷涂方法，充分发挥粘结剂与填料各自的优势，制备了具有稳定性能的 PDMS / pal@SiO2-F 超双疏涂层。涂层对多种液体表现出良好的超双疏性，其中水、白矿油接触角分别达到 160°和 158.2°。

  • （3）得益于精密的表面结构设计，粘结剂固定微米颗粒，微米颗粒为纳米结构提供保护作用，使得涂层在经历油浸、腐蚀性测试后，双重粗糙结构不被破坏，仍能稳定地捕获气垫，表现出良好的疏油疏水性能。

  • （4）涂层缺乏极端工况下的性能测试，在极端条件下的性能表现仍有待验证。

  • 参考文献

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    • [3] LI Q,ZHANG X,BEN S,et al.Bio-inspired superhydrophobic magnesium alloy surfaces with active anti-corrosion and self-healing properties[J].Nano Research,2022,16(2):3312-3319.

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  • 基本信息

    中图分类号: TB333；TB37
    DOI: 10.11933/j.issn.1007-9289.20230816001

    基金信息

    国家科技重大专项（J2019-VII-0015-0155）；
    中央高校基本科研业务费（2023ZKPYTD01, 2021YQJD23）；
    大学生创新创业项目（202304019）；
    National Science and Technology Major Project of China (J2019-VII-0015-0155)；
    Fundamental Research Funds for the Central Universities (2023ZKPYTD01, 2021YQJD23)；
    College Students’ Innovative Entrepreneurial Training Plan Program (202304019)；

    引用信息

    高兴华，黄啸，张晓强，等. 基于坡缕石制备的稳定超双疏涂层[J]. 中国表面工程，2024，37(4)：151-160.

    GAO Xinghua, HUANG Xiao, ZHANG Xiaoqiang, et al. Preparation of stable superamphiphobic coatings based on palygorskite[J]. China Surface Engineering, 2024, 37(3): 151-160.

    稿件历史

    收稿日期: 2023-08-16
    录用日期: 2024-01-19

  • 参考文献

    • [1] QIAO Z,REN G,CHEN X,et al.Fabrication of robust waterborne superamphiphobic coatings with antifouling,heat insulation,and anticorrosion[J].ACS Omega,2023,8(1):804-818.

    • [2] MAO Y,GUIDOIN R,BROCHU G,et al.Facile fabrication of phospholipid-functionalized nanofiberbased barriers with enhanced anti-adhesion efficiency[J].Colloids and Surfaces B:Biointerfaces,2021,203:111728.

    • [3] LI Q,ZHANG X,BEN S,et al.Bio-inspired superhydrophobic magnesium alloy surfaces with active anti-corrosion and self-healing properties[J].Nano Research,2022,16(2):3312-3319.

    • [4] ZHU P,ZHU L,GE F,et al.Sprayable superhydrophobic coating with high mechanical/chemical robustness and anti-corrosion[J].Surface and Coatings Technology,2022,443:128609.

    • [5] 陈茜茜,汪怀远,张文博,等.改性硅藻土及PDMS对环氧涂层的阻垢耐蚀性能的影响[J].中国表面工程,2019,32(4):102-108.CHEN Qianqian,WANG Huaiyuan,ZHANG Wenbo,et al.Effects of modified celatom and PDMS on antiscaling and corrosion resistance of epoxy coatings[J].China Surafce Engineering,2019,32(4):102-108.(in Chinese)

    • [6] WONG T S,KANG S H,TANG S K,et al.Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity[J].Nature,2011,477(7365):443-447.

    • [7] DAI X,SONG Z,LI P,et al.Bioinspired superhydrophilic/underwater superoleophobic surfaces with robust wax-prevention,self-cleaning,and oil/water separation functions[J].New Journal of Chemistry,2023,47(4):2096-2106.

    • [8] PENG J,YUAN S,GENG H,et al.Robust and multifunctional superamphiphobic coating toward effective anti-adhesion[J].Chemical Engineering Journal,2022,428:131162.

    • [9] DONG J,ZHANG J.Biomimetic super anti-wetting coatings from natural materials:superamphiphobic coatings based on nanoclays[J].Sci Rep,2018,8(1):12062.

    • [10] WANG T,LV C,JI L,et al.Designing re-entrant geometry:construction of a superamphiphobic surface with Large-sized particles[J].ACS Appl Mater Interfaces,2020,12(43):49155-49164.

    • [11] ELLINAS K,TSEREPI A,GOGOLIDES E.Durable superhydrophobic and superamphiphobic polymeric surfaces and their applications:A review[J].Adv Colloid Interface Sci,2017,250:132-157.

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