中国腐蚀与防护学报, 2017, 37(3): 233-240
doi: 10.11902/1005.4537.2016.017
混酸刻蚀-氟化处理制备X80管线钢双疏表面及其耐蚀性研究

Fabrication of Amphiphobic Surface of Pipeline Steel by Acid Etching and Its Anti-corrosion Properties
任继栋, 高荣杰, 张宇, 刘勇, 丁甜

摘要:

通过酸性溶液对X80管线钢表面进行化学刻蚀,形成具有一定结构的微观粗糙形貌;然后通过低表面能物质十七氟癸基三乙氧基硅烷的修饰,降低钢材基底的表面能,从而成功地制备出超疏水疏油的双疏功能表面。研究了酸性刻蚀和氟化处理对表面形貌及其润湿性的影响,并通过电化学测试研究了双疏表面的耐蚀性能。结果表明:经过4 h的酸性刻蚀与氟化处理,所制备的超疏水疏油表面与去离子水,丙三醇,乙二醇和十六烷的接触角分别达到161°,156°,151.5°和146°,实现了超疏水与疏油的双疏效果。相比较未经处理的X80管线钢试样,双疏表面的腐蚀电位发生了正向移动,而腐蚀电流密度降低了两个数量级,说明双疏试样耐腐蚀性能得到了显著提高。

关键词: X80管线钢 ; 混酸刻蚀 ; 氟化处理 ; 超疏水疏油 ; 耐蚀性

Abstract:

Pipeline steel has been widely used in modern industry such as the transportation of natural gas and oil. However, its service life is mainly affected by the corrosion because of its hydrophilic and oleophilic properties. In this study, the surface of X80 pipeline steel was converted to be of super-hydrophobicity and oleophobicity by acid etching and fluoride modification. The steel was first etched by a mixed acid solution to roughen its surface, and then modified with a kind of low surface energy material, 1H, 1H, 2H, 2H-Perfluorodecyltriethoxysilane. The fluoride modification can reduce the surface energy, which is an essential step to prepare the amphiphobic surface. The influence of acid etching and modification on the morphology and the wetting behavior of the modified surface was characterized and the corrosion behavior of the amphiphobic surface was studied by potentiodynamic scanning. The result showed that the modified amphiphobic surface exhibits excellent both of hydrophobicity and oleophobicity, for substances such as water, glycerin and ethylene glycol, as well as hexadecane. After 4 h etching and fluoride modification, the contact angles of the modified steel with deionized water, glycerin, ethylene glycol and hexadecane were 161°, 156°, 151.5° and 146° respectively. The modified surface can enhance the corrosion resistance of the pipeline steel and such amphiphobic surface can be easily repaired.

Key words: X80 pipeline steel ; acid etching ; fluoroalkyl silane ; amphiphobicity ; anti-corrosion

材料的润湿性是物体表面的一个重要特征,在人们的日常与工农业生产中都发挥着重要的作用。润湿通常是指固体表面上的气体被液体取代的过程。常用接触角 (CA) 作为液体对固体润湿程度的判据,将CA<90°的表面称为亲液表面,把CA>90° 的表面称为疏液表面。特别地,CA=0°为完全润湿表面;CA=180°为完全不润湿表面。通过对实际运用中固体表面润湿现象的研究,人们提出了超亲液和超疏液的概念。当CA<5°时,固体表面为超亲液表面;当CA>150°时,固体表面为超疏液表面[1-8]。自然界中许多动植物表面具有疏水疏油甚至是超疏水疏油的特性,比如荷叶、蝴蝶的翅膀、蝉的翼面和水黾的腿表面等。研究自然界动植物现有的超疏水表面结构,研究结构与性能之间的关系,对人工制备具有超疏水功能的表面有重要的意义[9-15]

固体表面的润湿性主要由其化学组成和表面形貌共同决定。通过在不同材料的表面构建合适的微观粗糙形貌,结合含有氟碳基团的低表面能物质进行表面修饰,可以在材料基底上获得性能不同的超疏水疏油表面[16-18]。一般说来,在材料表面构建超疏水疏油表面可采用两步法,首先在材料表面构建合适的微观粗糙形貌,再利用氟硅烷等低表面能物质修饰粗糙表面[19-21],从而达到表面超疏水疏油的目的,构筑表面不同的微观粗糙形貌可采用刻蚀法、水热法、电化学法等[22-27]

改变管线钢表面润湿性在管道运输领域具有广泛的应用前景。管线钢主要应用于原油与天然气的运输等,然而管道内表面容易受到腐蚀介质的破坏,影响管道的使用寿命。而通过在管线钢内表面上构建超疏水疏油表面,使其具有疏液和自清洁功能,减少与腐蚀介质的接触,可以有效地解决上述问题,还存在降低运输成本的可能。

本文通过混合酸液的刻蚀方法,成功地在X80管线钢表面制备出超疏水疏油表面,并通过电化学测试方法研究了双疏表面在3.5% (质量分数) NaCl溶液中的耐蚀性能。

1 实验方法

实验采用X80管线钢作为研究对象,样品尺寸为20 mm×10 mm×3 mm,整个表面用环氧树脂固封后用抛光机打磨至完整地裸露一个表面。混酸溶液配置方法如下:在磁力搅拌的作用下,将20 mL双氧水和30 mL浓度为10 mol/L的尿素溶液缓慢的倒入80 mL去离子水中,然后加入70 mL浓度为25 mol/L的草酸溶液,再滴入若干滴丙三醇,最后依次加入700 μL硫酸和50 μL盐酸并搅拌均匀。以上所用的试剂纯度规格全部为分析纯。

将预处理过的X80钢试样放入酸性溶液中刻蚀一定的时间,刻蚀结束后取出,分别用蒸馏水和无水乙醇洗净、吹干备用。配制一定体积分数的十七氟癸基三乙氧基硅烷 (HFTTMS) 的乙醇溶液:使用移液枪量取45 μL的氟硅烷,注入到15 mL乙醇溶液中,然后超声分散20 min。将刻蚀后的试样浸泡在氟化液中修饰20 min,修饰结束后取出,放入60 ℃真空干燥箱中烘干30 min即可。

通过JC2000C1型接触角测量仪表征试样与去离子水、丙三醇、乙二醇和十六烷的接触角,每一种液体与试样的接触角测量5次,最后取平均值。通过JSM-6700F型冷场发射扫描电子显微镜 (FE-SEM) 观察试样经过酸性刻蚀后的表面微观形貌。通过D8 ADVANCE 型X射线衍射仪 (XRD) 表征酸性刻蚀前后样品的化学组分。通过INCA Energy, Oxford135Ins 型能谱仪 (EDS) 和ESCALAB 250Xi 型X射线光电子能谱 (XPS) 表征氟化处理前后样品表面化学成分及存在状态。通过CHI600E型电化学分析仪测试试样的动电位极化曲线。

2 结果与讨论

X80管线钢经过酸性刻蚀4 h后表面形貌如图1所示。可以看出,刻蚀后的表面交错分布着类似陨石坑状的凹陷和凸起,凹陷的外围呈圆环或者圆弧状凸起,其直径约在几十微米到一百微米。从图1b可以看出,表面存在粗糙不平的凹坑和若干条酸液腐蚀产生的裂纹,表面显现出更加细小的凸起以及层片状结构。从图1c可以明显地看出,层片状结构相互交错。由图1d可知,层片状的长度约为几个微米,层片状的壁厚在100~200 nm之间。由于层片状的相互交错,从而形成大量的空隙。

4种典型的液相在经不同工艺处理后的试样表面的接触角变化如表1和图2所示。混酸刻蚀之前,试样与去离子水、丙三醇、乙二醇和十六烷的接触角分别为48°,45.5°,41°和1°,表现为亲液的性质。经过4 h刻蚀之后,试样表面变得粗糙不平,又由于金属的表面能比较高,往往高于绝大多数液体,所以无论是水滴还是油滴,滴落在刻蚀后的表面后会迅速地铺展而润湿表面,表现为超亲液性质。而经过氟硅烷修饰之后,由于氟硅烷官能团具有极低的表面能和极好的疏液性,试样与这4种液体的接触角分别为161°,156°,151.5° 和 146°,使得亲液表面变为双疏表面。若不经过酸性刻蚀形成微纳米结构,即使用氟硅烷修饰,X80管线钢与4种液体的接触角仅能达到116°,104°,94°和69.5°。经过酸性刻蚀和氟化处理后的试样,与水和丙三醇的滚动角小于5°,与乙二醇的滚动角小于10°,与十六烷没有滚动角,液滴会一直黏附在试样表面。

图1 酸性刻蚀4 h后管线钢表面形貌的SEM像

Fig.1 SEM images of the surface of X80 pipeline steel after acid etching for 4 h (a) and the magnified images of Fig.4a (b~d)

表1 不同表面张力的液体与不同表面状态的X80管线钢的接触角
Table 1 CAs of four typical liquids on the surfaces of X80 pipeline steel treated by different methods
Liquid Surface tension / mNm-1 / 20° CA / °
Untreated Treated
Water 72.8 48.0 161.0
Glycerol 63.6 45.5 156.0
Ethylene glycol 47.7 41.0 151.5
Hexadecane 25.7 1.0 146.0

表1 不同表面张力的液体与不同表面状态的X80管线钢的接触角

Table 1 CAs of four typical liquids on the surfaces of X80 pipeline steel treated by different methods

图2 4种液体在X80管线钢原始表面以及双疏表面接触角的变化及液滴在双疏表面接触角的宏观照片

Fig.2 Contact angles of four typical liquids on the original and amphiphobic surfaces of X80 pipeline steel (a) and photo of droplets on the amphiphobic surface (b)

X80管线钢经过处理后润湿性的改变可以通过Cassie等[28]和Wenzel[29]理论模型来解释:刻蚀后表面粗糙的微纳米层片状结构,使得凹陷处存在空气,这种固体表面可以看成由固体和空气组成的复合表面。由Cassie理论可知,液滴在与基底接触的过程中,不能够完全的相互接触,形成固、液、气的三相接触,这就使得水滴,丙三醇和乙二醇在基底表面上有较大的接触角和较小的滚动角,表现出较低的粘滞性。而十六烷表面张力相比另外几种液体较低,使得其与基底接触时更容易处在Wenzel状态,液滴与基底会倾向于完全接触,从而滚动角较大,表现出一定的粘滞性。

图3是试样经酸性刻蚀前后的XRD谱。可以看出,试样表面的相组成没有发生变化,主要为Fe的衍射峰,其晶格参数为a=b=c=28.664 nm,这说明酸性刻蚀并不影响试样表面的相组成,仅仅是改变了表面形貌。

图3 酸性刻蚀前后X80管线钢的XRD谱

Fig.3 XRD patterns of X80 pipeline steel before and after acid etching

氟化处理前后试样表面的EDS结果见图4a和b,氟化处理之后试样表面的XPS谱见图4c和d。从图4a可以看出,刻蚀之后,试样表面主要含有Fe和C两种元素,是X80管线钢的基本组分。在经氟硅烷修饰之后 (图4b),试样表面检测出了F和Si两种元素。由图4c的XPS全谱扫描可检测到C,F,Si和O 4种元素,其中F1s的峰值在688.3 eV处。图4d是C1s的精细谱,从中可以发现有3种类型的C,峰值在293.04,290.75和284.90 eV处,分别对应着—CF3,—CF2和—CH2。因此,由EDS结果和XPS谱可以确定氟硅烷成功地修饰在试样表面。由于—CF3与—CF2是具有最低表面能的基团[20,30,31],所以成功引入氟碳基团成为制备双疏表面、降低表面能的关键。

图4 X80管线钢经酸性刻蚀和氟化处理后表面的EDS分析结果,氟化处理后表面的XPS全谱和C1s的精细谱

Fig.4 EDS analysis results of the surfaces treated by acid etching (a) and fluoridization (b), XPS survey (c) and C1s fine spectrum (d) of the amphiphobic surface

通过电化学三电极体系测试了X80管线钢初始试样和酸性刻蚀4 h并经氟化处理的双疏试样在3.5%NaCl溶液中的极化曲线。测试之前,试样需要浸泡在NaCl溶液中约40 min,以使电极电位稳定。极化曲线测试结果如图5所示,与之相对应的电化学拟合参数如表2所示。通过比较可以看出,双疏表面试样的腐蚀电位 (Ecorr=-0.290 V) 相比原始试样的电位 (Ecorr=-0.693 V) 发生了正向移动;而腐蚀电流密度Icorr从1.73×10-3 A/cm2降低到了4.11×10-5 A/cm2,降低了两个数量级。这表明双疏表面相比于原始的管线钢表面具有更好的耐蚀性。这主要因为双疏表面粗糙的微观形貌,凹凸不平及层片状结构可以捕获空气,由Cassie理论模型可知,空气垫的存在可以使液体及液体中的腐蚀离子 (Cl-) 很难与基体接触。随着试样在NaCl溶液中浸泡时间的延长,其腐蚀电位开始负移,腐蚀电流密度开始增大。浸泡2 h后,腐蚀电位Ecorr=-0.537 V,腐蚀电流密度Icorr=7.75×10-4 A/cm2,仍然比原始管线钢试样低一个数量级,如图5b所示。浸泡4 h后,Ecorr=-0.720 V,Icorr=5.63×10-3 A/cm2,此时腐蚀电位比原始试样的更负,而腐蚀电流密度也高于原始试样的,如图4c所示,说明在3.5%NaCl溶液中浸泡4 h后,所制备双疏表面的试样其耐蚀性不如初始管线钢。可以推断,此时水溶液已经穿透双疏膜的屏障,两者由Cassie态接触变成了Wenzel态接触[32,33],从而使试样的耐蚀性下降。这主要因为粗糙的结构大多致密性较差,超疏水疏油膜难以在整个表面形成稳定可靠的物理屏障,特别是存在Cl-时,水分子会从一些缺陷的部位渗入到基底的微纳米级的粗糙结构中,导致双疏膜的失效和腐蚀的加速。另一方面,浸入溶液中的双疏表面,由于水压的存在,微观结构所能捕获的空气也容易被“挤出”,从而加速了双疏功能膜的失效。随后,对浸泡4 h后的试样做进一步的处理,将其表面洗净、吹干,再进行第二次的氟化处理,最后测试其在3.5%NaCl溶液中的极化曲线,见图5d,其腐蚀电位 (Ecorr=-0.304 V) 与第一次处理时所测量的数值较接近,而腐蚀电流密度 (Icorr=1.80×10-5 A/cm2) 有所下降。这也就说明了,经3.5%NaCl溶液浸泡4 h后,由于试样粗糙的表面形貌失去疏水的能力,耐蚀性比未经处理过的钢材还差,但经过二次的氟化处理后,再一次具有超疏水疏油的能力,恢复到之前较高的耐蚀性。

图5 原始试样和双疏表面试样在3.5%NaCl溶液中浸泡40 min,2 h和4 h后的动电位极化曲线及双疏试样浸泡4 h后经再次氟化处理后的极化曲线

Fig.5 Potentiodynamic polarization curves for the original and amphiphobic treated samples after immersion in 3.5% NaCl solution for 40 min (a), 2 h (b) and 4 h (c), and for the sample tested in Fig.5c but subsequently re-fluoridized (d)

表2 极化曲线的电化学拟合参数
Table 2 Fitting electrochemical parameters of the potentiodynamic curves
Sample lg (Icorr / Acm-2) Ecorr / V Icorr / Acm-2
X80 steel / 40 min -2.7623 -0.693 1.73×10-3
Amphiphobic surface / 40 min -4.3860 -0.290 4.11×10-5
Amphiphobic surface / 2 h -3.1105 -0.537 7.75×10-4
Amphiphobic surface /4 h -2.2495 -0.720 5.63×10-3
Remodified surface -4.7448 -0.304 1.80×10-5

表2 极化曲线的电化学拟合参数

Table 2 Fitting electrochemical parameters of the potentiodynamic curves

为了进一步探索所制备具有双疏表面试样的耐蚀性与表面形貌之间的关系,研究了原始X80管线钢和经过酸性刻蚀4 h以及氟化处理的双疏试样在室温下3.5%NaCl溶液中浸泡一段时间后表面微观形貌的变化,结果见图6和7。X80管线钢的表面形貌如图6a所示,表面整体比较平整;在3.5%NaCl溶液中浸泡2 h后,表面出现一层微观细小的腐蚀产物;而经过8 h的浸泡后,腐蚀产物增多,并覆盖在整个基底表面,由放大图像可见,腐蚀产物呈现类似花瓣状结构。

经酸性刻蚀和表面氟化所制备的X80管线钢双疏试样,经过在3.5%NaCl溶液中浸泡后,表面形貌变化见图7。可知,经过2,8和16 h浸泡,双疏试样的表面形貌几乎没有变化,表面均交错分布着类似陨石坑状的凹陷和凸起;而经过24 h的浸泡后可见,表面的凸起程度有所降低,陨石坑状结构的分布数量明显下降,这说明双疏试样在3.5%NaCl溶液中浸泡24 h后,表面发生了一定的腐蚀,表面结构受到一定程度的破坏。通过对比图6和7可知,相比于X80管线钢的原始试样,通过酸性刻蚀和表面氟化法制备的双疏试样具有更好的耐3.5%NaCl溶液腐蚀性能。

图6 X80管线钢在3.5%NaCl溶液中浸泡不同时间后的SEM像

Fig.6 SEM images of X80 pipeline steel after immersion in 3.5%NaCl solution for 0 h (a), 2 h (b) and 8 h (c), and the magnified image of area I in Fig.6c

图7 具有双疏表面的试样在3.5%NaCl溶液中浸泡2,8,16和24 h后表面的SEM像

Fig.7 SEM images of X80 pipeline steel with amphiphobic surface after immersion in 3.5%NaClsolution for 2 h (a), 8 h (b), 16 h (c) and 24 h (d)

3 结论

(1) 通过混酸刻蚀和氟硅烷修饰的方法在X80管线钢制备出了超疏水疏油表面,其与离子水、丙三醇、乙二醇和十六烷的接触角分别达到了161°,156°,151.5°和146°。

(2) 酸性刻蚀仅仅改变试样的表面形貌,形成微纳米的粗糙结构,为实现超疏水疏油提供了结构基础;经过氟硅烷修饰,引入—CF3和—CF2低表面能基团,降低试样表面的表面能,从而实现了超疏水疏油功能。

(3) 与原始X80管线钢试样相比,具有双疏表面试样的耐3.5%NaCl溶液腐蚀性能得到提高。

The authors have declared that no competing interests exist.

参考文献

[1] Liu K S, Tian Y, Jiang L.Bio-inspired superoleophobic and smart materials: Design, fabrication, and application[J]. Prog. Mater. Sci., 2013, 58: 503
Through evolution, nature has arrived at what is optimal. Inspired by the biomaterials with special wettability, superhydrophobic materials have been well-investigated and -covered by several excellent reviews. The construction of superoleophobicity is more difficult than that of superhydrophobicity because the surface tension of oil or other organic liquids is lower than that of water. However, superoleophobic surfaces have drawn a great deal of attention for both fundamental research and practical applications in a variety of fields. In this contribution, we focus on recent research progress in the design, fabrication, and application of bio-inspired superoleophobic and smart surfaces, including superoleophobic鈥搒uperhydrophobic surfaces, oleophobic鈥揾ydrophilic surfaces, underwater superoleophobic surfaces, and smart surfaces. Although the research of bio-inspired superoleophobicity is in its infancy, it is a rapidly growing and enormously promising field. The remaining challenges and future outlook of this field are also addressed. Multifunctional integration is a inherent characteristic for biological materials. Learning from nature has long been a source of bio-inspiration for scientists and engineers. Therefore, further cross-disciplinary cooperation is essential for the construction of multifunctional advanced superoleophobic surfaces through learning the optimized biological solutions from nature. We hope this review will provide some inspirations to the researchers in the field of material science, chemistry, physics, biology, and engineering.
DOI:10.1016/j.pmatsci.2012.11.001      URL     [本文引用:1]
[2] Barthwal S, Lim S H.Fabrication of long-term stable superoleophobic surface based on copper oxide/cobalt oxide with micro-nanoscale hierarchical roughness[J]. Appl. Surf. Sci., 2015, 328: 296
We have demonstrated a simple and cost-effective technique for the large-area fabrication of a superoleophobic surface using copper as a substrate. The whole process included three simple steps: First, the copper substrate was oxidized under hot alkaline conditions to fabricate flower-like copper oxide microspheres by heating at a particular temperature for an interval of time. Second, the copper-oxide-covered copper substrate was further heated in a solution of cobalt nitrate and ammonium nitrate in the presence of an ammonia solution to fabricate cobalt oxide nanostructures. We applied this second step to increase the surface roughness because it is an important criterion for improved superoleophobicity. Finally, to reduce the surface energy of the fabricated structures, the surfaces were chemically modified with perfluorooctyltrichlorosilane. Contact-angle measurements indicate that the micro鈥搉ano binary (MNB) hierarchical structures fabricated on the copper substrate became super-repellent toward a broad range of liquids with surface tension in the range of 21.5鈥72mN/m. In an attempt to significantly improve the superoleophobic property of the surface, we also examined and compared the role of nanostructures in MNB hierarchical structures with only micro-fabricated surfaces. The fabricated MNB hierarchical structures also displays thermal stability and excellent long-term stability after exposure in air for more than 9 months. Our method might provide a general route toward the preparation of novel hierarchical films on metal substrates for various industrial applications.
DOI:10.1016/j.apsusc.2014.11.182      URL     [本文引用:]
[3] Genzer J, Efimenko K.Creating long-lived superhydrophobic polymer surfaces through mechanically assembled monolayers[J]. Science, 2000, 290: 2130
[本文引用:]
[4] Yoshimitsu Z, Nakajima A, Watanabe T, et al.Effects of surface structure on the hydrophobicity and sliding behavior of water droplets[J]. Langmuir, 2002, 18: 5818
Hydrophobicity and sliding behavior of water droplets were investigated on various hydrophobic pillarlike and groove structures prepared on a silicon wafer by dicing and subsequently coating with fluoroalkylsilane. The dominant hydrophobicity mode was changed from Wenzel's mode to Cassie's mode at a smaller roughness than that expected from the calculation based on the sinusoidal surface by Johnson and Dettre. The effect of water intrusion on the microstructure due to droplet weight was revealed to be an important factor governing the water sliding angle on the surface. In a comparison of the sliding behavior of water droplets over pillarlike and groove structures, it was demonstrated that a proper design of the surface with respect to shape and extent of the three-phase line is more effective than the increase of contact angles merely by decreasing the solid-water contact area.
DOI:10.1021/la020088p      URL     [本文引用:]
[5] Singh S, Houston J, van Swol F V, Brinker C J. Superhydrophobicity: Drying transition of confined water[J]. Nature, 2006, 442: 526
[本文引用:]
[6] Gao X F, Yao X, Jiang L.Effects of rugged nanoprotrusions on the surface hydrophobicity and water adhesion of anisotropic micropatterns[J]. Langmuir, 2007, 23: 4886
A facile laser-etching method was used for the one-step creation of various controllable dimensions of anisotropic micropatterns consisting of an alternating arrangement of microgrooves and microstripes with rugged nanoprotrusions, which after modified with fluoroalkylsilane reagent, showed perfect isotropic superhydrophobicity without apparent CA hystereses, water adhesion, and drag resistance, other than the conventional view of anisotropic surface microstructures with anisotropic surface dewetting. The detailed experiments and analyses have indicated that the introduction of the rugged nanoprotrusions on the surface of microstripes provided ideal 3D roughness, which could not only enhance the apparent contact angles close to 180 degrees by the "point" contact fashion to maximally reduce the liquid-solid contact area but, most importantly, make droplets easily roll off the surface without apparent CA hysteresis by regulating the triple-phase contact line (TCL) to become extremely discrete. These findings would be helpful in understanding the role of complex micro- and nanostructures on natural superhydrophobic biosurfaces and guiding the design of perfect artificial superhydrophobic materials for technological innovations such as the raindrop easy-cleaning, aquatic super-floating, and drag-reducing coatings.
DOI:10.1021/la0630357      PMID:17375941      URL     [本文引用:]
[7] Deng X, Mammen L, Butt H J, et al.Candle soot as a template for a transparent robust superamphiphobic coating[J]. Science, 2012, 335: 67
Coating is an essential step in adjusting the surface properties of materials. Superhydrophobic coatings with contact angles greater than 150° and roll-off angles below 10° for water have been developed, based on low-energy surfaces and roughness on the nano- and micrometer scales. However, these surfaces are still wetted by organic liquids such as surfactant-based solutions, alcohols, or alkanes. Coatings that are simultaneously superhydrophobic and superoleophobic are rare. We designed an easily fabricated, transparent, and oil-rebounding superamphiphobic coating. A porous deposit of candle soot was coated with a 25-nanometer-thick silica shell. The black coating became transparent after calcination at 600°C. After silanization, the coating was superamphiphobic and remained so even after its top layer was damaged by sand impingement.
DOI:10.1126/science.1207115      PMID:22144464      URL     [本文引用:]
[8] Tuteja A, Choi W, Ma M L, et al.Designing superoleophobic surfaces[J]. Science, 2007, 318: 1618
[本文引用:1]
[9] Blossey R.Self-cleaning surfaces—virtual realities[J]. Nat. Mater., 2003, 2: 301
In the 19th century, Oscar Wilde stated "We live, I regret to say, in an age of surfaces". Today, we do so even more, and we do not regret it: key advances in the understanding and fabrication of surfaces with controlled wetting properties are about to make the dream of a contamination-free (or 'no-clean') surface come true. Two routes to self-cleaning are emerging, which work by the removal of dirt by either film or droplet flow. Although a detailed understanding of the mechanisms underlying the behaviour of liquids on such surfaces is still a basic research topic, the first commercial products in the household-commodity sector and for applications in biotechnology are coming within reach of the marketplace. This progress report describes the current status of understanding of the underlying mechanisms, the concepts for making such surfaces, and some of their first applications.
DOI:10.1038/nmat856      PMID:12728235      URL     [本文引用:1]
[10] Xiu Y H, Zhu L B, Hess D W, et al.Hierarchical silicon etched structures for controlled hydrophobicity/superhydrophobicity[J]. Nano Lett., 2007, 7: 3388
Abstract Silicon surface hydrophobicity has been varied by using silane treatments on silicon pyramid surfaces generated by KOH anisotropic etching. Results demonstrated that by altering the surface hydrophobicity, the apparent contact angle changed in accord with the Wenzel equation for surface structures with inclined side walls. Hierarchical structures were also constructed from Si pyramids where nanostructures were added by Au-assisted electroless HF/H2O2 etching. Surface hydrophobicity and superhydrophobicity were achieved by surface modification with a variety of silanes. Stability of the Cassie state of superhydrophobicity is described with respect to the Laplace pressure as indicated by the water droplet meniscus in contact with the hierarchical structures. The contact angle hysteresis observed is also discussed with respect to water/substrate adhesion.
DOI:10.1021/nl0717457      PMID:17929875      URL     [本文引用:]
[11] Yuan Z Q, Xiao J Y, Wang C Q, et al.Preparation of a superamphiphobic surface on a common cast iron substrate[J]. J. Coat. Technol. Res., 2011, 8: 773
AbstractA superamphiphobic (super-repellent) surface with both water and rapeseed oil contact angle higher than 150° was prepared on a common cast iron substrate. The water and rapeseed oil contact angles were 15802±021.9° and 15102±021.7°, respectively. The sliding angles of water and rapeseed oil on the superamphiphobic surface were 2° and 16°, respectively. Scanning electron microscope images showed that many interesting microflower-like microstructures comprised many nanorods with the average diameter of about 20002nm, which were distributed on the superamphiphobic cast iron substrate. Each nanorod was composed of many smaller nanostructures and nano particles, which created interesting micro–nano binary structures similar to the surface microstructures of lotus leaves. When kept in an ambient environment for 602months, no rust was observed on the superamphiphobic cast iron substrate surface, which showed excellent corrosion resistance.
DOI:10.1007/s11998-011-9365-7      URL     [本文引用:]
[12] Li J, Liu X H, Ye Y P, et al.Fabrication of superhydrophobic CuO surfaces with tunable water adhesion[J]. J. Phys. Chem., 2011, 115C: 4726
In this Article, superhydrophobic CuO surfaces with di02erent topographies have been fabricated by combining both a simple solution-immersion process and self-assembly of 04uoroalk- ylsilane. We regulate the solution-immersion process by changing the immersion time, the growing temperature, and the solution compositions to control di02erent topographies of CuO surfaces. The as-prepared superhydrophobic surfaces possess tunable water adhesion that ranges from extremely low to very high, on which the sliding angle is 3 ( 1, 12 ( 1, 28 ( 2, 39 ( 2, and 90 (the water droplet is 03rmly pinned on the superhydrophobic surface without any movement at any tilted angles), respectively. Our work provides a facile and promising strategy to fabricate superhydrophobic surfaces with tunable adhesion.
DOI:10.1021/jp111296n      URL     [本文引用:]
[13] Qiu R, Zhang D, Wang P.Superhydrophobic-carbon fibre growth on a zinc surface for corrosion inhibition[J]. Corros. Sci., 2013, 66: 350
A superhydrophobic-carbon fibre (CF) layer with enhanced corrosion inhibition ability was catalytically grown on a Zn surface. Cu, which was produced by a galvanic replacement reaction, acted as a catalyst for CF growth. The contact angle and water repellence properties of the grown materials were measured to determine their superhydrophobicity. The potentiodynamic polarisation technique revealed the corrosion inhibition capabilities of the different materials used. Compared with bare Zn, the superhydrophobic Zn-CF material showed enhanced corrosion inhibition properties. During immersion in NaCl solution, perforations caused by capillary condensation decreased the superhydrophobicity of the materials and limited their corrosion inhibition capabilities. (C) 2012 Elsevier Ltd. All rights reserved.
DOI:10.1016/j.corsci.2012.09.041      URL     [本文引用:]
[14] Liu C S, Su F H, Liang J Z.Facile fabrication of a robust and corrosion resistant superhydrophobic aluminum alloy surface by a novel method[J]. RSC Adv., 2014, 4: 55556
This work reports a novel method involving anodic oxidation and a self-assembly process for controllable fabrication of a robust superhydrophobic aluminum (Al) alloy surface. The superhydrophobic surface with a water contact angle of 157.5 卤 0.5掳 and a sliding angle of 3 卤 0.7掳 is derived from its hierarchical micro-nanostructure and the assembly of low surface energy fluorinated components on it. Furthermore, the transformation from superhydrophilicity to superhydrophobicity can be achieved by adjusting the modification process for the constructed surface. The anti-scratch tests show that the superhydrophobic surface has good mechanical stability. It maintains superhydrophobicity after mechanical abrasion against P400 grit SiC sandpaper for 0.4 m and P800 grit sandpaper for 0.8 m, at the applied pressure of 3.60 kPa. The potentiodynamic polarization and electrochemical impedance spectroscopy tests show that the as-prepared superhydrophobic surface has excellent corrosion resistance. In addition, the as-prepared superhydrophobic surface has self-cleaning ability and good long-term stability. It is believed that the facile fabrication process offers an effective and promising application for fabricating a robust, anticorrosive and large scale superhydrophobic Al alloy surface.
DOI:10.1039/c4ra09390a      URL     [本文引用:]
[15] Badre C, Pauporté T, Turmine M, et al.Tailoring the wetting behavior of zinc oxide films by using alkylsilane self-assembled monolayers[J]. Superlattices Microstruct., 2007, 42: 99
Zinc oxide (ZnO) films with well-controlled morphologies have been prepared by electrochemical deposition. The different morphologies investigated are (i) flat and compact films, (ii) arrays of hexagonal nanocolumns, (iii) mesoporous films with open pores, and (iv) mesoporous films with pores filled with a surfactant (sodium dodecyl sulfate). Increasing the volume of voids in the film or the roughness gives rise to a dramatic increase in the layer wettability. The presence of surfactant in the film and/or the post-deposition binding of an alkylsilane (octadecylsilane) yield hydrophobic surfaces with contact angles measured as high as 145 鈭 after an optimized silane adsorption process.
DOI:10.1016/j.spmi.2007.04.018      URL     [本文引用:1]
[16] Sun T L, Feng L, Gao X F, et al.Bioinspired surfaces with special wettability[J]. Accounts Chem. Res., 2005, 38: 644
Biomimetic research indicates that many phenomena regarding wettability in nature, such as the self-cleaning effect on a lotus leaf and cicada wing, the anisotropic dewetting behavior on a rice leaf, and striking superhydrophobic force provided by a water strider's leg, are all related to the unique micro- and nanostructures on the surfaces. It gives us much inspiration to realize special wettability on functional surfaces through the cooperation between the chemical composition and the surface micro- and nanostructures, which may bring great advantages in a wide variety of applications in daily life, industry, and agriculture. This Account reviews recent progress in these aspects.
DOI:10.1021/ar040224c      PMID:16104687      URL     [本文引用:1]
[17] Chen X H, Kong L H, Dong D, et al.Fabrication of functionalized copper compound hierarchical structure with bionic superhydrophobic properties[J]. J. Phys. Chem., 2009, 113C: 5396
Hierarchical structure of flower-like CuO standing on Cu(OH)
DOI:10.1021/jp809616d      URL     [本文引用:]
[18] Nosonovsky M.Multiscale roughness and stability of superhydrophobic biomimetic interfaces[J]. Langmuir, 2007, 23: 3157
[本文引用:1]
[19] Jin C D, Li J P, Han S J, et al.A durable, superhydrophobic, superoleophobic and corrosion-resistant coating with rose-like ZnO nanoflowers on a bamboo surface[J]. Appl. Surf. Sci., 2014, 320: 322
Bamboo remains a vital component of modern-day society; however, its use is severely limited in certain applications because of its hydrophilic and oleophilic properties. In this work, we present a method to render bamboo surfaces superamphiphobic by combining control of ZnO nanostructures and fluoropolymer deposition while maintaining their corrosion resistance. Large-scale rose-like ZnO nanoflowers (RZN) were planted on the bamboo surface by a hydrothermal method. After fluoroalkylsilane (FAS) film deposition to lower the surface energy, the resulting surface showed superamphiphobicity toward water, oil, and even certain corrosive liquids, including salt solutions and acidic and basic solutions at all pH values. The as-prepared superamphiphobic bamboo surface was durable and maintained its superhydrophobic property with water contact angles >150掳 when stored under ambient condition for two months or immersed in a hydrochloric acid solution of pH 1 and a sodium hydroxide solution of pH 14 for 3h at 50掳C.
DOI:10.1016/j.apsusc.2014.09.065      URL     [本文引用:1]
[20] Nishino T, Meguro M, Nakamae K, et al.The lowest surface free energy based on-CF3 alignment[J]. Langmuir, 1999, 15: 4321
Free energy was measured for the surface of regular aligned closest hexagonal packed -CF3 groups. n-Perfluoroeicosane was vapor deposited onto glass, which gave epitaxially grown single-like crystallites with their molecular axes perpendicular to the glass surface. The dynamic contact angle of water on its surface was 119 degrees, which corresponds to a surface free energy of 6.7 mJ/m(2). This value is considered to be the lowest surface free energy of any solid, based on the hexagonal closed alignment of -CF3 groups on the surface.
DOI:10.1021/la981727s      URL     [本文引用:1]
[21] Wu X D, Zheng L J, Wu D.Fabrication of superhydrophobic surfaces from microstructured ZnO-based surfaces via a wet-chemical route[J]. Langmuir, 2005, 21: 2665
The fabrication of a superhydrophobic surface is demonstrated via a wet chemical route, and this method offers advantages of being cleanroom free, cost efficiency, and wide applicability. The preferable growth of ZnO crystalline forms a microstructured surface, and a variety of alkanoic acids were adopted to tune the surface wettability. Although all surfaces show an advancing contact angle greater than 150°, they substantially differ in the wetting mechanisms. It is found that only when the length of alkanoic acid is greater than 16, the microstructured surface shows a stable superhydrophobicity, in which the Cassie state dominates. While for those moderate-length alkanoic acids (C861C14), their corresponding surfaces have a tendency to fall into the Wenzel state and display a great contact angle hysteresis.
DOI:10.1021/la050275y      PMID:15779932      URL     [本文引用:1]
[22] Tian H, Yang T S, Chen Y Q.Fabrication and characterization of superhydrophobic thin films based on TEOS/RF hybrid[J]. Appl. Surf. Sci., 2009, 255: 4289
Preparation of superhydrophobic silica-based thin film by adjusting different concentration of reverse (W/O) emulsion of resorcinol formaldehyde resin (re-RF) which was hybridised with silica sol has been developed. The hybrid films were coated by the mixing solution which included precursor solution (sol–gel process) and re-RF (sol–gel process). Rough surfaces were obtained by removing the organic polymer at high temperature and then the hydrophobic groups bonded onto the films were obtained by the reaction with trimethylchlorosilane (TMCS). Characteristic properties of the as-prepared cross-section and surface of the films were analyzed by scanning electron microscopy (SEM) and atom force microscopy (AFM). The experimental parameters are mainly varied the weight ratio of re-RF to silica sol from 0.2 to 4.0. The result showed that the contact angle of the modified silica film was greater than 160° when the weight ratio of re-RF to silica sol was 2.0.
DOI:10.1016/j.apsusc.2008.11.040      URL     [本文引用:1]
[23] Li H J, Wang X B, Song Y L, et al.Super-“amphiphobic” aligned carbon nanotube films[J]. Angew. Chem.-Int. Edit., 2001, 40: 1743
[本文引用:]
[24] Nicolas M, Guittard F, Géribaldi S.Synthesis of stable super water- and oil-repellent polythiophene films[J]. Angew. Chem.-Int. Edit., 2006, 45: 2251
Eine blumenkohlartige Oberflche (siehe Bild, Ma&szlig;stab: 8 μm) und Perfluorkohlenstoffketten am Polymerr&uuml;ckgrat bewirken, dass der Film aus dem gezeigten fluorierten Polythiophen, der elektrochemisch auf einer Indiumzinnoxid-Oberflche abgeschieden wurde, sowohl superwasser- als auch &ouml;labsto&szlig;end ist. Der Einschub ist ein Foto eines Wassertropfens auf der Oberflche (Kontaktwinkel>150°).
DOI:10.1002/anie.200503892      PMID:16506255      URL     [本文引用:]
[25] Feng L, Li S H, Li Y S, et al.Super-hydrophobic surfaces: From natural to artificial[J]. Adv. Mater., 2002, 14: 1857
ABSTRACT Super-hydrophobic surfaces, with a water contact angle (CA) greater than 150掳, have attracted much interest for both fundamental research and practical applications. Recent studies on lotus and rice leaves reveal that a super-hydrophobic surface with both a large CA and small sliding angle () needs the cooperation of micro- and nanostructures, and the arrangement of the microstructures on this surface can influence the way a water droplet tends to move. These results from the natural world provide a guide for constructing artificial super-hydrophobic surfaces and designing surfaces with controllable wettability. Accordingly, super-hydrophobic surfaces of polymer nanofibers and differently patterned aligned carbon nanotube (ACNT) films have been fabricated.
DOI:10.1002/adma.200290020      URL     [本文引用:]
[26] Zhu X T, Zhang Z Z, Xu X H, et al.Facile fabrication of a superamphiphobic surface on the copper substrate[J]. J. Colloid Interface Sci., 2012, 367: 443
A simple solution-immersion technique was developed for the fabrication of a superamphiphobic surface on the copper sheet. Hierarchical structure composed of nanorod arrays and microflowers was formed on the copper surface by an alkali assistant oxidation process; after fluorination, the surface became super-repellent toward water and several organic liquids possessing much lower surface tension than that of water, such as hexadecane. Such superamphiphobicity is attributed to the synergistic effect of their special surface chemicals and microscopic structures, which allows for the formation of a composite interface with all probing liquids tested. We also discuss the effects of surface chemical constituent and geometrical structure on hydrophobicity and oleophobicity; such information allows us to engineer surfaces with specific oleophobic behavior. Additionally, the stability of the composite interface on the created superamphiphobic surface is studied by the compression and immersion test.
DOI:10.1016/j.jcis.2011.10.008      PMID:22074690      URL     [本文引用:]
[27] Li H, Rong S R, Liu E Y, et al.Fabrication and characterization of bionic amphiphobic functional surface on X70 pipeline steel[J]. Microsyst. Technol., 2015, 21: 2003
The amphiphobic surface has extremely broad application prospects in industrial production and daily life, such as preventing the adhering and fouling of materials and prolonging service life. In order to prepare an amphiphobic surface on X70 pipeline steel, a simple method was presented. The rough surface was created by shot blasting and chemical etching, consisting of micro-nano composite structures. The surface was then chemically modified by a low surface energy material, which contains a fluorocarbon group. The surface morphology, roughness, chemical composition, and wettability with distilled water and peanut oil were studied by field emission scanning electron microscopy, confocal microscopy, energy dispersive spectrometer, and contact angle measurement instruments. The results indicated that a micro-nano composite structure was created on the steel surface after shot blasting and chemical etching. The amphiphilic surface with micro-nano structure turned into an oleophobic and superhydrophobic surface after being chemically modified by low surface energy material. The maximum contact angles of the amphiphobic surface with distilled water and peanut oil were up to 15002±021° and 14002±021°, respectively.
DOI:10.1007/s00542-014-2330-5      URL     [本文引用:1]
[28] Cassie A B D, Baxter S. Wettability of porous surfaces[J]. Trans. Faraday Soc., 1944, 40: 546
[本文引用:1]
[29] Wenzel R N.Resistance of solid surfaces to wetting by water[J]. Ind. Eng. Chem., 1936, 28: 988
URL     [本文引用:1]
[30] Gao L C, McCarthy T J. Ionic liquids are useful contact angle probe fluids[J]. J. Am. Chem. Soc., 2007, 129: 3804
[本文引用:1]
[31] Xie Q, Xu J, Feng L, et al.Facile creation of a super-amphiphobic coating surface with bionic microstructure[J]. Adv. Mater., 2004, 16: 302
ABSTRACT The facile creation of a super-amphiphobic coating surface with bionic microstructure was discussed. The two easily synthesized polymeric materials, poly(methyl methacrylate) (PMMA) and fluorine-end-capped polyurethane (FPU) were captured for the coating. The scanning electron microscopy (SEM) was used to observe the microstructure of the polymer surface obtained by castings. It was found that the coating film prepared from a FPU/PMMA mixture had a rough micro-nano binary structure (MNBS), that was, every micro-papilla (300-700 nm) on the polymeric surface.
DOI:10.1002/adma.200306281      URL     [本文引用:1]
[32] Wang P, Zhang D, Qiu R, et al.Super-hydrophobic film prepared on zinc and its effect on corrosion in simulated marine atmosphere[J]. Corros. Sci., 2013, 69: 23
Zinc-laurylamine complex film with super-hydrophobicity is fabricated on zinc surface with electrolysis method. Super-hydrophobicity of film results from papillae and ridge-like structures, which form due to uneven corrosion of zinc at high anodic potential. The film obtained can maintain super-hydrophobic property in solution system, and can inhibit corrosion effectively. However, saline water penetrates into super-hydrophobic film during deliquescence process of NaCl particle in simulated marine environment. This behavior is induced by capillary condensation in groove of film, and it declines the advantage of using super-hydrophobic film as corrosion barrier in marine atmosphere. (C) 2012 Elsevier Ltd. All rights reserved.
DOI:10.1016/j.corsci.2012.10.025      URL     [本文引用:1]
[33] Song J L, Xu W J, Lu Y, et al.Fabrication of superhydrophobic surfaces on Mg alloy substrates via primary cell corrosion and fluoroalkylsilane modification[J]. Mater. Corros., 2013, 64: 979
The present work reports a simple and safe two-step process to render magnesium (Mg) alloy surfaces superhydrophobic via primary cell corrosion and subsequently cover it with a fluoroalkylsilane (FAS) film. The surfaces were characterized by scanning electron microscopy (SEM), optical microscopy, energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared spectrophotometry (FTIR), X-ray diffraction (XRD), and optical contact angle measurements. The power generated via the primary cell corrosion of copper and Mg alloys was also measured using a digital multimeter. The results show that micro/nanometer-scale binary rough structures and an FAS film with a low surface energy were present on the Mg alloy surfaces, both of which confer good superhydrophobicity with a water contact angle of 162.8 degrees and a tilting angle of 2 degrees. The micro/nanometer-scale binary rough structures consisted of micrometer-scale grains, cluster-like structures composed of nanometer-scale needles, and network-like structures composed of nanometer-scale sheets. Superhydrophobicity was analyzed by the Cassie-Baxter theory. Findings show that only about 6.3% of the water surface was in contact with the Mg alloy substrates, while the remaining 93.7% was in contact with the air cushion. The unique advantage of the proposed method is that power can be generated during the machining process of the superhydrophobic surfaces on the Mg alloy substrates.
DOI:10.1002/maco.201106454      URL     [本文引用:1]
资源
PDF下载数    
RichHTML 浏览数    
摘要点击数    

分享
导出

相关文章:
关键词(key words)
X80管线钢
混酸刻蚀
氟化处理
超疏水疏油
耐蚀性

X80 pipeline steel
acid etching
fluoroalkyl silane
amphiphobicity
anti-corrosion

作者
任继栋
高荣杰
张宇
刘勇
丁甜

REN Jidong
GAO Rongjie
ZHANG Yu
LIU Yong
DING Tian