超疏水低粘着铜表面制备及其防覆冰性能

用喷砂处理在铜片表面形成微米级丘陵状凹坑,再用表面氧化处理在铜片表面制备菊花花瓣状CuO纳米片.通过喷砂-表面氧化处理在铜片表面成功构建了微米-纳米复合结构,这种表面氟化后与水滴的接触角高达161°,滚动角低至1°,显示出优异的超疏水性和很低的粘着性.低温下,这种表面与水滴间的热量交换较小,水滴不易凝结,有效地提高了抗结霜性.抗结霜性良好的超疏水铜有望在热交换器或低温运行设备等领域获得应用,这种简便的超疏水铜表面的制备方法也给其它工程材料超疏水表面的工业化制备提供了一个思路.     

铝合金表面原位自组装超疏水膜层的制备及耐蚀性能

采用阳极氧化法在铝合金表面原位构造粗糙结构, 经表面自组装硅氧烷后得到超疏水自清洁表面, 与水滴的接触角最大可达157.5°±2.0°, 接触角滞后小于3°. 通过傅立叶变换红外(FT-IR)光谱分析仪、场发射扫描电子显微镜(FE-SEM)、能谱仪(EDS)、原子力显微镜(AFM)和接触角测试对阳极氧化电流密度、硅氧烷溶液中水的含量和自组装时间等参数进行了分析, 并得到制备超疏水自清洁表面的最优工艺参数. FE-SEM及AFM的测试结果表明, 由自组装硅氧烷膜层的无序性形成的纳米结构和阳极氧化构造的微米级粗糙结构与硅氧烷膜层的低表面能的协同作用构成了稳定的超疏水表面. 电化学测试(动电位极化)的结果表明, 原位自组装超疏水膜层极大地提高了铝合金的耐蚀性.     

花生叶表面的高黏附超疏水特性研究及其仿生制备

花生是一种常见的豆科作物.与低黏附超疏水的荷叶不同,花生叶表面同时具有超疏水和高黏附特性.水滴在花生叶表面的接触角为151±2°,显示出超疏水特性.此外,水滴可以牢固地附着在花生叶表面,将花生叶翻转90°甚至180°,水滴均不会从表面滚落,显示了良好的黏附性(黏附力超过80μN).研究发现,花生叶表面呈现微纳米多级结构,丘陵状微米结构表面具有无规则排列的纳米结构.花生叶表面特殊的微纳米多尺度结构是其表面呈现高黏附超疏水特性的关键因素.结合实验数据,对花生叶表面特殊浸润性机理进行了简要阐述.受此启发,利用聚二甲基硅氧烷复形得到了与花生叶表面微结构类似的高黏附疏水表面.本文以期为仿生制备高黏附超疏水表面提供新思路.     

基于水滴模板法的微纳复合超疏水结构制备的研究

利用粒子辅助水滴模板法的实施获得规则蜂窝状图案化多孔结构模板,并进一步利用聚二甲基硅氧烷(PDMS)复制转移技术获得表面具有微米尺寸蜂窝状突起阵列的反向图案化结构.以这种图案化突起结构作为微米尺寸所提供的微米级粗糙度为基础,设计了2种的简单的二次纳米结构的引入过程,最终实现了微米级阵列和纳米级粗糙度的复合.第一种方法借助银镜反应来实现纳米银结构的化学沉积,最终在PDMS阵列表面获得了致密的纳米银颗粒沉积层,并成功获得了表面接触角达166度的超疏水性质.第二种方法利用了聚电解质/二氧化硅粒子层层静电自组装的方法引入纳米结构,结果在仅仅进行了2个组装循环的条件下即可获得超疏水性质的表面复合结构.通过简单的实验设计试图提供一种基于水滴模板法的微纳复合超疏水结构的普适性制备方法.     

用含氟丙烯酸酯无规共聚物制备超疏水膜

用微乳液聚合法制备了丙烯酸全氟烷基乙酯和甲基丙烯酸甲酯的无规共聚物,并对其进行了表征.采用溶剂挥发成膜法一步制备了具有超疏水性的该聚合物膜,水滴在该聚合物膜上的静态接触角可达151°~160°,滚动角小于3°.通过扫描电子显微镜观察发现该聚合物膜表面分布了许多乳突状突起和微孔洞,并具有微米和纳米尺度相结合的复合杂化结构.该类超疏水表面的形成是由适度粗糙的表面和低表面能相互结合引起的.探讨了该类超疏水膜的形成机理.     

形状记忆聚合物表面微结构及黏附性能的可逆调控

采用模板法在形状记忆聚合物表面构筑了微纳米等级结构,获得了一种具有低黏附性的超疏水表面.在外压作用下,表面微结构发生坍塌,失去超疏水性,同时呈高黏附性.在120℃热处理后,表面微结构恢复到原始状态,同时表面恢复到低黏附状态.通过外压及热处理过程可实现对表面微结构及其黏附性能的可逆调控.研究结果表明,表面不同的微结构状态赋予了表面不同的黏附性能,即在原始表面上,液滴处于低黏附的Cassie态,而在坍塌结构表面上水滴处于高黏附的Wenzel态.     

CaCO_3颗粒模板法制备聚合物超亲水/超疏水表面

以碳酸钙(CaCO3)颗粒层为模板,运用简单的热压和酸蚀刻相结合的方法制备聚合物超亲水/超疏水表面.首先在玻璃基底上均匀铺撒一层CaCO3颗粒,以此作为模板,通过热压线性低密度聚乙烯(LLDPE)使CaCO3颗粒均匀镶嵌在聚合物表面,获得了超亲水性质;进一步经酸蚀得到了具有微米和亚微米多孔结构的表面,其水滴静态接触角(WCA)可达(152.7±0.8)°,滚动角小于3°,具备超疏水性质.表面浸润性能和耐水压冲击性能研究表明该超疏水表面具有良好的稳定性和持久性.用同样工艺微模塑/酸蚀刻其它疏水性聚合物,得到类似结果.     

双级微结构上二氧化硅粒子对微注压成型PP表面润湿特性的影响

提出一种柔性复制法,采用微注射压缩(μ-ICM)成型具有微拓扑结构的仿生聚丙烯(PP)表面.通过复制模板上的双级微结构,所成型的PP材料表面上呈现具有锥形顶面的双级微结构,即微棱和高纵横比的微锥体.由于微锥体之间的间隙较大,水滴浸润其间隙的上方,这使该表面呈现中等黏附的超疏水特性.在μ-ICM过程中,涂覆在模板上的二氧化硅纳米粒子(SNPs)被转移到熔体中,并牢牢附着于微结构表层,赋予其表面亚微米或微米粗糙度,形成多层次微结构.在附着有亲水SNPs的微结构上,高表面自由能使水滴完全浸润微锥体之间的间隙,表面的水接触角为161.9°、滚动角大于90°,呈现极高黏附的超疏水特性(花瓣效应);在附着有疏水SNPs的微结构上,水滴受疏水SNPs的排斥而减弱与表面之间的黏附作用,表面的水接触角为163.5°、滚动角为3.5°,呈现极低黏附的超疏水特性(荷叶效应).     

软模板印刷法制备超疏水性聚苯乙烯膜

首次利用软模板印刷的方法,以微米-亚微米-纳米复合结构的PDMS为软模板,在平滑聚苯乙烯表面上成功制备了同样具有微米-亚微米-纳米复合结构的超疏水表面,该表面与水的接触角高达161.2º。软模板印刷方法可以用在其它热塑性聚合物如聚丙烯、聚甲基丙烯酸甲酯和聚碳酸酯等材料上,是一种简单有效地制备超疏水性表面的方法。     

静电纺丝制备超疏水TiO2纳米纤维网膜

采用静电纺丝技术构筑粗糙表面, 再使用廉价的低表面能物质硅油在煅烧过程中进行同步修饰, 制备出接触角大于150°, 滚动角小于5°的TiO2超疏水表面. 该超疏水表面具有由TiO2纳米纤维和微米尺寸颗粒状硅油高温分解产物织构而成的纳米纤维网膜结构, 这种特殊的微纳米复合粗糙结构和疏水性硅油分解产物的修饰作用导致TiO2纳米纤维网膜的超疏水性. 这种超疏水的TiO2材料为超疏水材料在防水织物、无损失液体运输和微流体等领域的应用提供了新的研究视野.     

二氧化硅纳米颗粒/硅树脂复合超疏水功能涂层的制备和性能研究

将二氧化硅纳米颗粒和硅树脂制成混合液,采用喷涂法(spray-coating)制备出了具备超疏水性的复合涂层.研究了二氧化硅、硅树脂不同含量配比对涂层疏水性能的影响,结果表明复合涂层的接触角随二氧化硅含量的增加而增加.在二氧化硅含量大于3%(质量分数)时,涂层显现超疏水性;当二氧化硅含量为3%(质量分数)、硅树脂含量为7%(质量分数)时,涂层与水的接触角达到151.6°,滚动角接近0°.通过扫描电子显微镜(SEM)观察涂层表面的微观结构,发现超疏水性的涂层具备微-纳复合阶层结构,类球状突起粒径在5μm左右,类球状突起上分布纳米团聚颗粒,直径约为50 nm.这种类似荷叶表面的微(纳复合阶层结构,结合硅树脂的低表面能,使得复合涂层具备了超疏水性能.     

One step preparation of superhydrophobic polymeric surface with polystyrene under ambient atmosphere

Brassica oleracea-like polymer surface is facilely fabricated by one-step casting process using amorphous polystyrene (PS) under ambient atmosphere. The obtained coatings show excellent superhydrophobicity and only possess unitary micro-scale structure, similar to the natural brassica leaf. In addition, a simple topography analysis also roughly verifies superhydrophobic structure of branched and intermingled sticks and bumps. This process provides a fairly easy procedure for preparing superhydrophobic surface from common plastics. Moreover, it demonstrates that the micro/nano-binary structure is not necessary for superhydrophobicity, while unitary micro-scale structure for a polymer surface can exhibit outstanding water repellency as natural lotus.     

Nanostructures increase water droplet adhesion on hierarchically rough superhydrophobic surfaces

Hierarchical roughness is known to effectively reduce the liquid-solid contact area and water droplet adhesion on superhydrophobic surfaces, which can be seen for example in the combination of submicrometer and micrometer scale structures on the lotus leaf. The submicrometer scale fine structures, which are often referred to as nanostructures in the literature, have an important role in the phenomenon of superhydrophobicity and low water droplet adhesion. Although the fine structures are generally termed as nanostructures, their actual dimensions are often at the submicrometer scale of hundreds of nanometers. Here we demonstrate that small nanometric structures can have very different effect on surface wetting compared to the large submicrometer scale structures. Hierarchically rough superhydrophobic TiO(2) nanoparticle surfaces generated by the liquid flame spray (LFS) on board and paper substrates revealed that the nanoscale surface structures have the opposite effect on the droplet adhesion compared to the larger submicrometer and micrometer scale structures. Variation in the hierarchical structure of the nanoparticle surfaces contributed to varying droplet adhesion between the high- and low-adhesive superhydrophobic states. Nanoscale structures did not contribute to superhydrophobicity, and there was no evidence of the formation of the liquid-solid-air composite interface around the nanostructures. Therefore, larger submicrometer and micrometer scale structures were needed to decrease the liquid-solid contact area and to cause the superhydrophobicity. Our study suggests that a drastic wetting transition occurs on superhydrophobic surfaces at the nanometre scale; i.e., the transition between the Cassie-Baxter and Wenzel wetting states will occur as the liquid-solid-air composite interface collapses around nanoscale structures. Consequently, water adheres tightly to the surface by penetrating into the nanostructure. The droplet adhesion mechanism presented in this paper gives valuable insight into a phenomenon of simultaneous superhydrophobicity and high water droplet adhesion and contributes to a more detailed comprehension of superhydrophobicity overall.     

硼砂-对苯二甲酸电解液中AZ91D镁合金的阳极氧化处理

研究了硼砂-对苯二甲酸环保型电解液中AZ91D镁合金的阳极氧化.考察了对苯二甲酸对镁合金阳极氧化过程及其氧化膜性能的影响,并利用扫描电镜(SEM)、X射线衍射(XRD)、能量散射谱(EDS)、动电化极化和电化学交流阻抗谱(EIS)等进行了分析表征.结果表明,对苯二甲酸的浓度对阳极氧化成膜过程、氧化膜的表面形貌、厚度、相结构和耐腐蚀性能都有重要影响.在硼酸盐电解液中加入适量的对苯二甲酸后,氧化电流密度降低,过度放电现象受到了明显的抑制,所制得的阳极氧化膜的质量也有了显著改善.氧化膜表面变得光滑、致密,膜厚度略有降低.氧化膜与镁合金基底的结合更紧密,而且其耐腐蚀性能也得到了明显增强.该研究对于镁合金阳极氧化处理工艺的环保化及阳极氧化膜质量的提高都具有积极意义.     

Fabrication of super-oil-repellent dual pillar surfaces with optimized pillar intervals

Hierarchical dual pillar surfaces with optimized pillar intervals are fabricated by a novel combined process of the oblique angle magnetron sputtering deposition of Al-Nb alloys and their anodizing. The pillar intervals are controlled by the deposition angle and cell size of a scalloped substrate for oblique angle deposition. Anodizing of the deposited pillar surfaces develops a nanopillar oxide layer, producing the hierarchical dual pillar surfaces. After being coated with a fluoroalkyl phosphate layer to reduce the surface free energy, hierarchical surfaces with submicrometer pillar intervals greater than 400 nm show super liquid repellency even for hexadecane with a low surface tension of 27.5 mN m(-1), although the submicrometer pillar surfaces with smaller submicrometer pillar intervals and without nanopillars were not super-oil-repellent. In contrast, the dual pillar surfaces show superhydrophobicity regardless of the submicrometer pillar intervals. Thus, the present study demonstrates the importance of the pillar intervals (gap size between pillars) to realize the superoleophobicity.     

Relationships between structure and activity of carbon as a multifunctional support for electrocatalysts

We report on new insights into the relationships between structure and activity of glassy carbon (GC), as a model material for electrocatalyst support, during its anodization in acid solution. Our investigation strongly confirms the role of CFGs in promotion of Pt activity by the "spill-over" effect related to CO(ads) for methanol electrooxidation (MEO) on a carbon-supported Pt catalyst. Combined analysis of voltammetric and impedance behaviour as well as changes in GC surface morphology induced by intensification of anodizing conditions reveal an intrinsic influence of the carbon functionalization and the structure of a graphene oxide (GO) layer on the electrical and electrocatalytic properties of activated GC. Although GO continuously grows during anodization, it structurally changes from being a graphite inter-layer within graphite ribbons toward a continuous GO surface layer that deteriorates the native structure of GC. As a consequence of the increased distance between GO-spaced graphite layers, the GC conductivity decreases until the case of profound GO exfoliation under drastic anodizing conditions. This exposes the native, yet abundantly functionalized, GC texture. While GC capacitance continuously increases with intensification of anodizing conditions, the surface nano-roughness and GO resistance reach the highest values at modest anodizing conditions, and then decrease upon drastic anodization due to the onset of GO exfoliation. We found for the first time that the activity of a GC-supported Pt catalyst in MEO, as one of the promising half-reactions in polymer electrolyte fuel cells, strictly follows the changes in GC nano-roughness and GO-induced GC resistance. The highest GC/Pt MEO activity is reached when optimal distance between graphite layers and optimal degree of GC functionalization bring the highest amount of CFGs into intimate contact with the Pt surface. This confirms the promoting role of CFGs in MEO catalysis.     

Mechanical and superhydrophobic stabilities of two-scale surfacial structure of lotus leaves

To understand why lotus leaf surfaces have a two-scale structure, we explore in this paper two stability mechanisms. One is the stability of the Cassie-Baxter wetting mode that generates the superhydrophobicity. A recent quantitative study (Zheng et al., Langmuir 2005, 21, 12207) showed that the larger the slenderness ratio of the surface structures was, the more stable the Cassie-Baxter wetting mode would be. On the other hand, it is well-known that more slender surface structures can only sustain lower critical water pressures for structure buckling, or Euler instability, while in the natural environments, the water pressure impacting on the lotus surface can reach a fairly high value (105 Pa in a heavy rain). Our analysis reveals that the two-scale structure of the lotus leaf surfaces is necessary for keeping both the structure and the superhydrophobicity stable. Furthermore, we find that the water-air interfacial tension makes the slender surface structure more instable and the two-scale structure a necessity.     

Facile fabrication of colored superhydrophobic coatings by spraying a pigment nanoparticle suspension

Superhydrophobic coatings were prepared by spraying a pigment nanoparticle suspension. By changing the type of pigment nanoparticles, the colors of the coating could be controlled. The particle size of the pigments, which determines the surface structure of the coatings, played an important role in exhibiting superhydrophobicity. The spray-coating process is applicable to a variety of materials (e.g., copper, glass, paper, coiled wire, and tied thread), and the superhydrophobicity was repairable.     

Surface modification of titanium with thermally treated polydimethylsiloxane coating and the effect on resin to titanium adhesion

In this study, titanium surface modification by a thermal treatment using a polydimethylsiloxane (PDMS) coating was investigated. The surfaces of four titanium samples were surface treated by polishing, sandblasting, and coating with a PDMS with a thermal treatment at 800 and 1100 °C. The titanium surfaces were characterized by X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy. The effect of the surface treatments on adhesion of resin to titanium was assessed by shear adhesion strength test. XPS analysis showed that there was a change of elemental composition of titanium surfaces after surface treatment. Binding energy shifts for Si2p and O1s were observed after sandblasting and thermally treated PDMS. Therefore, chemical states of Si and O were changed. Atomic force microscopy analysis revealed that the surface topography of the Ti samples was different, and surface roughness was increased after sandblasting and thermal treatment of PDMS coating. Shear adhesion strength test results showed that the adhesion between resin and titanium is affected by the treatment temperature of PDMS coating. The highest adhesion is obtained at 1100 °C (14.7 ± 1.57 MPa). Copyright © 2014 John Wiley & Sons, Ltd.