喷涂法制备功能性超疏水复合涂层及其性能研究

以常用工程材料硅树脂BP与St(o)ber法合成的二氧化硅(SiO2)分散液为原料,运用喷涂法(spray-coating)制备出了功能性微/纳粗糙(MNR)结构的超疏水涂层,其接触角可以达到146.5°,滚动角小于1°(测试液滴量为15μL).通过分析喷涂法制备复合涂层所需的条件,得出喷涂液pH＝7.7-8.0时,在...     

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.     

二氧化硅／环氧树脂复合涂层的制备及其疏水性能

采用喷涂技术,在马口铁表面喷涂环氧树脂和二氧化硅复合涂层,研究了二氧化硅的含量对表面疏水性的影响,复合涂层的疏水性随二氧化硅含量的增加而增加．当二氧化硅质量分数增大到40％时,所制备的复合涂层与水的接触角约为141°且具有较小的滚动角．     

超疏水聚硅氧烷涂层的制备及其性能

采用溶胶-凝胶法,以甲基三乙氧基硅烷(MTES)为有机硅前驱体,通过酸-碱催化水解-缩合得到聚有机硅氧烷凝胶,经浸涂-提拉成膜技术在玻璃表面制备超疏水聚硅氧烷涂层。通过红外光谱(FT-IR)、水接触角(WCA)和场发射扫描电子显微镜(FE-SEM)等分析技术对涂层进行了结构表征、疏水性测试和表面形貌观察。结果表明,涂层内部形成带有甲基和残余硅羟基基团的网络结构。当n(MTES)∶n(EtOH)∶n(H2O)分别为1∶35∶8和1∶45∶8时,在室温制备的涂层对水的接触角可分别高达160°和162°,滚动角均低至7°,并且涂层在250℃以下的热处理过程中,其疏水性基本保持不变。FE-SEM观察证实了涂层表面分布着许多孔径为0.5～1.0μm的微孔和粒径为50～100 nm的纳米颗粒聚集体,具有微-纳米尺寸相结合的双重结构。此外涂层还具有较高的透明性、对腐蚀性液体具有超疏水性。研制得到的超疏水涂层有望用于玻璃、织物、金属和塑料等基底表面作为保护和防腐蚀涂膜。     

具有微纳米结构超疏水表面润湿性的研究

本文综述了近年来具有微纳米结构超疏水表面的研究进展。介绍了具有微纳米结构超疏水表面的制备方法,表面结构对超疏水性能的影响,周期性结构表面超疏水的条件,超疏水表面接触角滞后以及功能化超疏水表面等方面的研究,探讨了这一领域存在的问题及可能的发展方向。     

A Polymer Composite Film with Reversible Responsive Behaviors

Summary: A responsive polymer composite film was generated by the use of reversibly switchable surface morphology of polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) films in response to different block selective solvents on the rough isotactic poly(propylene) (i‐PP) substrate. The maximum difference of the water contact angle of the composite films increased from 22.6° of PS‐b‐PMMA films on the smooth substrate to 42.6° when they were treated by PS and PMMA selective solvents, respectively. The mechanisms of the responsive extent enhanced and the superhydrophobicity of the composite films were discussed in detail.

Schematic illustration of how to fabricate a wettability‐responsive composite film: (a) on the flat Si substrate, (b) on the rough PP substrate.     

仿生超疏水性表面的生物应用

自然给科学家和工程师带来仿生的灵感和启发. 近年来, 受自然界中荷叶的启发, 在充分考虑表面形貌和化学组成协同效应的基础上, 人们已经制备出许多仿生超疏水性表面, 这些表面在抗结冰、微流体、生物相容性等领域具有很多潜在的应用价值. 仿生超疏水性表面在生物领域的应用逐渐崭露头角, 研究发现, 超疏水性表面所俘获的空气能够减缓药物释放的速率, 因此利用此类表面作为药物的载体有望实现长期供药. 超疏水特性能在一定程度改善和提高生物体与材料表面之间的相互作用, 例如, 血小板几乎不在超疏水表面上进行粘附和活化避免了造成血栓和血凝, 因此仿生超疏水性表面可用于制备人造血管和与血液相接触的仪器. 细胞和生物分子在不同特殊润湿性表面具有不同的行为和现象, 如粘附、繁殖、吸附等差异, 这有助于进一步探索研究细胞和生物分子的信息功能, 是当前仿生超疏水性表面应用的重要研究方向之一. 本综述简单介绍了经典的润湿模型, 重点总结了仿生超疏水表面在生物领域的应用, 其主要包括控制药物释放、提高血液相容性、蛋白质吸附研究、细胞行为研究、生物分子和细胞微图案化等. 最后, 对仿生超疏水性表面在生物领域研究应用进行了展望.     

复合粒子涂膜表面疏水性能分形评价

采用接枝法和非均相乳液聚合与溶胶-凝胶法相结合技术,制备了不同形状的复合粒子,经低表面能的物质修饰后,其涂膜表面具有超疏水性。采用分形理论对涂膜表面疏水性进行评价,用分形维数表征涂膜表面微观形貌与疏水性能之间的关系,结果表明对于粗糙结构表面,分形维数较粗糙度因子能更好地反映表面形貌对水接触角的影响。     

阻燃超疏水棉纤维的制备及性能

将氢氧化镁(Mg(OH)₂)凝胶沉积到棉纤维上,以提高棉纤维表面粗糙度和阻燃性能,随后将含有Mg(OH)₂的棉纤维浸渍到聚二甲基硅氧烷(PDMS)溶液,获得阻燃超疏水棉织物。 并对棉纤维进行了傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)、疏水性、热稳定性、阻燃性能和耐久性测试。 结果表明,Mg(OH)₂负载到织物上,使得织物表面具有一定的微/纳米结构,形成了粗糙涂层。 当Mg(OH)₂浓度为1.0 mol/L时,Mg(OH)₂/PDMS改性的织物接触角(CA)可达158°,极限氧指数(LOI)提升至24.5%,导热系数为0.0525 W/(m·K), 具有超疏水和阻燃性能。 整理后织物经过20次洗涤,100次磨擦,极端条件处理后,CA仍大于150°,LOI值高于23%,显示了较好的耐久性。     

Preparation and characterization of PVDF microporous membrane with highly hydrophobic surface

Using the mixture of triethyl phosphate (TEP) and N,N‐dimethylacetamide (DMAc) as solvent, PVDF microporous membranes with highly hydrophobic surface were prepared by a modified NIPS method with a dual coagulation process. The effects of the exposure time on these membranes before being immersed into the coagulation bath and the composition in the coagulation bath on precipitation rate, membrane morphology, membrane hydrophobicity, membrane mechanical property, and membrane performance were studied. The morphologies and hydrophobicities of PVDF microporous membranes were investigated by scanning electron microscopy (SEM) and contact angle (CA) measurement. The precipitation processes were observed by light transmittance measurement. The pore size distribution was determined by liquid permeation technique. PVDF microporous membrane obtained by passing evaporation period of 60 min before being immersed into the water bath showed a high water CA of 122.1°. Using ethanol (EtOH) as coagulation bath, the water CAs of the top surface and bottom surface of the membrane increased to 125.9 and 132.6°, respectively. To further improve PVDF membrane hydrophobicity, a dual coagulation process was used and the mixed solvent (TEP–DMAc) was added into the first coagulation bath for 30 sec. Increase in the TEP–DMAc content led to the change in the morphology type of the membrane, that is, from an asymmetric structure with a dense top surface to a symmetric structure with a skinless top surface, and the pore size distribution widened greatly. By increasing the mass ratio of TEP to DMAc, the denseness of the membrane surface decreased significantly. Adding 60 wt% of TEP–DMAc to the first coagulation bath and the mass ratio of TEP to DMAc was 60:40, the CA reached to a maximum as high as 136.6°, and PVDF microporous membrane showed a high porosity of 80% and an excellent mechanical property of 3.14 MPa tensile strength and 61.79% elongation ratio. Copyright © 2009 John Wiley & Sons, Ltd.     

Fabrication of Superhydrophobic Surface with Different Metal Films on Aluminum Alloy

A simple technique was developed for the fabrication of a superhydrophobic surface on the aluminum alloy sheets. Different hierarchical structures(Ag, Co, Ni and Zn) were formed on the aluminum surface by the galvanic replacement reactions. After the chemical modification of them with fluorination, the wettability of the surfaces was changed from superhydrophilicity to superhydrophobicity. Scanning electron microscopy(SEM), energy dispersive spectrometry(EDS) and water contact angle measurement were performed to characterize the morphological characteristic, chemical composition and superhydrophobicity of the surfaces. The as-prepared superhydrophobic surfaces showed a water contact angle as high as ca.160° and sliding angle as low as ca.3°. We hope the method to produce superhydrophobic surface can be used in many fields.     

超疏水性表面的制备及应用进展

近年来,受荷叶、水黾腿、壁虎脚等天然超疏水生物表面特性的启发,研究者们进行了大量仿生超疏水表面材料的制备及应用研究。超疏水性表面因其特殊的微纳分层结构,具有自清洁、防覆冰、防腐蚀、减阻等优异性能。本文阐述了表面润湿、疏水的基本机理,以及超疏水表面研究的理论基础,对超疏水表面制备的最新研究进展进行了综述,并揭示了研究中存在的问题。最后,介绍了超疏水表面在涂料、织物、防腐、抗菌及防雾等领域中的应用,展望了其未来的研究方向和前景。     

聚丙烯／尼龙6原位复合材料的形态与表面,界面特性

以聚丙烯为基体、尼龙６为分散相共混得到分散相成纤的原位复合材料。显微形态观察发现在考察的浓度范围内微纤的直径基本与分散相含量无关。提高拉伸作用和增大剪切作用使微纤变细。当分散相含量越大，纤维数目越多时，水在复合材料表面的接触角越小，材料的吸水率越高。     

溶胶凝胶法制备仿生超疏水性薄膜

通过溶胶-凝胶(Sol-Gel)法和自组装(Self-assembled)制备了具有超疏水性的薄膜, 水滴在该薄膜上的平衡静态接触角为155°～157°, 滑动角为3°～5°. 通过扫描电子显微镜(SEM)观察薄膜微观表面, 发现该薄膜表面分布了双层结构(Binary structure)的微纳米粗糙度的微凸体, 上表层微米微凸体的平均直径为0. 2 μm, 下表层纳米微凸体的平均直径约为13 nm, 其分布与荷叶表面的结构极其相似. 用X射线光电子能谱(XPS)对薄膜表面元素进行了成分分析, 结果表明, 其表面存在大量的F, Cl等元素, 它能显著降低薄膜表面的表面能. 薄膜超疏水性的原因可能是, 通过硅片经溶胶粒子表面制备的薄膜具有合适的表面粗糙度, 再经过全氟辛基三氯甲硅烷(FOTMS)化学修饰后, 薄膜表面能进一步降低, 这两个条件的有机结合就使得薄膜产生了超疏水性.     

Design and fabrication of thin polymer coating on cotton fabric surface to impart hydrophobicity: An admicellar polymerization approach

The fluorinated poly(trifluoroethylmethacrylate) thin polymers were successfully prepared through free radical initiating admicellar polymerization approach using fluorosurfactant and 2,2,2-trifluoroethylmethacrylate (TFEM, monomer) system, which was initiated with potassium persulfate (KPS) initiator. The structure of the resultant polymer and morphology of the modified cotton fabric surfaces were confirmed by SEM and EDX analysis. The surface wettability of the modified cotton fabric was characterized by a water drop stay time and contact angle (CA) measurement. The coated cotton fabric exhibited excellent hydrophobicity with a water contact angle of 137.79°.     

Superhydrophobic Surfaces Produced by Carbon Nanotube Modified Polystyrene Composite Coating

The present work investigates the enhancement of water repellency on engineering materials surfaces using nanoscale roughness inherent in multi-walled carbon nanotubes (MWCNTs) together with a hydrophobic polystyrene coating via a simple spraying-based technique. The coatings show both a high contact angle and a small sliding angle for water droplets. The different surfaces obtained exhibit contact angles from 125° up to 153° depending on the preparation conditions. The observations of the topology by scanning electron microscopy reveal that the nanostructure created by the MWCNTs and the microstructure induced by the deposition of polystyrene particles forming a two-level structure that conceptually mimics the lotus leaf surface are necessary to create stable superhydrophobic surfaces.     

Superhydrophobic polymer‐particle composite films produced using various particle sizes

Hydrophilic alumina (Al₂O₃) nanoparticles (25, 35, and 150 nm) are dispersed in different concentrations in solutions of a commercial hydrophobic poly(alkyl siloxane) (Silres BS‐290), and the suspensions are sprayed on glass surfaces. Static contact angles (θ_S), measured on surfaces of siloxane‐nanoparticle composite films that were prepared from dilute dispersions, increase rapidly with particle concentration. Composite films prepared from concentrated dispersions exhibit a maximum, constant θ_S (at saturation θ_S is 160°), which is not affected by the size of the particles. These films exhibit also very small contact angle hysteresis (5°), which is also independent of the particle size. Consequently, the same superhydrophobic character can be induced in siloxane films using nanoparticles, which can range from a few up to several tenths of nanometers. However, the particle size and more precisely the particle specific surface area affects dramatically the minimum critical particle concentration, which must be used in the dispersions to induce superhydrophobicity on the surface of the composite films, that is, to achieve θ_S = 150°. It is shown that critical particle concentration decreases exponentially with specific surface area. This result can be important for manufacturers of superhydrophobic surfaces who are interested in having a good control on the wettability of the composite films. Copyright © 2012 John Wiley & Sons, Ltd.     

Significant change in water contact angle of electrospray‐synthesized SiO2 films depending on their surface morphology

Amorphous SiO₂ films were deposited by means of an electrospray technique. The relation between the water contact angle (WCA) of the deposited SiO₂ films and the surface morphology is investigated. The feeding rate of the electrospray process greatly affects the morphology of the synthesized SiO₂ films. There is also a significant change in the WCA on the surface of the films: the rougher the surface, the greater the WCA. A model based on the Cassie–Baxter formulation is used to explain the change observed in the WCA on the SiO₂ films. Copyright © 2012 John Wiley & Sons, Ltd.     

Preparation of Superhydrophobic ZnO Films on Zinc Substrate by Chemical Solution Method

Superhydrophobic surface was prepared on the zinc substrate by chemical solution method via immersing clean pure zinc substrate into a water solution of zinc nitrate hexahydrate[Zn(NO₃)₂·6H₂O] and hexamethylenetetraamine( C₆H₁₂N₄) at 95 ℃ in water bath for 1.5 h, then modified with 18 alkanethiol. The best resulting surface shows superhydrophobic properties with a water contact angle of about 158° and a low water roll-off angle of around 3°. The prepared samples were characterized by powder X-ray diffraction(XRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy(EDX), transmission electron microscopy(TEM), and scanning electron microscopy(SEM). SEM images of the films show that the resulting surface exhibits flower-shaped micro- and nano-structure. The surfaces of the prepared films were composed of ZnO nanorods which were wurtzite structure. The special flower-like micro- and nano-structure along with the low surface energy leads to the surface superhydrophobicity.