氨基硅ASO-702在再生纤维素表面的膜形貌及其定向排列方式

以再生纤维素作基质,在其表面组装了N-环己基-γ-氨丙基聚二甲基硅氧烷(ASO-702),分别用X射线光电子能谱(XPS)、原子力显微镜(AFM)以及接触角测定仪对ASO-702的膜形貌进行了观察和表征.结果表明,在再生纤维素基质表面,氨基硅ASO-702能形成均一相疏水膜,该膜能有效降低再生纤维基质表面的粗糙度.XPS和接触角测定仪对纤维表面分析的结果表明,在处理后的棉纤维表层确有ASO-702硅膜存在,而且该膜疏水,接触角达到91.5°.从而进一步证明了氨基硅在纤维表面的定向排列成膜方式为:硅甲基朝外、Si-O偶极键及阳离子化氨基指向纤维表面.     

聚(3,3,3-三氟丙基)甲基/N-β-氨乙基-γ-氨丙基甲基硅氧烷的合成及其构筑的超疏水织物

以KOH为催化剂,实现了1,3,5-三甲基-1,3,5-三(3,3,3-氟丙基)环三硅氧烷(DF3)和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷(APAEDMS)的本体聚合,得到了侧链含(3,3,3-三氟丙基)和N-β-氨乙基-γ-氨丙基的聚甲基硅氧烷(FASO),并以其为低能物质,结合凝胶-溶胶法将普通棉织物构筑为接触角为156°的超疏水织物。红外光谱(IR)和核磁共振(1 H-NMR)分析表明FASO具有预期的化学结构,处理前后织物表面SEM和疏水性分析表明:织物自身具有的微米尺度二维粗糙度和FASO修饰所形成的低能表面是织物变疏水的主要原因,纳米SiO2在纤维束表面构建的纳米尺度粗糙度,可将水在纤维-水接触面间所占分率由34.7%降低到10%,接触角由134.5°提高到156°。最后,用X-射线光电子能谱(XPS)对超疏水织物的表面成分进行了分析。     

纳米纤维素修饰的碳纳米纤维制备及其疏水性研究

为拓展碳纳米纤维在环境清洁领域的应用，提高碳纳米纤维的水接触角，改善膜表面的疏水性能，获得疏水性较好的碳纳米纤维薄膜，利用静电纺丝法将纳米纤维素(CNFs)与碳纳米纤维前驱体复合，获得具有低表面能和良好疏水性能的纳米碳纤维/纳米纤维素复合纤维膜。通过对纳米纤维素含量进行调控，经预氧化和碳化处理后得到一系列具有规则三维空间网络结构的复合纤维膜，并探究不同纳米纤维素含量对复合纤维膜疏水性能的影响。结果表明：纳米纤维素修饰复合纤维膜随着碳化程度的提高其表面能呈现逐渐降低的趋势，其对水的接触角也逐渐增大，疏水效果得到较大幅度提升。随着纳米纤维素含量继续增加，复合纤维膜的水接触角呈上升趋势，未添加前接触角为36.13°,当纳米纤维素添加质量为20%时，水接触角最大为132.14°,提高了366%。     

Vi-PDMS/S-SiO2超疏水聚酯纤维织物的制备及性能研究

目的 基于普通织物材料防水性较差的问题,制备一种具有超疏水涂层的聚酯纤维织物,并对其性能进行研究。方法 以聚酯纤维织物为基材,基于紫外光固化技术通过浸涂法,使用商用气相纳米SiO₂颗粒(S-SiO₂)、端乙烯基聚二甲基硅氧烷(Vi-PDMS)在织物表面构筑微纳粗糙结构,获得超疏水的织物。采用扫描电子显微镜、水接触角测量仪对其微观结构和疏水性能进行表征,并通过机械摩擦实验对其超疏水稳定性进行考察。结果 当Vi-PDMS和S-SiO₂质量比为1∶4时,选择交联剂为三羟甲基丙烷三丙烯酸酯(TMPTA)制备的聚酯纤维织物表面的水接触角可达到151°,滚动角可达9°;且经过40次循环摩擦后,其表面水接触角仍大于140°,具有一定的耐磨性。结论 基于紫外光固化技术,采用操作简便的浸涂法制备的聚酯纤维织物具有优异的超疏水性能和一定的耐磨性,为织物超疏水性能研究提供参考,有望应用于超疏水聚酯纤维织物领域。     

静电纺丝制备超疏水/超亲油空心微球状PVDF纳米纤维及其在油水分离中的应用

采用静电纺丝技术制备了超疏水超亲油具有空心微球结构的聚偏二氟乙烯(PVDF)纳米纤维。通过扫描电镜(SEM)对样品的表面形貌及纤维直径的变化进行了表征。通过视频显微镜对纳米纤维表面与水的接触角和水滴照片进行测量与拍照。研究了不同结构的PVDF纳米纤维对润滑油的吸附性能。结果表明:PVDF/N,N-二甲基甲酰胺/H_2O静电纺丝溶液中水含量达到2.5%时得到具有空心微球结构的纳米纤维,纤维表面的水接触角为153.55°,其吸油率达到21.48g/g。     

基于再生纤维素基质组装的氨基硅膜形貌及其定向排列方式

用原子力显微镜AFM、光电子能谱仪XPS等研究了组装在再生纤维素基质(cel)表面的N-β-氨乙基-γ-氨丙基聚二甲基硅氧烷(ASO-1)的膜形貌、表面相化学组成及疏水性.结果发现,受基质表面不平整性的影响,组装在cel表面的氨基硅膜(ASO-1/cel),微观上会表现出一种类似于基质的粗糙形貌.而XPS分析和接触角测定结果表明,ASO-1/cel表面强烈疏水,在其表层明显存在由氨基硅ASO-1所产生的Si2p、Cls、Nls和Ols XPS峰.据此推测,ASO-1在cel表面的定向排列成膜方式为:硅甲基朝外伸向空气、Si-O偶极键以及极性氨基指向基质界面.     

Al2O3微滤膜的超疏水改性研究

采用多层自组装技术在Al₂O₃微滤膜表面制备TiO₂纳米涂层, 并利用1H,1H,2H,2H-全氟辛基乙基三乙氧基硅烷(PFDS)对其表面进行氟化处理, 获得超疏水改性膜。通过X射线衍射仪, 傅立叶变换红外光谱仪, 原子力显微镜, 水接触角测试仪和扫描电子显微镜对改性膜进行表征。分析了TiO₂纳米涂层的晶型结构, 探讨了TiO₂沉积时间与改性膜表面粗糙度和疏水性之间的关系, 研究了PFDS改性次数对膜表面形貌和疏水性能的影响规律。结果表明: 在600℃退火1 h后, 获得锐钛矿结构的TiO₂纳米涂层。随TiO₂沉积时间的延长, 膜表面粗糙度增大, 水滴在膜表面的接触由Wenzel状态转变为Cassie状态; 当TiO₂沉积时间为50?min, PFDS改性3次时, 获得理想的微纳米二级超疏水表面形貌, 水接触角达到174.5°。     

聚丙烯超疏水纤维膜的制备及其在油水分离中的应用

利用磁控溅射法在聚丙烯(PP)纤维膜上溅射SiO2纳米粒子,制备超疏水超亲油纤维膜,用于油水分离领域中。在PP纤维膜上溅射SiO2纳米粒子增加表面粗糙度,降低表面能达到超疏水的效果。通过调节溅射功率,改变疏水效果,当溅射功率为100W时,纤维膜的疏水性能最好,对水的接触角高达162.8±2.1°,对油的接触角为0°。更重要的是,PP-SiO2纤维膜在油水分离过程中仅仅依靠重力驱动,能够使油和水快速分离并且重复使用10次之后依然保持超疏水性,分离效率保持在90%左右,这将在工业油污和海洋溢油处理中,提供了新的材料。     

钢铁表面超疏水膜的制备与表征

采用水热法结合氟硅烷修饰直接在钢铁表面制备超疏水膜。疏水膜的疏水性与钢铁基底的微纳米结构有重要关系。结果表明,以乙二胺为溶剂,经140℃水热反应4h和160℃水热反应5h,可以在钢铁表面制得具有次级网状结构的正八面体、花状等微纳米精细结构,再经氟硅烷修饰后表现出良好的超疏水性,与水滴的接触角分别达到156.49和165.31°。XRD的分析结果表明,该微纳米结构的主要成分是Fe3O4,它的形成一方面提供了制备超疏水表面所必须的微纳米精细结构,另一方面又为与氟硅烷发生反应生成牢固的薄膜创造了条件。电化学分析结果表明,超疏水膜层的存在显著降低了钢铁基底的腐蚀倾向。     

超疏水-超亲油纤维膜的构筑及其在油水分离中的应用

在水溶液中,氧化石墨烯(GO)/阳离子聚丙烯酰胺(CPAM)复合膜通过一个独特的自组装过程制备,随后在室温下,硼氢化钠溶液快速还原中,产生基质负载的导电性纤维膜。利用电解原理在导电性纤维膜表面上镀上一薄层Cu微纳米颗粒。在光滑的纤维骨架表面通过复合Cu微纳米颗粒构筑具有一定粗糙度的微纳米结构,同时在Cu微纳米颗粒表面修饰上低表面能的硬脂酸,制备具有超疏水-超亲油界面特性的复合材料,接触角到达153°,以实现高效油水分离的目的。     

碱式硫酸镁晶须复合SiO2纳米粒子制备高/低黏附性超疏水涂层

超疏水材料因性能独特,应用前景广阔而被广泛关注。本文采用碱式硫酸镁晶须(MOSWs)与二氧化硅纳米粒子制备超疏水涂层,首先对MOSWs及50 nm、500 nm SiO₂进行表面改性以降低表面能,然后基于混料实验将三者按比例混合以构造表面粗糙度,以接触角、滚动角及平均粗糙度R_a为响应变量建立回归模型,分析了混合分量的形貌、尺寸与混合比例对响应变量的影响,并探讨了超疏水涂层微观结构对水滴黏附性的影响以及粗糙度与超疏水性能之间的关系。结果表明：MOSWs复合SiO₂纳米粒子可制备具有不同黏附性的超疏水涂层,单独使用MOSWs可制备高黏附性超疏水涂层,其接触角达152.59°,涂层水平倒置水滴不滴落;而MOSWs与50 nm SiO₂以相同质量分数混合,可制备低黏附性超疏水涂层,其接触角达163.25°,滚动角可趋近0°。所制备涂层的平均粗糙度R_a值位于5～10μm之间时,接触角较大,滚动角较小,超疏水性能较佳。     

Robust Flower‐Like TiO2@Cotton Fabrics with Special Wettability for Effective Self‐Cleaning and Versatile Oil/Water Separation

Inspired by the hierarchical structure of the mastoid on the micrometer and nanometer scale and the waxy crystals of the mastoid on natural lotus surfaces, a facile one‐step hydrothermal strategy is developed to coat flower‐like hierarchical TiO₂ micro/nanoparticles onto cotton fabric substrates (TiO₂@Cotton). Furthermore, robust superhydrophobic TiO₂@Cotton surfaces are constructed by the combination of hierarchical structure creation and low surface energy material modification, which allows versatility for self‐cleaning, laundering durability, and oil/water separation. Compared with hydrophobic cotton fabric, the TiO₂@Cotton exhibits a superior antiwetting and self‐cleaning property with a contact angle (CA) lager than 160° and a sliding angle lower than 5°. The superhydrophobic TiO₂@Cotton shows excellent laundering durability against mechanical abrasion without an apparent reduction of the water contact angle. Moreover, the micro/nanoscale hierarchical structured cotton fabrics with special wettability are demonstrated to selectively collect oil from oil/water mixtures efficiently under various conditions (e.g., floating oil layer or underwater oil droplet or even oil/water mixtures). In addition, it is expected that this facile strategy can be widely used to construct multifunctional fabrics with excellent self‐cleaning, laundering durability, and oil/water separation. The work would also be helpful to design and develop new underwater superoleophobic/superoleophilic materials and microfluidic management devices.     

Fabrication of sticky and slippery superhydrophobic surfaces via spin-coating silica nanoparticles onto flat/patterned substrates

Silica nanoparticles were spin-coated onto a flat/patterned (regular pillar-like) substrate to enhance the surface roughness. The surface was further modified by a self-assembled fluorosilanated monolayer. The advancing/receding contact angle and sliding angle measurements were performed to determine the wetting behavior of a water droplet on the surface. It is interesting to find that a transition from a Wenzel surface to a sticky superhydrophobic surface is observed due to the spin-coating silica nanoparticles. A slippery superhydrophobic surface can be further obtained after secondary spin-coating with silica nanoparticles to generate a multi-scale roughness structure. The prepared superhydrophobic substrates should be robust for practical applications. The adhesion between the substrate and nanoparticles is also examined and discussed.     

基于聚多巴胺的超疏水棉织物的一锅法制备及其油水分离性能

将棉织物浸入多巴胺、硝酸银、十六烷基三甲氧基硅烷的乙醇溶液中,取出烘干制备出超疏水棉织物。用扫描电子显微镜和X射线光电子能谱表征其表面形貌和元素,用接触角测量仪测量其接触角并进行摩擦或液体浸泡(如酸、碱、沸水)实验检测其耐用性。结果表明,聚多巴胺的强附着性使原位生成的银纳米粒子能经受摩擦或不同液体的浸泡,从而使超疏水织物具有良好的耐用性。超疏水棉织物还具有良好的油水分离性能,其油水分离效率高达97%,油流量最高可达15.93 m³·m^-2·h^-1。     

Differential superhydrophobicity and hydrophilicity on a thin cellulose layer

Here we have developed cellulosic materials (cotton fabric or paper) with differential superhydrophobicity and hydrophilicity on each side of the surfaces by coating with polyvinylidene fluoride and fluorinated silane molecules using electro-spraying. Such materials are advantageous in various textile and medical applications.Analysis of surface morphology indicated that, not only surface chemical property and roughness, but also particle diameter affects surface superhydrophobicity. Smaller particle diameter enhances superhydrophobicity, if the surface roughness and surface chemical property remain constant. By controlling these three factors, superhydrophobicity with a water contact angle of more than 160° can be achieved at one side of a thin cellulosic material while maintaining the hydrophilicity (contact angle is 0°) at the opposite side.     

Morphologies and Superhydrophobicity of Hybrid Film Surfaces Based on Silica and Fluoropolymer

Fluoropolymer and different kinds of silica particles were used for controlling surface chemistry and morphology, respectively. A superhydrophobic surface originated from strawberry-like or quincunx-shaped composite silica particles was obtained. The dual size particles are obtained by utilizing the graft of different modified silica particles with epoxy functional group and amine functional group, This makes the surface of film form a composite interface to have irregular binary structure which plays an essential role in trapping air between the substrate surface and the liquid droplets to be necessary for high contact angle and low contact angle hysteresis. The maximum contact angle for water on the hybrid film is about 174±2° and the contact angle hysteresis is less than 2°. The surface morphologies, roughness and the wettability on the surface of films containing different structural silica particles were compared. It was shown that the hierarchical irregularly structure with a low roughness factor and high air-trapped ratio is indispensable for superhydrophobic surface. Although this structural surfaces based on composite silica particles play a vital role in governing the surface wettability, it is necessary to combine with a low surface energy to make the surface superhydrophobic.     

PVDF/SiO2/PDMS涂层超疏水纺织品性能

目的 针对普通纺织品材料防水性和防污性较差的问题,制备具有自清洁功能的超疏水涂层纺织品,并研究其性能.方法 以涤纶织物为基材,通过非溶剂诱导相分离法,使用聚偏氟乙烯和疏水纳米二氧化硅复合液在纺织品表面构筑微纳粗糙结构,采用聚二甲基硅氧烷对其进行疏水化处理,获得自清洁超疏水涂层纺织品.采用扫描电子显微镜、X射线能量散射光谱和视频光学接触角测量仪等对其结构和性能进行表征,并通过机械摩擦、洗涤、酸/碱/盐溶液浸渍和紫外光照等方法对其表面超疏水稳定性进行考察.结果 当聚偏氟乙烯质量分数为2％,疏水纳米二氧化硅质量分数为0.4％,聚二甲基硅氧烷质量分数为1％时,制备的纺织品的表面接触角可达(162.2°±0.8°),滚动角达(2.0°±0.4°),具有优异的超疏水自清洁效应;经72 h酸/碱/盐溶液浸渍、196 h紫外光照、2500次摩擦和120次家庭水洗后,其表面接触角仍大于150°,表现出优异的超疏水稳定性.结论 采用简便的非溶剂相分离法制备的涂层纺织品具有优异的自清洁性能,并且其超疏水性能具有机械耐久性和化学稳定性,有望应用于纺织材料包装领域.     

Superhydrophobic surfaces on cotton textiles by complex coating of silica nanoparticles and hydrophobization

By the complex coating of amino- and epoxy-functionalized silica nanoparticles on epoxy-functionalized cotton textiles to generate a dual-size surface roughness, followed by hydrophobization with stearic acid, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, or their combination, superhydrophobic surfaces were prepared. The static water contact angle of the most superhydrophobic sample as prepared reaches 170° for a 5 μL droplet. The wettability and morphology were investigated by contact angle measurement and scanning electron microscopy. Characterizations by Fourier transformation infrared spectroscopy, and thermal gravimetric analysis were also conducted.     

A non-fluorinated mechanochemically robust volumetric superhydrophobic nanocomposite

The widespread use of water-repellent superhydrophobic surfaces is limited by the inherent fragility of their micro-and nanoscale roughness, which is prone to damage and degradation. Here, we report a non-fluorinated volumetric superhydrophobic nanocomposites that demonstrate mechanochemical robustness. The nanocomposites are produced through the addition of microscale diatomaceous earth and nanoscale fumed silica particles to high-temperature vulcanized silicone rubber. The water-repellency of the surface and bulk of nanocomposites having 120 phr of filler was determined based on the water contact angle and contact angle hysteresis. We compared the water-repellency of nanocomposites of differing diatomaceous earth to fumed silica mass ratios. Increasing the amount of diatomaceous earth enhanced the water-repellency of the nanocomposite surface, whereas an increased amount of fumed silica improved the water-repellency of the bulk material. Moreover, increasing the diatomaceous earth/fumed silica mass ratio improved the cross-linking density and hardness values of the nanocomposite.Despite being subjected to a range of mechanical durability tests, including sandpaper abrasion,knife scratching, tape peeling, water jet impact, and sandblasting, the nanocomposite maintained a water contact angle of 163. and contact angle hysteresis of 2°. When the water-repellency of the prepared nanocomposites eventually deteriorated, we restored their superhydrophobicity by removing the upper surface of the nanocomposite. This extraordinary robustness stems from the embedded low surface energy micro/nanostructures distributed throughout the nanocomposite. We also demonstrated the chemical stability, UV resistance, and self-cleaning abilities of the nanocomposite to illustrate the potential for real-life applications of this material.     

Wettability control of ZnO nanoparticles for universal applications

Herein, a facile approach for the fabrication of a superhydrophobic nanocoating through a simple spin-coating and chemical modification is demonstrated. The resulting coated surface displayed a static water contact angle of 158° and contact angle hysteresis of 1°, showing excellent superhydrophobicity. The surface wettability could be modulated by the number of ZnO nanoparticle coating cycles, which in turn affected surface roughness. Because of its surface-independent characteristics, this method could be applicable to a wide range of substrates including metals, semiconductors, papers, cotton fabrics, and even flexible polymer substrates. This superhydrophobic surface showed high stability in thermal and dynamic conditions, which are essential elements for practical applications. Furthermore, the reversible switching of wetting behaviors from the superhydrophilic state to the superhydrophobic state was demonstrated using repeated chemical modification/heat treatment cycles of the coating films.