In-situ growth of silica nanoparticles on cellulose and application of hierarchical structure in biomimetic hydrophobicity

Monodispersed silica nanoparticles were prepared by a simple two-step method with hydrolysis and condensation. The materials were characterized by dynamic light scattering (DLS), SEM and TEM. Through in-situ growth of silica nanoparticles on cotton fabrics, a dual-scaled surface with nanoscaled roughness of silica and microscaled roughness of cellulose fiber was generated. After the modification of the low surface energy, the wettability of smooth silicon slide, silicon slide with nanoscaled roughness of silica particles, cotton fabric, and cotton fabric with silica particles was evaluated by the tests of the contact angle (CA) and the advancing and receding contact angle (ARCA). The cotton fabric with dual-scaled roughness exhibits a static CA of 149.8° for 4 μL water droplet and a hysteresis contact angle (HCA) of 1.8°. The results of CA and HCA show that microscaled roughness plays a more important role than nanoscaled roughness for the value of CA and HCA. The results in the hydrostatic pressure test and the rain test show the important contribution of nanoscaled roughness for hydrophobicity.     

Wettability characterization of transparent MgF<Subscript>2</Subscript> nanoparticle coatings with SiO<Subscript>2</Subscript> binder covered with fluoroalkylsilane self-assembled monolayers

SiO₂-added MgF₂ nanoparticle coatings with various surface roughness properties were formed on silica-glass substrates from autoclaved sols prepared at 100–180 °C. The samples were exposed to fluoro-alkyl silane (FAS) vapor to give hydrophobicity. All nanoparticle samples before FAS treatment had transmittances higher than 93% and such values were preserved even after FAS treatment. We examined root mean square roughnesses of the nanoparticle coatings with a Scanning Probe Microscope. We also examined their static and dynamic wettabilities with a contact angle meter and calculated their adhesive energies and surface free energies (SFEs). The surface roughness of the nanoparticle coating increased with the increase of the autoclave temperature. In addition, higher autoclave temperature caused increases in the sliding angle and decreases in the SFE. Interestingly, the higher the contact angle was, the larger the sliding angle was, although smaller sliding angle was expected with a larger contact angle.     

液相法制备具有双尺寸粗糙度的超疏水铜表面

基于简单的液相法,以硫代硫酸钠和氯化铜为原料在铜片表面上构筑了具有微/纳米双尺寸粗糙度的硫化铜膜.用X射线衍射(XRD)仪、扫描电镜(SEM)、能量色散X射线(EDX)光谱仪及光学视频接触角仪对处理前后的铜表面进行了表征和分析.处理后的超亲水铜表面经硬脂酸修饰后具有超疏水效应,静态接触角高达161°,5μL水滴滚动角低至2.5°左右.超疏水性能归因于表面具有双尺寸粗糙度和低表面能的硬脂酸.该方法简单,无需复杂制备过程和苛刻设备,所得超疏水铜表面具有优异的不粘附性、长时间储存的稳定性和一定的耐摩擦性能.     

原位合成纳米SiO2增强阴离子聚酯型上浆剂及其对碳纤维复合材料层间剪切强度的影响

采用溶胶-凝胶法, 在侧链带有羧基的线性不饱和聚酯中加入正硅酸乙酯(TEOS), 使TEOS在酸性条件下发生水解反应, 原位合成纳米SiO₂增强阴离子型聚酯乳液(SEAPE). 利用傅里叶变换红外光谱(FTIR)仪、 激光粒度分析仪和冷冻扫描电子显微镜(Cryo-SEM)对SEAPE进行分析与表征. 将SEAPE与聚乙二醇单油酸酯润滑剂、 非离子型表面活性剂FC-4430及抗氧剂1010进行复配, 原位制备纳米SiO₂增强阴离子型聚酯乳液上浆剂(SEAPEs), 用扫描电子显微镜(SEM)、 视频动态接触角测量仪、 X射线能谱(EDS)仪和纤维强力仪对SEAPEs上浆后碳纤维的表面形貌、 表面能、 碳纤维(CF)表面元素及碳纤维增强不饱和聚酯(UPR)复合材料(CF/UPR)的层间剪切强度(ILSS)进行测试与表征. 结果表明, 当TEOS添加质量分数为5%时, SEAPEs上浆后的碳纤维有效增强了其与UPR的结合强度, CF/UPR复合材料的ILSS达到40.03 MPa, 与市售环氧树脂型上浆剂上浆后碳纤维增强UPR复合材料相比, ILSS提高90.1%. SEAPEs中原位生成的纳米SiO₂分散均匀, 乳液储存稳定, 上浆后SiO₂均匀吸附在碳纤维表面, 增加碳纤维表面能, 改善碳纤维与树脂间的浸润性, 可有效提高碳纤维增强不饱和聚酯树脂复合材料的ILSS.     

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。     

Surface modification of cellulose fibers with layer-by-layer self-assembly of lignosulfonate and polyelectrolyte: effects on fibers wetting properties and paper strength

To convert the hydrophilic cellulose fiber into hydrophobic, multilayers composed of cationic polyacrylamide (CPAM) and lignosulfonate (LS) were constructed on cellulose fiber surface using layer-by-layer (LBL) self-assembly technique. The presence of CPAM/LS multilayers were validated by zeta potential, X-ray photoelectron spectroscopy and atomic force microscopy (AFM). It was found that potential of fiber surface inversed after deposition of each layer, the contents of characteristic elements (i.e. S and N) of CPAM/LS multilayers increased with increasing bilayer number, furthermore, the calculated surface LS content increased linearly as a function of bilayers. AFM phase images indicated that the cellulose microfibrils on fiber surface were gradually covered by LS granules, resulting in an increase in fiber surface roughness as self-assembly proceeded. The wetting properties of modified cellulose fibers were detected by dynamic contact angle measurement. The results showed that the initial water contact angle gradually increased and the attenuation rate of the contact angle gradually decreased with the number of bilayers, suggesting that the controllable hydrophobicity of cellulose fiber can be achieved depending on the number of bilayers. It also showed that the polyelectrolyte presented in the outermost layer significantly influenced the wetting properties of cellulose fibers, and a higher hydrophobicity was observed when LS was in the outermost layer. Moreover, tensile strength test was performed on the handsheet prepared from LBL modified fibers to evaluate the effect of CPAM/LS multilayers on strength property of cellulose fiber networks. The tensile index of handsheet prepared from fibers modified with a (CPAM/LS)₅ multilayer increased by 12.4% compared with that of handsheet prepared from original fibers. The print density of handsheet increased with the number of bilayers, suggesting that printability of the handsheet was improved by constructing CPAM/LS multilayers on cellulose fiber surface. This strategy will have a positive impact and potential application value in printing process control of cellulose fiber-based products.     

Construction of Renewable Superhydrophobic Surfaces via Thermally Induced Phase Separation and Mechanical Peeling

We report a simple preparation method of a renewable superhydrophobic surface by ther-mally induced phase separation (TIPS) and mechanical peeling. Porous polyvinylidene fluo-ride (PVDF) membranes with hierarchical structures were prepared by a TIPS process under different cooling conditions, which were confirmed by scanning electron microscopy and mer-cury intrusion porosimetry. After peeling off the top layer, rough structures with hundreds of nanometers to several microns were obtained. A digital microscopy determines that the surface roughness of peeled PVDF membranes is much higher than that of the original PVDF membrane, which is important to obtain the superhydrophobicity. Water contact angle and sliding angle measurements demonstrate that the peeled membrane surfaces display super-hydrophobicity with a high contact angle (152°) and a low sliding angle (7.2°). Moreover, the superhydrophobicity can be easily recovered for many times by a simple mechanical peel-ing, identical to the original superhydrophobicity. This simple preparation method is low cost, and suitable for large-scale industrialization, which may offer more opportunities for practical applications.     

聚酯织物表面耐用超疏水涂层的制备及在油水分离中的应用

使用在含有甲基MQ(M:单官能团Si-O单元R₃SiO_1/2, Q:四官能团Si-O单元SiO₂)硅树脂与疏水SiO₂的二甲苯溶液中浸渍的方法,在聚酯织物表面制备了耐用超疏水涂层。经过处理后,微米级聚酯纤维表面被紧密的疏水纳米颗粒包裹,通过这种方法降低了纤维的表面能。聚酯织物展现出良好的超疏水特性,与水滴的静态接触角为156°,滚动角为5°。得到的超疏水聚酯织物在机械磨损、酸碱环境及紫外线照射条件下,表现出了良好的稳定性。此外,用超疏水聚酯织物作为过滤材料得到的油水分离效率达99%以上。该方法为大面积工业制备超疏水织物提供了新的思路。     

Highly Hydrophobic Conducting Nanocomposites Based on a Fluoropolymer with Carbon Nanotubes

A procedure was suggested for preparing highly hydrophobic conducting coatings based on fluoropolymers with carbon nanotubes of two types: Taunit-MD and carbon nanotubes functionalized with alkyl groups. The surface resistance, contact angle, sliding angle, and surface roughness were measured; structural features of the nanocomposites were studied. The properties of the coatings obtained depend on the concentration and type of the carbon nanotubes used. Introduction of functionalized carbon nanotubes into a fluoropolymer matrix allows preparation of coatings with higher values of the sliding angle and electrical resistance. The contact angle and sliding angle depend on the surface roughness and structure in different fashions.     

聚苯硫醚超疏水复合涂层的制备与性能

利用工业原料聚苯硫醚微粉和疏水性二氧化硅纳米粉末,采用喷涂法在瓷砖表面制备了疏水复合涂层.研究了热处理温度、组分配比对涂层表面形貌、粗糙度和接触角的影响,发现随着热处理温度升高,涂层表面粗糙度增大,随着疏水性二氧化硅含量的增加,由于表面聚集的疏水性二氧化硅增多,涂层疏水性增强,在热处理温度为280℃、疏水性二氧化硅与聚苯硫醚质量比为1∶1时,可获得超疏水涂层,涂层的接触角大于150°,滚落角小于4°,pH值为1～14的水溶液在其表面都具有很高的接触角.超疏水涂层具有良好的自清洁效果,并且经落沙法实验测定,超疏水涂层耐刮伤性能良好.     

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.     

Wetting of heterogeneous surfaces of block copolymers containing fluorinated segments

 The wetting of well-characterized heterogeneous surfaces of block copolymers has been studied by low-rate dynamic contact angle measurements using axisymmetric drop-shape analysis. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to investigate the roughness, the heterogeneity and the chemical composition of the surfaces. By changing the block length of polysulfone and semifluorinated polyester segments in the block copolymers, the surface heterogeneity of thin films prepared on silicon wafers could be controlled. Tapping-mode AFM measurements showed that soft, hydrophobic domains of varying size on the submicrometer length scale were obtained on these surfaces (60–250 nm). The mean roughness was of the order of several nanometers. The results of the contact angle measurements showed that neither roughness nor heterogeneity had a significant effect on the advancing contact angle of water, at the scale of the features present; however, the contact angle hysteresis increased with increasing percentage of the soft domains. We assume that liquid retention by the solid upon retraction of the three-phase line is the main cause for the observed increase in contact angle hysteresis. Concerning the molecular composition of these block copolymer surfaces, angle-resolved XPS analysis showed a surface segregation of fluorine within the surface region. A direct correlation was found between the fluorine content of the block copolymer surfaces and the advancing contact angle of water. Received: 26 May 2000 Accepted: 3 January 2001     

Boundary slip and wetting properties of interfaces: correlation of the contact angle with the slip length

Correlations between contact angle, a measure of the wetting of surfaces, and slip length are developed using nonequilibrium molecular dynamics for a Lennard-Jones fluid in Couette flow between graphitelike hexagonal-lattice walls. The fluid-wall interaction is varied by modulating the interfacial energy parameter epsilonr=epsilonsfepsilonff and the size parameter sigmar=sigmasfsigmaff, (s=solid, f=fluid) to achieve hydrophobicity (solvophobicity) or hydrophilicity (solvophilicity). The effects of surface chemistry, as well as the effects of temperature and shear rate on the slip length are determined. The contact angle increases from 25 degrees to 147 degrees on highly hydrophobic surfaces (as epsilonr decreases from 0.5 to 0.1), as expected. The slip length is functionally dependent on the affinity strength parameters epsilonr and sigmar: increasing logarithmically with decreasing surface energy epsilonr (i.e., more hydrophobic), while decreasing with power law with decreasing size sigmar. The mechanism for the latter is different from the energetic case. While weak wall forces (small epsilonr) produce hydrophobicity, larger sigmar smoothes out the surface roughness. Both tend to increase the slip. The slip length grows rapidly with a high shear rate, as wall velocity increases three decades from 100 to 10(5) ms. We demonstrate that fluid-solid interfaces with low epsilonr and high sigmar should be chosen to increase slip and are prime candidates for drag reduction.     

POSS基杂化含氟丙烯酸酯共聚物涂膜的表面相分离与疏水性研究

采用自由基溶液聚合法成功合成了多面体低聚倍半硅氧烷(POSS)基杂化含氟丙烯酸酯共聚物,并采用核磁共振仪(NMR)和凝胶渗透色谱仪(GPC)表征了共聚物,其中POSS和含氟单体分步加入到反应中.首先将共聚物溶解到三氟三氯乙烷(F113)和乙酸乙酯的混合溶剂中配制成溶液,然后通过直接在玻璃片上滴落共聚物溶液制备了共聚物涂膜.采用扫描电子显微镜(SEM)、X-射线光电子能谱(XPS)、原子力显微镜(AFM)和接触角测量仪考察了F113和乙酸乙酯的配比对共聚物涂膜表面形貌、表面元素组成、表面粗糙度以及表面疏水性的影响.实验数据表明POSS在表面能够聚集成纳米颗粒并能极大增强涂膜表面粗糙度和疏水性.共聚物表面同时存在POSS聚集与有机相微相分离两类相分离行为,并形成了复合粗糙结构.虽然POSS和含氟段竞争迁移到表面,但是随着混合溶剂中F113的增多,涂膜表面含氟量越来越多,同时POSS在表面的聚集体越来越少,表面平均粗糙度越来越小,最终涂膜的疏水性越来越强,这说明F113有助于提升氟的趋表迁移能力,使涂膜表面含氟链段占据较多的表面空间,从而抑制了POSS在表面聚集分布.当使用纯F113作为溶剂时,共聚物涂膜的表面氟含量为45.25%,平均粗糙度为93.4 nm,此时静态水接触角最大为135.0?,表现出优异的疏水性.     

Preparation of durable superhydrophobic surface by sol–gel method with water glass and citric acid

Durable superhydrophobic surface on cotton fabrics has been successfully prepared by sol–gel method. Cellulose fabric was first coated with silica sol prepared with water glass and citric acid as the acidic catalyst. The silica coated fabric was then padded with hydrolyzed hexadecyltrimethoxysilane afterwards obtaining low surface energy. Water contact angle and hydrostatic pressure were used to characterize superhydrophobicity and washing durability. Scanning electron microscopy was used to characterize the surface morphology changes after certain washing times. All results showed good durable hydrophobicity on cellulose fabrics. In addition, the influence of citric acid and sodium hypophosphite (NaH₂PO₂) on the durability of hydrophobicity was also investigated. The durability of treated cotton improved with the increase of concentration of citric acid in the presence of NaH₂PO₂. It could be concluded that citric acid acted as multi-functional heterogeneous grafting chemicals to improve washing durability of hydrophobicity by forming the ester bonds between cotton fabric and silica sol and improved the durability of hydrophobicity.     

Superhydrophobicity on two-tier rough surfaces fabricated by controlled growth of aligned carbon nanotube arrays coated with fluorocarbon

Considerable effort has been expended on theoretical studies of superhydrophobic surfaces with two-tier (micro and nano) roughness, but experimental studies are few due to the difficulties in fabricating such surfaces in a controllable way. The objective of this work is to experimentally study the wetting and hydrophobicity of water droplets on two-tier rough surfaces for comparison with theoretical analyses. To compare wetting on micropatterned silicon surfaces with wetting on nanoscale roughness surfaces, two model systems are fabricated: carbon nanotube arrays on silicon wafers and carbon nanotube arrays on carbon nanotube films. All surfaces are coated with 20 nm thick fluorocarbon films to obtain low surface energies. The results show that the microstructural characteristics must be optimized to achieve stable superhydrophobicity on microscale rough surfaces. However, the presence of nanoscale roughness allows a much broader range of surface design criteria, decreases the contact angle hysteresis to less than 1 degrees , and establishes stable and robust superhydrophobicity, although nanoscale roughness could not increase the apparent contact angle significantly if the microscale roughness dominates.     

Study of temperature distribution of sliding block with asperity surface

In this study, a numerical thermal model is developed for sliding block contact under various loads, sliding velocities and surface roughness. The temperature distributions are shown for perfectly insulated thermal conditions along noncontact surfaces. For a particular five‐peaks contact model, the maximum temperature at the central peak is slightly lhigher than the others. The temperature profile decreases as the distance to the symmetry axis increases, and then decreases dramatically at the noncontact area. It is clear to see that the maximum temperature locates at the symmetry central peak of the asperity contact area instead of the leading head of the smooth surface. The maximum temperature rise parameter increases as the pressure, sliding velocity and asperity roughness increased or conductivity decreased. This phenomenon becomes obvious for cases at high pressure, velocity and roughness and low conductivity. Particularly, the influence of roughness is not significant for low velocity. Similar results are found for the maximum temperature rise parameter difference between peaks or peaks/valleys. The simulation results of this asperity surface sliding block contact model are able to provide essential information for the components of microelectro—mechanical systems (MEMS) and biochemical reaction mechanism. Copyright © 2011 John Wiley & Sons, Ltd.     

Mimicking the lotus effect: influence of double roughness structures and slender pillars

Surface roughness is known to amplify hydrophobicity. The apparent contact angle of a drop on a rough surface is often modeled using either Wenzel's or Cassie's formulas. These formulas, along with an appropriate energy analysis, are critical in designing superhydrophobic substrates for applications in microscale devices. In this paper we propose that double (or multiple) roughness structures or slender pillars are appropriate surface geometries to develop "self-cleaning" surfaces. The key motivation behind the double structured roughness is to mimic the microstructure of superhydrophobic leaves (such as lotus). Theoretical analysis similar to that presented in the paper can be used to obtain optimal geometric parameters for the rough surface. The calculation procedure should result in surface geometries with excellent water repellent properties.     

Antiwettability enhancement of PVDF-HFP membrane via superhydrophobic modification by SiO2 nanoparticles

Pore wetting is undesirable in the membrane gas–liquid separation process as it deteriorates the gas removal flux. To alleviate the affinity of a membrane surface toward a liquid solvent, its hydrophobicity needs to be enhanced. In this study, a superhydrophobic polyvinylidene fluoride-co-hexafluoropropylene membrane was synthesized via a simple and facile nonsolvent-induced phase inversion process. Hydrophobic nano-SiO₂ particles were used as solvent additives to improve the wetting resistance of the membrane. The results revealed that blended nano-SiO₂ membranes exhibited enhanced surface hydrophobicity in terms of water contact angle. Such improvement was attributed to the enhancement of surface roughness via the formation of hierarchical multilevel protrusions. Besides, the embedment of nanoparticles in polymer spherulitic globules also contributed to the reduction in surface energy of the membrane. As a result, the blended nano-SiO₂ membrane achieved superhydrophobicity with a water contact angle of up to 151°.     

Fabricating superhydrophobic surfaces by molecular accumulation of polysiloxane on the wool textile finishing

In the present study, a novel and simple method of obtaining superhydrophobic surface through the migration of organic siloxane segments in the acrylate side chains to the outmost layer and forming the nano-protuberance on the micro-roughness wool fabrics was described. The chemical compositions and morphologies of the untreated/treated fabrics were characterized by the scanning electron microscopy and X-ray photoelectric energy spectroscopy. Meanwhile, the surface hydrophobicity was evaluated by the static contact angle measurement. The scanning electron microscopy photographs showed that the fiber surfaces of the treated fabrics were obviously granulated, and a wax film covered on the fibers could be observed. X-ray photoelectron spectroscopy analyses and static contact angle measurement further testified that the component of the wax was almost siloxane and that the surfaces of the treated fabrics had superhydrophobic property. The above results indicated that this method could be extended to prepare superhydrophobic surfaces by migrating the low-surface-energy matter and fabricating the nanoscale roughness on the micro-roughness material surfaces.