超疏水性薄膜的制备及其抗生物污染性试验

超疏水性材料由于其表面高度不润湿的特性(表观接触角大于150°)引起了人们的普遍关注.近年来,在高疏水性材料的研究开发中涉及了两个重要的分支,即膜层的高光学透明性和耐久性.报告了研制耐用及具有高光学透明性(在可见光范围内透明度＞99%)的超疏水性材料的工艺,并探讨了该材料用于防生物污染领域的可行性.     

Preparation and characterization of superhydrophobic surfaces based on hexamethyldisilazane-modified nanoporous alumina

Superhydrophobic nanoporous anodic aluminum oxide (alumina) surfaces were prepared using treatment with vapor-phase hexamethyldisilazane (HMDS). Nanoporous alumina substrates were first made using a two-step anodization process. Subsequently, a repeated modification procedure was employed for efficient incorporation of the terminal methyl groups of HMDS to the alumina surface. Morphology of the surfaces was characterized by scanning electron microscopy, showing hexagonally ordered circular nanopores with approximately 250 nm in diameter and 300 nm of interpore distances. Fourier transform infrared spectroscopy-attenuated total reflectance analysis showed the presence of chemically bound methyl groups on the HMDS-modified nanoporous alumina surfaces. Wetting properties of these surfaces were characterized by measurements of the water contact angle which was found to reach 153.2 ± 2°. The contact angle values on HMDS-modified nanoporous alumina surfaces were found to be significantly larger than the average water contact angle of 82.9 ± 3° on smooth thin film alumina surfaces that underwent the same HMDS modification steps. The difference between the two cases was explained by the Cassie-Baxter theory of rough surface wetting.     

Preparation and characterization of superhydrophobic surface based on polydimethylsiloxane (PDMS)

Biomimetic superhydrophobic surfaces exhibit excellent self-cleaning properties due to their special micro/nano-scale binary structures. In order to prepare the superhydrophobic surface of the polydimethylsiloxane (PDMS), a facile fabrication method for replicating micro/nano-scale binary aluminium structures into PDMS is presented. The microscopic morphology, composition, surface roughness (Ra) and wettability of the sample surface were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, roughness measurement equipment and contact angle meter respectively. Based on the measurements of the contact angles of deionized water (DI water) and ethanediol, surface free energies of the coatings were estimated according to the Owens two-liquid method. The superhydrophobic PDMS exhibited lower surface free energy than flat PDMS with a DI water contact angle (WCA) of 165°. The surface roughness (Ra) increased with the increasing of etching time in the range 0–80?min, and then decreased with the change of etching time, similar to the variation of contact angle with etching time. Moreover, the prepared surface had different micro-morphologies and its wettability was changed by regulating the chemical etching time. In addition, the superhydrophobic PDMS also showed good self-cleaning properties and the bouncing effect of the water droplets.     

铜基超疏水表面防覆冰/抗霜冻特性分析

超疏水表面具有良好的防覆冰性能,有望改善低温条件下设备和设施的可靠性。本文采用氨气腐蚀法,制备具有微纳结构的铜表面,通过低表面能氟硅烷修饰后,金属铜表面表现出超疏水特性,其水接触角可达152.1°。利用电镜扫描、接触角测量、结冰和结霜实验分别对超疏水铜表面的表面结构、湿润性能和防覆冰性能进行研究。结果表明,超疏水表面的防覆冰/抗霜冻性能不仅与表面的粗糙度有关,还受液滴在固体表面的湿润状态的影响。当液滴在具有微-纳米结构的超疏水表面处于Cassie状态时,液滴与金属表面的接触面积小,液滴结冰速率较慢,金属表面同时具有较好的防覆冰和抗结霜性;而当液滴在金属疏水表面处于Wenzel状态时,霜晶与固体表面的接触面积增加,加快霜层的生长,金属表面的抗结霜性明显降低。     

光热超疏水材料的制备与防、除冰性能研究

户外设备表面结冰给人类生活和生产带来了众多不便,研究具有防结冰性能和除冰性能的新一代防、除冰材料对于户外设备的持久稳定运行具有重要意义。本文利用模板法将三氧化二钛（Ti₂O₃）粉末和聚二甲基硅氧烷（PDMS）混合制备具有规则阵列结构的光热超疏水材料,并研究其防结冰性能与光热除冰性能。得益于Ti₂O₃优异的光热性能,制备的材料在100 mW/cm²光照条件下的光热温升可达55℃,冻结在表面的液滴可在200 s内融化,具有优异的光热转换与光热除冰性能。而PDMS材料固化后本征疏水,加规则阵列微结构后赋予材料优异的超疏水性能,其接触角高达153°,滚动角小于5°。无光照时的结冰延迟时间长达1300 s,是无光热材料表面结冰延迟时间的3倍。而在光照时由于其优异的光热性能,液滴在长达6 h的结冰测试中尚未结冰,表明材料具有优异的光热防结冰性能。研究结果论证了利用自然界丰富太阳能进行除冰的可能性,为户外设备表面除冰技术提供新的方式。     

Synthesis and characterization of core‐shell particles containing a perfluoroacrylate copolymer rich in the shell

A simple synthetic method for preparing the core‐shell latex particles containing fluorinated shell was presented. Polymerization was achieved by a low‐sheer monomer‐starved emulsion polymerization process, thus facilitating mobility and subsequent polymerization of perfluoroacrylate (FA) along with methyl methacrylate (MMA) and n‐butyl acrylate (nBA) monomers. The structure and thermal behavior of the resulting perfluoroacrylate copolymer were investigated by FTIR, NMR, and DSC. Furthermore, PCS, TEM as well as SFM, were carried out to characterize the surface morphology of the particles. These studies illustrated that the incorporation of FA into MMA/nBA particle morphologies facilitated surface phase separation during coalescence, resulted in F‐containing film‐air interfaces. Thus, surface properties with a significant increase in the contact angles could be produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of superhydrophobic wood surfaces

Superhydrophobic films were developed on wood substrates with a wet chemical approach. Growth of zinc oxide (ZnO) nanorods was found differentially in the cross‐sectional walls and inner lumenal surfaces. The surface roughness of the prepared films on the inner lumenal surface conformed to the Cassie–Baxter wetting model, whereas the roughness across the microsurface of the cell wall was in conformity with the hydrophobic porous wetting model. The space between the ZnO nanorods and the microstructure of the wood surface constituted the nanoscale and microscale roughness of the ZnO nanofilm, respectively. The water contact angle of the prepared wood surfaces was up to 153.5°. In the prepared films, monolayers of stearic acid molecules were self‐assembled on the ZnO nanorods, which in turn, were attached to the wood surface via dimeric bonds. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

疏水性聚酯薄膜的制备及表面形貌分析

利用NaOH溶液化学刻蚀聚酯薄膜成功制得疏水性薄膜.研究了聚酯在碱性溶液中发生水解反应时外界条件对刻蚀结果的影响规律,分析了外界化学条件引起表面微观物理形貌的变化及其所对应的表面特性.结果表明,薄膜经pH为12的碱液在40℃下超声刻蚀5 min左右,并用无水乙醇浸泡,可达到与水接触角120°以上的疏水效果.     

Ice adhesion on different microstructure superhydrophobic aluminum surfaces

The adhesion of ice to high -voltage overhead transmission lines should be small to ensure ease of ice shedding under small external forces. In this work, we studied the influence of the microstructure of superhydrophobic surfaces on the strength of ice adhesion at a working temperature of ?6?°C. Compared to a bare aluminum surface, the microstructure superhydrophobic aluminum surfaces did decrease ice adhesion strength. The superhydrophobic aluminum surfaces with a larger number of micro-holes produced the lowest strength of ice adhesion; its ice adhesion strength was ～163.8 times lower than that for the bare aluminum samples. Furthermore, such microstructure aluminum surfaces had water contact angles larger than 150° and water sliding angles of less than 8.2° even at a working temperature of ?6?°C. The low values of the ice adhesion strength of the above samples were mainly attributed to the superhydrophobic property, which was obtained by creating a structure of micro-nanoscale holes on the aluminum surface after treatment with a low- surface-energy fluoroalkylsilane (FAS).     

铝合金表面耐久性超疏水防护膜的制备与表征

通过酸刻蚀-沸水浴处理构筑微纳米分级结构,进而通过喷涂含有磷酸铝胶黏剂(AP)和低表面能物质——全氟辛基三氯硅烷(PFOTS)的悬浮液增强结合力并降低表面能,从而在国产7B04铝合金表面制备了耐久性超疏水防护膜。利用场发射扫描电子显微镜(FESEM)、X射线光电子能谱仪(XPS)、傅里叶变换红外光谱仪(FTIR)、接触角测试仪(CA)、电化学阻抗谱(EIS)等技术以及多种环境模拟实验对样品进行了表征,结果显示,制备的防护膜表面水静态接触角(WCA)高达158.4°,滑动角(SA)为0°,呈现出超疏水和低黏附性;膜层电阻(Rc)约为101.55 kΩ·cm2,在NaCl腐蚀介质中的电荷转移电阻(Rt)增大了近2个数量级,表现出优异的防护性能;样品可以经受多种破坏,具有理想的机械耐久性、化学耐久性和环境耐久性。     

Contact angle measurements on oxidized polymer surfaces containing water-soluble species

Advancing and receding contact angle measurements on polymer surfaces can be performed using a number of different methods. Ballistic deposition is a new method for both rapidly and accurately measuring the receding contact angle of water. In the ballistic deposition method, a pulsed stream of 0.15-μL water droplets is impinged upon a surface. The water spreads across the surface and then coalesces into a single 1.8-μL drop. High-speed video imaging shows that, on most surfaces, the water retracts from previously wetted material, thereby forming receding contact angles that agree with the receding angles measured by the Wilhelmy plate technique. The ballistic deposition method measures the receding angle within one second after the water first contacts the surface. This rapid measurement enables the investigation of polymer surface properties that are not easily probed by other wettability measurement methods. For example, meaningful contact angles of water can be obtained on the water-soluble low-molecular-weight oxidized materials (LMWOM) formed by the corona and flame treatment of polypropylene (PP) films. Use of the ballistic deposition method allows for a characterization of the wetting properties and an estimation of the surface energy components of LMWOM itself. Both corona- and flame-generated LMWOM have significant contact angle hysteresis, almost all of which is accounted for by the non-dispersive (polar) component of the surface rather than by the dispersive component. Surface heterogeneity is thus associated primarily with the oxidized functionalities added to the PP by the corona and flame treatments.     

Preparation and characterization of durable superhydrophobic protective coatings on aluminum alloy

The durable superhydrophobic protective coatings on the 7B04 aluminum alloy surface was prepared by using acid etching and boiling water bath to construct micro-nano hierarchical structure, and then spraying suspension containing aluminum phosphate adhesive (AP) and perfluorooctyltrichlorosilane (PFOTS) to increase adhesion and reduce surface energy. The samples were characterized by field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), contact angle measurement (CA), electrochemical impedance spectroscopy(EIS) and a variety of the environmental simulation experiments. The results showed that the static water contact angle (WCA) of the surface is 158.4° and the slide angle (SA) is about 0°, suggesting superhydrophobicity and low adhesion to water. The coating resistance (R_c) was as high as 101.55 kΩ· cm² and the charge transfer resistance (R_t) in NaCl corrosion medium increased by nearly two orders of magnitude, showing excellent protective performance. The sample can withstand a variety of damages, with ideal mechanical durability, chemical durability and environmental durability.     

Effect of DC glow discharge treatment on the surface energy and surface resistivity of thin film of polypropylene

A change in the surface energy and surface resistivity of a thin film of polypropylene (PP) of thickness 100 μm was investigated, using direct current (DC) glow discharge. The thin film of the PP was treated for various discharge powers and treatment time and the modification in the surface energy and the surface resistivity was observed. To investigate the modification in the surface energy after DC glow discharge treatment, contact angle of two test liquids formamide and de‐ionized water over the surface of PP film was measured. By measuring the contact angle the change in surface energy and its two polar and dispersive components have been measured. It was observed that at a given power level of DC glow discharge surface energy and its polar component increases with increase of the treatment time, attains a maximum value, and then becomes almost constant. Correspondingly, with increase in surface energy, a decrease in surface resistivity was observed. Also, a change in surface morphology was observed by atomic force microscopy and by FT‐IR spectra generation of polar groups at the surface of PP film. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 767–772, 2007     

电镀锡薄钢板氧化膜和钝化膜的分析检测方法

介绍了电镀锡薄钢板氧化膜和钝化膜的分析检测方法,包括传统的化学分析方法、电化学分析方法和现代表面分析技术,如X射线光电子能谱(XPS)、俄歇电子能谱(AES)、辉光放电光谱(GDS)以及电子探针微区分析(EPMA)等。     

Adhesion Strengths of Epoxy Molding Compounds to Gold-plated Copper Leadframes

In the present study, the effects of plasma cleaning on the adhesion strength of molding compounds to gold-plated copper leadframes are presented. Important process parameters such as the type of gasses used and the time exposed in air before molding are specifically evaluated. The leadframe pullout test is performed to measure interfacial bonding strengths. The liquid droplet test is used to measure contact angles and atomic force microscope (AFM) is employed to characterize quantitatively the roughness of modified surfaces to correlate with the bond strength measurements. The results indicate that plasma cleaning of leadframes has three major ameliorating effects, namely, surface cleaning due to the removal of contaminants, enhanced chemical compatibility with molding compounds and surface roughening with associated larger surface contact area for better mechanical interlocking. Exposure of plasma-cleaned leadframes in air before molding is detrimental to interface bond quality, a finding suggesting that molding operations should be carried out immediately after cleaning. The experimental results show that roughness on the nano-scale is an important surface characteristic that has a strong correlation with interface bonding strengths.     

Effects of fictive temperature on the leaching of soda lime silica glass surfaces

The fictive temperature of glass characterizes the glass network structure and its thermal history, and thereby can influence ion and water transport in the glass surface. In this study, IR specular reflectance (SR), refractive index, and density measurements were used to characterize and confirm the effects of glass sample processing, especially the fictive temperature/thermal‐history variations. The subsequent acid leaching of these glasses created leached surface layers due to interdiffusion and reaction of hydrous species in the surface; the hydrogen depth profiles obtained with secondary ion mass spectrometry (SIMS) confirmed enhanced leaching with increasing fictive temperature. Attenuated total reflectance (ATR) in the mid‐ and near‐IR indicated increases in both SiOH and H₂O species with increasing fictive temperature. The relative intensities and shapes of the ATR peaks were found to vary between the samples suggesting that speciation of the hydrous reaction products (eg, strong and weakly hydrogen‐bonded OH) is also influenced by the original fictive temperature of the glass, but could not be quantitatively determined.     

Preparation and characterization of nitrogen-doped mesoporous titania with high specific surface area

Nitrogen-doped mesoporous titania aerogel photocatalysts were prepared by supercritical drying technique with carbon dioxide (SCCO₂) and calcination the urea impregnated TiO₂ aerogel at 773 K under NH₃ or N₂ + NH₃aq gaseous atmosphere. The pore properties were investigated from nitrogen adsorption measurement at 77 K. The prepared N-doped TiO₂ aerogel had a high specific surface area (116 m²/g), a total pore volume (0.33 cm³/g) and a sharp pore radius distribution (r_peak = 4.2 nm). The doping of the nitrogen atom into the TiO₂ lattice is expected from X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), and UV–Vis spectroscopy. Nitrogen states in the lattice and crystalline structure were measured using X-ray photoelectron spectroscopy and X-ray diffractometry. The N-doped TiO₂ aerogel absorbed well into the visible region up to 600 nm.     

Surface segregation in blends containing poly(dimethylsiloxane)-polystyrene block copolymers

The surface composition of polystyrene blends containing poly(dimethylsiloxane)-polystyrene block copolymers have been analyzed using X-ray photoelectron spectroscopy (XPS), contact angle measurements, and time-of-flight secondary ion mass spectrometry (TOFSIMS). The three techniques showed the surface of the blend samples to be identical to pure poly(dimethylsiloxane) homopolymer, despite the fact that the systems each contained only a 2% bulk concentration of siloxane. The high surface sensitivity of TOFSIMS—which probes the samples to depths of a few angstroms—indicates an enrichment of-Si(CH₃)₃ groups at the surface. These are the terminal groups of the PDMS part of the block. Their enrichment at the surface of the samples is presumably due to their low surface energy, in addition to the tendency for end groups to be at the surface due to free volume considerations.Presented at the XXVIth Silicon Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

EDTA modified glassy carbon electrode: Preparation and characterization

EDTA-phenoxyamide modified glassy carbon electrode (EDTA-GC) was prepared at a glassy carbon electrode by surface synthesis. In the first step, nitrophenyl was grafted to the glassy carbon (GC) surface via the electrochemical reduction of its tetraflouroborate diazonium salt. In the second step, nitrophenyl-modified electrode (NP-GC) was subjected to the cathodic potential scan to reduce the nitro to amine group. p-Aminophenyl modified glassy carbon electrode (AP-GC) was dipped into a EDTA solution containing 1-ethyl-3(3-(dimethlyamino)propyl)-carbodiimide (EDC) as an activating agent. Thus formed ((2-anilino-2-oxoethyl){2-[bis(carboxymethyl)amino]-ethyl}amino)acetic acid modified GC electrode was denoted as EDTA-GC and characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ellipsometry and X-ray photoelectron spectroscopy (XPS). Complexation of the EDTA-GC surface with Pb²⁺ ions was investigated if this electrode could be used as a metal sensor.     

有机–无机杂化超疏水涂层的制备

采用溶胶-凝胶法,以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为前驱体、硅丙树脂为成膜物质,制备了有机-无机杂化超疏水材料.在对用该材料获得超疏水涂层的研究中,考察了硅丙树脂的含量,比值n(MTES)/n(TEOS)、n(C_2H_5OH)/n(TEOS)和n(NH_3·H_2O)/n(TEOS)对涂层性能的影响.测试结果表明,当硅丙树脂加入量占总物料量的25%(质量分数),摩尔比n(TEOS)∶n(MTES)∶n(C_2H_5OH)∶n(NH_3·H_2O)为1∶4∶30∶10时,涂层具有良好的疏水性和均匀的外观结构,涂层静态水接触角可达156°.