Fabrication of durable hydrophobic surfaces through surface texturing

Low surface energy polymer thin-films can be applied to surfaces to increase hydrophobicity and reduce friction for a variety of applications. However, wear of these thin films, resulting from repetitive rubbing against another surface, is of great concern. In this study, we show that highly hydrophobic surfaces with persistent abrasion resistance can be fabricated by depositing fluorinated carbon thin films on sandblasted glass surfaces. In our study, fluorinated carbon thin films were deposited on sandblasted and as-received smooth glass using deep reactive ion etching equipment by only activating the passivation step. The surfaces of the samples were then rubbed with FibrMet abrasive papers in a reciprocating motion using an automatic friction abrasion analyzer. During the rubbing, the static and kinetic friction forces were also measured. The surface wetting properties were then characterized using a video-based contact angle measuring system to determine the changes in water contact angle as a result of rubbing. Assessment of the wear properties of the thin films was based on the changes in the water contact angles of the coated surfaces after repetitive rubbing. It was found that, for sandblasted glass coated with fluorinated carbon film, the water contact angle remained constant throughout the entire rubbing process, contrary to the smooth glass coated with fluorinated carbon film which showed a drastic decrease in water contact angle with the increasing number of rubbing cycles. In addition, the static and kinetic friction coefficients of the sandblasted glass were also much lower than those of the smooth glass.     

聚(2-甲氧基-5-辛氧基)对苯乙炔/TiO2纳米复合材料的光物理性能研究

通过原位强碱诱导下的脱氯化氢缩合聚合法制备了一系列不同纳米TiO2含量的聚(2-甲氧基-5-辛氧基)对苯乙炔/纳米二氧化钛(PMOCOPV/TiO2)光电复合材料。红外光谱和拉曼光谱证实了在纳米TiO2表面的包覆层为PMOCOPV。紫外-可见吸收光谱表明随着TiO2含量的增加PMOCOPV/TiO2纳米复合材料的吸收强度提高。高分辨透射电镜观察发现PMOCOPV/TiO2是具有核-壳结构的纳米复合粒子,直径约30 nm,其中PMOCOPV包覆层的厚度约为8~10 nm。荧光光谱研究表明,PMOCOPV/TiO2纳米复合材料的最大发射波长随着TiO2含量的增加发生红移,荧光寿命约为1 ns,且随着TiO2含量的增加荧光强度和荧光寿命得到显著提高,并通过PMOCOPV/TiO2纳米复合材料中的激子离化和电荷传输过程以及复合材料中的电势能级探讨了PMOCOPV/TiO2的荧光量子效率和荧光强度增加的机理。     

Fabrication of superhydrophobic nanostructured surface on aluminum alloy

A superhydrophobic surface was prepared by consecutive immersion in boiling water and sputtering of polytetrafluoroethylene (PTFE or Teflon®) on the surface of an aluminum alloy substrate. Immersion in boiling water was used to create a micro-nanostructure on the alloy substrate. Then, the rough surface was coated with RF-sputtered Teflon film. The immersion time in boiling water plays an important role in surface morphology and water repellency of the deposited Teflon coating. Scanning electron microscopy images showed a “flower-like” structure in first few minutes of immersion. And as the immersion time lengthened, a “cornflake” structure appeared. FTIR analyses of Teflon-like coating deposited on water treated aluminum alloy surfaces showed fluorinated groups, which effectively reduce surface energy. The Teflon-like coating deposited on a rough surface achieved with five-minute immersion in boiling water provided a high static contact angle (～164°) and low contact angle hysteresis (～4°).     

Transmission X‐ray scattering as a probe for complex liquid‐surface structures

The need for functional materials calls for increasing complexity in self‐assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase‐coexistence and domain morphologies, has become increasingly important to controlling self‐assembly processes, including those at liquid surfaces. The traditional X‐ray scattering methods for liquid surfaces, such as specular reflectivity and grazing‐incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X‐ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibility of this approach, transmission small‐ and wide‐angle X‐ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First‐order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered‐monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X‐ray beams available at synchrotron facilities, support the possibility of using scanning‐probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.     

A Fluorescence Study of New Angular Polycyclic Blue Light-Emitting pyrazolo[3,4-<Emphasis Type="Italic">h</Emphasis>][1,6]naphthyridine and their Interaction with Bovine Serum Albumin (BSA)

The blue light-emitting pyrazolo[3,4-h][1,6]naphthyridines has been synthesized by Friedländer condensation of 4-amino-3-(4-phenyl)-1-phenyl-1H-pyrazolo[3,4-b]pyridine-5-carbaldehyde (o-aminoaldehyde) 1 with different cyclic ketones and 1,3-diketones. The synthesized angular polycyclic naphthyridine derivatives were studied for Semi-empirical, thermal, UV–vis and fluorescence spectroscopic properties on binding with bovin serum albumin (BSA). These fluorescence properties together with the neutral, hydrophobic nature of these compounds make these fluorophores good fluorescence probe for studying the micropolarity of proteins like BSA and in general the ligand-protein interactions. All of them displays bright absorption at 394 nm &; emission in visible region (491 nm). Quantum yields of all synthesized compounds were calculated.     

Adsorption of firefly luciferase at interfaces studied by total internal reflection fluorescence spectroscopy

The adsorption of luciferase onto silica surfaces was studied by total internal reflection fluorescence (TIRF) spectroscopy. Two model surfaces were used: hydrophilic and hydrophobic silica. Luciferase adsorbed differently on these two surfaces. Initial kinetics of luciferase adsorption onto the hydrophilic surface showed that luciferase adsorbs over an adsorption energy barrier of 3 kT The quantum yield of luciferase fluorescence decreased at the hydrophilic silica surface, which indicated that the protein conformation was altered during adsorption. Luciferase adsorption onto the hydrophobic silica surface proceeded with a small adsorption energy barrier and the fluorescence efficiency of adsorbed protein remained unchanged after adsorption. The affinity of luciferase for luciferin was measured using quenching of luciferase fluorescence with luciferin. The binding constant of the adsorbed luciferase-luciferin complex at the hydrophilic silica surface was two orders of magnitude smaller than the respective binding constant in the solution. Adsorbed luciferase showed an absence of ATP-dependent visible luminescence, indicating that the adsorbed enzyme was not active at either of the two silica surfaces.     

[Zn（Phen）（5-Fu）_2]（NO_3）_2与牛血清白蛋白相互作用的荧光光谱

以Zn（）为中心离子,5-氟脲嘧啶（5-Fu）和邻菲口罗啉（Phen）为配体,合成了[Zn（Phen）（5-Fu）2]（NO3）2配合物,并利用荧光光谱考察了该配合物与牛血清白蛋白（BSA）的相互作用。实验结果表明,配合物与BSA作用可导致BSA内源荧光猝灭,其猝灭机理为静态猝灭,结合常数Ka=1.56×106L/mol,结合位点数n=1.40,且该配合物能够猝灭BSA分子表面94.0%的色氨酸（Trp）残基,是良好的BSA猝灭剂。     

Femtosecond laser processing of nitride-based thin films to improve their tribological performance

The ability of femtosecond laser pulses to pattern coated tribological surfaces in order to improve their wear behavior was investigated. Experiments were performed with a Ti:sapphire laser (wavelength: 800 nm, energy density: 2 J/cm², pulse duration: 100 fs) on TiN- and on TiCN-coated surfaces. Morphological analyses of the laser-treated surfaces were carried out and did not reveal any film delamination or other coating damage after laser processing. Tribological tests simulating rapidly increasing contact pressures under boundary friction were performed on both unpatterned and laser-patterned coated surfaces using a steel counter body. The patterned surfaces showed significantly better tribological performance with respect to stability and the value of the friction coefficient during testing. EDX analyses of the tested unpatterned samples revealed complete coating removal and material transfer from the counter body to the sample surface. In the case of the laser-patterned surfaces, only slight coating damage and an accumulation of debris from the steel counter body in the laser-induced pores were observed. PACS 42.62.Cf; 81.40.Wx     

Fabrication of superhydrophilic or superhydrophobic self-cleaning metal surfaces using picosecond laser pulses and chemical fluorination

Bioinspired superhydrophilic/phobic self-cleaning surfaces have recently drawn a lot of interest in both fundamental and applied research. A hybrid method to produce the self-cleaning property of micro/nanostructured surface using ultra-fast laser pulses followed by chemical fluorination is proposed. The typical micro/nanocomposite structures that form from microporous arrays and microgroove groups have been processed by picosecond laser on titanium alloy surface. The surface hydrophilic/phobic and self-cleaning properties of micro/nanostructures before and after fluorination with fluoroalkyl-silane were investigated using surface contact angle measurements. The results indicate that surface properties change from hydrophilic to hydrophobic after fluorination, and the micro/nanostructured surface with increased roughness contributes to the improvement of surface hydrophobicity. The micro/nanomodification can make the original hydrophilic titanium alloy surface more hydrophilic or superhydrophilic. It also can make an originally hydrophobic fluorinated titanium alloy surface more hydrophobic or superhydrophobic. The produced micro/nanostructured titanium alloy surfaces show excellent self-cleaning properties regardless of the fluorination treatment, although the fluorinated surfaces have slightly better self-cleaning properties. It is found that surface treatment using ultra-fast laser pulses and subsequent chemical fluorination is an effective way to manipulate surface wettability and obtain self-cleaning properties.     

Water condensation on zinc surfaces treated by chemical bath deposition

Water condensation, a complex and challenging process, is investigated on a metallic (Zn) surface, regularly used as anticorrosive surface. The Zn surface is coated with hydroxide zinc carbonate by chemical bath deposition, a very simple, low-cost and easily applicable process. As the deposition time increases, the surface roughness augments and the contact angle with water can be varied from 75° to 150°, corresponding to changing the surface properties from hydrophobic to ultrahydrophobic and superhydrophobic. During the condensation process, the droplet growth laws and surface coverage are found similar to what is found on smooth surfaces, with a transition from Cassie-Baxter to Wenzel wetting states at long times. In particular, it is noticeable in view of corrosion effects that the water surface coverage remains on order of 55%.     

Atomic control of water interaction with biocompatible surfaces: the case of SiC(001)

The interaction of water with Si- and C- terminated beta-SiC(001) surfaces was investigated by means of ab initio molecular dynamics simulations. Irrespective of coverage, varied from 1/4 to 1 monolayer, we found that water dissociates on the Si-terminated surface, substantially modifying the clean surface reconstruction, while the C-terminated surface is nonreactive and hydrophobic. Based on our results, we propose that STM images and photoemission experiments may detect specific changes induced by water on both the structural and electronic properties of SiC(001) surfaces.     

含氮氟化类金刚石(FN-DLC)薄膜的研究：(Ⅲ)疏水性能分析

不同沉积条件下，在单晶硅基底上沉积了含氮氟化类金刚石(FN-DLC)薄膜，用静滴接触角/表面张力测量仪测量了水与FN-DLC膜表面的接触角.用X射线光电子能谱、Raman光谱和傅里叶变换吸收红外光谱(FTIR)分析了薄膜的组分和结构.用原子力显微镜观测了薄膜的表面形貌.结果表明，FN-DLC薄膜疏水性能主要取决于薄膜表面的化学结构、薄膜表面极化强度的强弱、以及薄膜的表面粗糙度的大小.sp³/sp²的比值减小，CF₂基团含量增加，薄膜粗糙度增加，接触角增大；反之，则接触角减小.在工艺上，沉积温度和功率的减小，气体流量比r(r=CF4/［CF₄+CH₄］)的增加，都会使水的浸润性变差，接触角增大. 关键词： 氟化类金刚石膜 疏水性 接触角     

XPS study of five fluorinated compounds deposited on calcarenite stone: Part I. Unaged samples

In this work the application of XPS technique to the study of five fluorinated compounds deposited on actual calcarenite samples is presented. It has been found that the composition derived from the high-resolution XPS spectra together with the results of the C 1s fitting, allow us to derive a surface chemical formula for each of the studied compounds. These formula are in good agreement with those reported in the manufacturer data sheets if one hypothesise an arrangement of these molecules on the surface of the calcarenite stone that take into account the content of the different hydrophobic groups. In addition, the thickness of the deposited film has been calculated on the basis of the Ca and C content as well as an estimation of the coverage degree has been done. The results of this XPS study has been compared with that obtained by means of the static contact angle test.     

Surface property modification of well-dispersed amphiphilic gold nanoparticles as individuals

Amphiphilic gold nanoparticles (AuNPs) functionalized with mixed monolayers consisting of hydrophobic and hydrophilic ligands find widespread applications in biosensing, drug delivery, and bioimaging. One important aspect of amphiphilic AuNPs in such applications is the tuning of the surface properties of these AuNPs by modifying the composition of the ligands. In this study, well-dispersed AuNPs as individuals with mixed monolayers of hydrophobic and hydrophilic ligands were synthesized and the ratios of hydrophilic and hydrophobic ligands on the AuNP surfaces with varying ligand lengths were investigated by electrostatic titration. We demonstrated that longer hydrophobic ligands have higher affinity for the AuNP surface, and that the relative ligand length plays an important role in determining the maximum hydrophobic coverage on the AuNP surface at which the ratio of the amount of hydrophobic to that of hydrophilic ligands on the AuNP surface is the largest, for AuNPs to remain as individuals. We expect that the AuNPs synthesized with diverse ratios of hydrophobic and hydrophilic ligands on the surface can be useful in biological applications.

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Structural- and chemical-phase-separation on single crystalline sapphire (0001) surfaces

Atomic force microscopy (AFM) was used to characterize morphology and chemistry on step-controlled single crystalline sapphire (0001) surfaces. Hydrophilicity on the surface can be evaluated using frictional force imaging. A sapphire surface that is covered with bunched steps accompanied with crossing steps clearly exhibits the phase-separation into two domains with different hydrophilicity, where an almost hydrophobic domain forms inside a hydrophilic area. By analyzing the histogram of the step height, we concluded that the difference in the hydrophilicity is associated with the surface reconstruction. We found that the phase-separation characterized by the hydrophilicity and charge potential self-organizes on the sapphire surface with specific step arrangements. We demonstrated selective adsorption of biomolecules on step-controlled surfaces as an example of the application.     

Humidity dependence of tribocharging of electrophotographic carriers coated with poly(vinylidene fluoride)-poly(methyl methacrylate) blends

In this study, the effect of humidity on the work function of ferrite carrier particles coated with blends of poly(vinylidene fluoride) and poly(methyl methacrylate) was investigated. Charging measurements made as a function of humidity using toner surface treated with hydrophobic and hydrophilic silica were analyzed using an extension of the surface state model of tribocharging. The carrier work function is a linear function of the ratio of poly(vinylidene fluoride) and poly(methyl methacrylate) in the carrier coating. In contrast to the work function of the surface treated toners used, the carrier work function is independent of humidity. The density of states of the charging sites on the carrier is large enough that the term containing it is much less than 1.0. Thus, unlike the toner, the carrier is in the so-called high density of states limit.     

High coverage states of oxygen adsorbed on Pt(100) and Pt(111) surfaces

Oxygen adsorption on the Pt(100) and Pt(111) surfaces was investigated using X-ray photo-emission and thermal desorption spectroscopies. Low pressure (ca. 10^?5 Pa) oxygen dosing at near ambient crystal temperature resulted in the formation of dissociated adsorbed species at saturation coverages of nominally 0.2–0.25 monolayer on both surfaces. The combination of higher pressure (ca. 10^?3 Pa) and higher surface temperature (570 K) dosing produced a three to five times higher saturation coverage than the low pressure dosing. The effect of dosing condition on the saturation coverage appears to reconcile apparent discrepancies for the Pt(100) surface in the literature. Characterization by XPS of the higher coverage state for oxygen showed that it is in the same chemical state as the oxygen adsorbed at very low coverage. Angle-resolved XPS has shown that in all cases the oxygen appears to reside on the surface with no significant penetration of oxygen into the bulk, as would be characteristic of oxidation. However, some penetration on the surface by oxygen, such as by a place-exchange type restructuring of the first two atomic layers, cannot be entirely ruled out.     

Fluorescence Enhancements on Silver Colloid Coated Surfaces

We observed a strong, more than 16-fold, enhancement of Texas Red-labeled BSA fluorescence emission when deposited on silver colloid coated surfaces (SCCS). The same labeled protein deposited on silver island films (SIFs) showed an approximate 8-fold fluorescence enhancement. The lifetimes of Texas Red-BSA fluorescence are significantly shorter on silvered surfaces than on uncoated quartz substrate indicating a strong change in radiative decay rate of the dyes. We also observed a 36-fold increased brightness of overlabeled fluorescein-HSA deposited on silver colloid coated surface. Stronger enhancement observed for overlabeled Fl-HSA protein indicates that presence of silver particles partially decreased self-quenching. Our results indicate that surfaces coated with silver colloids are valuable substrates for metal-enhanced fluorescence.     

Enhanced Ratiometric pH Sensing Using SNAFL-2 on Silver Island Films: Metal-enhanced Fluorescence Sensing

We have explored the opportunities for enhanced ratiometric pH sensing using the well-known carboxy seminaphthofluorescein (SNAFL-2) and silver island films (SiFs). Our results show that the metallic surfaces can provide up to a 40-fold increase in probe fluorescence intensity as compared to nonmetallic surfaces with the same probe coverage. However, while the S/N is significantly better for pH sensing, the emission wavelength ratiometric values are similar to that obtained in solution, due to the fact that the emission of both the acidic and basic forms of the probe are enhanced to similar extents. To the best of our knowledge this is the first report of enhanced ratiometric fluorescence sensing on metallic surfaces.     

Preparation and magnetic properties of anisotropic (Sm,Pr)Co5/Co composite particles

Anisotropic (Sm,Pr)Co₅/Co nanocomposite particles have been fabricated by chemical coating the 2 h ball milled (Sm,Pr)Co₅ flakes with Co nanoparticles. The Co nanoparticles were synthesized with mean particle sizes in the range of 20-50 nm. The nanocomposite particles present [0 0 1] out-of-plane texture and improved magnetic properties, e.g., an enhanced remanent magnetization of 72 emu/g for (Sm,Pr)Co₅/Co and 66 emu/g for (Sm,Pr)Co₅. In addition, by using the 8 h ball milled powders (much smaller than the 2 h ball milled powders) as the starting materials, Co nanoparticles can also be successfully coated on the surface of the flakes. A plausible mechanism for the formation of Co nanoparticles on the surface of (Sm,Pr)Co₅ flakes is discussed.