The surface energy of hydrophilic and hydrophobic adsorbents

Water vapor adsorption and heats of water wetting are studied for hydrophilic quartz, hydrophobic-hydrophilic talc, and hydrophobized Silochrom samples. Water contact angles on the materials under examination are found. The surface thermodynamic parameters of the sorbents are calculated from the data obtained. It is shown that boundary water layers on hydrophilic quartz surface are ordered to a higher extent, while those on hydrophobic basal surfaces of talc particles and hydrophobic surfaces of modified Silochrom samples are ordered to a lower extent relative to liquid water. An empirical equation relating the surface pressure of water films adsorbed on hydrophilic high-energy surfaces with the surface free energy of the latter is proposed. The values of surface free energy are estimated from this equation for a number of important hydrophilic adsorbents.     

Wetting of β-casein layers adsorbed at the solid–aqueous interface

The wetting by water of the adsorbed layer of β-casein on hydrophobised silica and pure (hydrophilic) silica surface was investigated by dynamic contact angle measurements based on the Wilhelmy plate principle. The results are discussed in relation to adsorption data obtained for the protein on similar surfaces by in situ ellipsometry. β-casein adsorption on a hydrophobic surface leads to a significant decrease of the contact angle, in particular in terms of the receding contact angle, which decreased by about 70°. This indicates a strong shielding of the hydrophobic surface by the hydrophilic domain of β-casein. Adding a specific enzyme, endoproteinase Asp-N, which previously has been proposed to remove a large fraction of the hydrophilic segments, results in a significantly decreased wettability of the solid surface. The layer is now more hydrophobic and the hysterises is much smaller. The receding contact angle after the proteolysis is roughly 70°. The results are consistent with the hypothesis that β-casein adsorbs at the hydrophobic surface to form a monolayer with the hydrophobic part of the protein anchored at the surface, leaving the hydrophilic segments dangling into the solution. Less dramatic effects are observed in terms of changes of the wettability on the hydrophilic surface. The surface is still quite hydrophilic both after adsorbing β-casein and exposing the layer to endoproteinase Asp-N. These results confirm the differences in the structure of β-casein layers on the hydrophobic and hydrophilic surface.     

Light-controlled directional liquid drop movement on TiO2 nanorods-based nanocomposite photopatterns

Patterned polymeric coatings enriched with colloidal TiO(2) nanorods and prepared by photopolymerization are found to exhibit a remarkable increase in their water wettability when irradiated with UV laser light. The effect can be completely reversed using successive storage in vacuum and dark ambient environment. By exploiting the enhancement of the nanocomposites hydrophilicity upon UV irradiation, we prepare wettability gradients along the surfaces by irradiating adjacent surface areas with increasing time. The gradients are carefully designed to achieve directional movement of water drops along them, taking into account the hysteresis effect that opposes the movement as well as the change in the shape of the drop during its motion. The accomplishment of surface paths for liquid flow, along which the hydrophilicity gradually increases, opens the way to a vast number of potential applications in microfluidics.     

Preillumination of TiO2 and Ta2O5 photoactive thin films as a tool to tailor the synthesis of composite materials

Illumination of TiO 2 thin films with UV light is known to induce the transformation of the surface of this material from partially hydrophobic into fully hydrophilic. The present work shows that this transformation is accompanied by other effects that may be used to control the synthesis of composite materials. For this purpose, TiO 2 and Ta 2O 5 transparent thin films with a columnar structure and open pores were prepared by electron evaporation at glancing angles. Transparent TiO 2 thin films with micropores (i.e., pores smaller than 2 nm) prepared by plasma enhanced chemical vapor deposition (PECVD) were also used. All these films became hydrophilic upon UV illumination. Rhodamine 6G and Rhodamine 800 dyes were irreversibly adsorbed within the columns of the TiO 2 and Ta 2O 5 thin films by immersion into a water solution of these molecules. Isolated and aggregated molecules of these two dyes were detected by visible absorption spectroscopy. The infiltration adsorption efficiency was directly correlated with the acidity of the medium, increasing at basic pHs as expected from simple considerations based on the concepts of the point of zero charge (PZC) in colloidal oxides. The infiltration experiments were repeated with columnar TiO 2 and Ta 2O 5 thin films that were subjected to preillumination with UV light. It was found that this treatment produced a modification in the type (isolated or aggregated) and amount of dye molecules incorporated into the pores. Moreover, the selective adsorption of a given dye in preilluminated areas of the films permitted the lithographic coloring of the films. Preillumination also controls the UV induced deposition of silver on the surface of the microporous TiO 2 thin films. It was found that the size distribution of the formed silver nanoparticles was dependent on the preillumination treatment and that a well-resolved surface plasmon resonance at around 500 nm was only monitored in the preilluminated films. A model is proposed to account for the effects induced by UV preillumination on the TiO 2 and Ta 2O 5 oxide surfaces. The possibilities of this type of light treatment for the tailored synthesis of nanocomposite thin films (i.e., dye-oxide, metal nanoparticles-oxide) are highlighted.     

Preparation of silica-on-titania patterns with a wettability contrast

The preparation of patterned inorganic surfaces consisting of silica (SiO2) and titania (TiO2) is described. The approach is based on a combination of standard photolithography and plasma-enhanced chemical vapor deposition. Silicon wafers coated with a titania layer (40 nm) were patterned by use of a positive photoresist and then a thin silica layer (10-40 nm) was plasma-deposited. The photoresist was removed by decomposition at 800 degrees C. The inorganic patterned surfaces possessed excellent high-temperature resistance. Since the silica patches were effectively dehydroxylated during the thermal treatment, the patterns consisted of moderately hydrophobic (silica) and hydrophilic (titania) domains with a significant wettability contrast (40 degrees for water). The surface was further hydrophobized with a self-assembled monolayer of fluoroalkylsilane (FAS) and exposed to UV light. The FAS layer was locally oxidized on the TiO2 patches and the wettability contrast was maximized to 120 degrees (the highest possible value on smooth surfaces).     

激光刻蚀sol-gelTiO_2薄膜的浸润性研究

应用355 nm脉冲激光在sol-gel TiO_2薄膜表面刻蚀出微米级的沟槽形貌，讨 论了具有微槽形貌TiO_2薄膜的浸润行为及其浸润性与亲水区域面积的关系，以及 紫外光照对具有微槽形貌TiO_2薄膜亲水性的影响。     

Photocatalytic synthesis of silver nanoparticles stabilized by TiO2 nanorods: a semiconductor/metal nanocomposite in homogeneous nonpolar solution

A novel colloidal approach toward semiconductor/metal nanocomposites is presented. Organic-soluble anatase TiO(2) nanorods are used for the first time to stabilize Ag nanoparticles in optically clear nonpolar solutions in the absence of specific ligands for silver. Metallic silver is generated upon UV illumination of deaerated TiO(2) solutions containing AgNO(3). The Ag nanoparticles can be obtained in different size-morphological regimes as a function of the irradiation time, due to light-induced photofragmentation and ripening processes. A mechanism for the colloidal stabilization of the silver nanoparticles is tentatively suggested, which regards the TiO(2) nanorods as inorganic stabilizers, thus acting in the same manner as conventional surfactant molecules. The proposed photocatalytic approach offers a convenient method for producing TiO(2)/Ag nanocomposite systems with a certain control over the metal particle size without the use of surfactants and/or additives. Stable colloidal TiO(2)-nanorod-stabilized Ag nanoparticles can be potentially available for a number of applications that require "clean" metal surfaces, such as homogeneous organic catalysis, photocatalysis, and sensing devices.     

Wettability conversion from superoleophobic to superhydrophilic on titania/single-walled carbon nanotube composite coatings

Superoleophobic surfaces were demonstrated on perfluorosilane-rendered titania (TiO(2))/single-walled carbon nanotube (SWNT) composite coatings. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed that SWNTs play a key role in the formation of overhanging structures and the nanoscale roughness on the coating surface, which compose the two critical morphologic factors for a superoleophobic surface. The wettability conversion from superoleophobic to superhydrophilic of the composite coatings was realized by the gradual decomposition of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) on the coating surface using UV irradiation. Contact angle measurement on both smooth TiO(2) surface and rough composite coating surface under different UV irradiation time revealed that the wetting behavior of the liquids on the composite coating surface passes from the Cassie to the Wenzel and finally to the inversed-Cassie regime. Different liquids show different irradiation time for the wetting state change. By controlling the UV irradiation dose, liquids with surface tension difference smaller than 5 mN/m can exist in completely converse wetting states on the same coating surface, that is, superphobic for one liquid while superphilic for another with lower surface tension. Mixed organic liquids with different surface tension can be completely separated through a coated grid using this wettability tuning technique.     

Inactivation of bacterial endospores by photocatalytic nanocomposites

A novel biocidal photocatalytic nanocomposite, composed of TiO(2) and multi-walled carbon nanotubes (MWNTs), was synthesized via wet chemistry followed by a heat treatment. Uniform anatase coatings on MWNTs were successfully obtained with a thickness of a few nanometers. The nanostructure of the composite was determined by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The needle-like shape of the nanocomposite provided more than three times higher photocatalytic specific surface area than commercial TiO(2) nanoparticles (Degussa P25) when dispersed in water. Moreover, under ultraviolet (UV) radiation the excited electrons can be trapped at the interface between the TiO(2) layer and MWNTs and they can also be scavenged through the conductive graphitic layers. Thus, an intense photochemical reaction yielding a powerful biocide can be expected. Irradiating bacterial endospores (Bacillus cereus) with solar UV lamps in presence of the novel photocatalyst successfully inactivated the spores while solar UV lamps only or solar UV Lamps with Degussa P25 showed no significant inactivating behavior. Performance of photocatalytic nanocomposites was assessed based on time to achieve 90% inactivation of spores (LD(90)) and also in terms of time required to achieve a 1.0 log(10) reduction of spores in the tail region of the inactivation curve.     

Surface energy of hydrophobic adsorbents

The adsorption of water vapor and the heat of wetting of hydrophilic hydromica and hydrophobized samples of kaolinite and Silochrom were studied. The contact angles for the wetting of the investigated materials with water were obtained. The thermodynamic characteristics of the surface of the sorbents and the interfacial region at their boundary with water were calculated from the obtained data. It was shown that the boundary water layers close to the hydrophilic surface of the hydromica are more ordered while those close to the hydrophobic surfaces of the modified samples of kaolinite, Silochrom, and the reference sample (extremely hydrophobic Teflon) are less ordered than liquid water. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 2, pp. 87–91, March–April, 2006.     

Cellulose-based liquid crystalline photoresponsive films with tunable surface wettability

We report on a new type of liquid crystalline cellulosic films with light controllable reversible wettability. The films are prepared from a thermotropic cellulose derivative functionalized with azo-containing groups. These groups exhibit dynamic changes in interfacial properties in response to UV irradiation. The UV irradiation induces trans-to-cis isomerization in the azobenzene moiety, which causes a conformational change in the upper molecular layers of the thin films. These changes originate a hydrophobic to comparatively hydrophilic transformation of the surface. The reversible wettability of the surface results from the cis/trans photo and thermal isomerization. The UV-vis absorption spectra, as well as contact angle measurements with UV irradiation, clearly support the understanding of the phenomenon. This type of surface design enables the amplification of molecular level conformational transitions to macroscopic changes in interface properties using the means of isomerism. This opens new opportunities in surface engineering using eco-friendly cellulose manipulation.     

Characteristics of polyelectrolyte multilayers: effect of PEI anchoring layer and posttreatment after deposition

The influence of a first (anchoring) layer and film treatment on the structure and properties of polyelectrolyte multilayer (PEM) films obtained from polyallylamine hydrochloride (PAH) and polysodium 4-styrenesulfonate (PSS) was studied. Branched polyethyleneimine (PEI) was used as an anchoring layer. The film thickness was measured by ellipsometry. Complementary X-ray reflectometry and AFM experiments were performed to study the change in the interfacial roughness. We found that the thickness of the PEM films increased linearly with the number of layers and depended on the presence of an anchoring PEI layer. Thicker films were obtained for multilayers having PEI as the first layer comparing to films having the same number of layers but consisting of PAH/PSS only. We investigated the wettability of PEM surfaces using direct image analysis of the shape of sessile water drops. Periodic oscillations in contact angle were observed. PAH-terminated films were more hydrophobic than films with PSS as the outermost layer. The effect of long time conditioning of PEM films in solutions of various pH's or salt (NaCl) concentrations was also examined. Salt or base solutions induced modification in wetting properties of the polyelectrolyte multilayers but had a negligible effect on the film thickness.     

Tailoring wettability change on aligned and patterned carbon nanotube films for selective assembly

The effects of oxygen reactive ion etching (RIE) on the surface wettability of aligned carbon nanotube (CNT) films have been systematically investigated. It was found that 3 s of RIE treatment could change the surface of CNT films from hydrophobic to more hydrophilic. The degree of modification in the surface wettability of the film could be controlled by the flow rate of O2 gas during the RIE process. It is proposed that such a surface hydrophobicity change is related to the opened structure and functionalized tip of as-treated CNTs by oxygen reactive ions. More importantly, after the RIE treatment, focused laser pruning was utilized to trim the surface layer of treated CNTs and revert them back to a hydrophobic surface. Combined with the laser pruning technique and O2 RIE treatment, CNT templates with interlaced wettability surfaces in a stripe pattern have been fabricated. It has been demonstrated that this interlaced and structured wettability pattern can be used to selectively assemble microspheres or quantum dots on the aligned CNT films with desired patterns.     

Fabrication and characterization of plasma processed surfaces with tuned wettability

Engineered surfaces with controlled hydrophilic/ hydrophobic character have been fabricated by tailoring the substrate topography and chemistry. In this method, the substrate to be treated was first coated by a photoresist, which was then surface-roughened using SF6 plasma etching. The resulting rough texture was then transferred to the underlying silicon surface by over-etching of the photoresist. At this point, the topographically modified surface was modified chemically by controlled deposition of a thin polymer layer using plasma processing. In this way, both the surface texture and the surface chemistry could be varied independently, producing surfaces with variable wetting character, including super-hydrophilicity and super-hydrophobicity, depending on the choice of plasma polymer deposited. Chemical characterization demonstrates a correlation between the surface chemistry and the wettability of the samples after etching. The surface elementary composition contained more C-F groups as the measured contact angle increased, indicating that the change of wettability is due to both the roughness and the surface energy of the deposited photoresist. In the case of materials deposited on the plasma-treated rough surfaces, the strengthening of the wetting character is only due to the created surface roughness, as XPS analyses showed no significant chemical difference as compared to the flat polymer.     

Wetting properties of model biological membranes

Various aspects of native and model biological membrane wettability are discussed. Among others hydration of mono-, bi-, and multi-layers of lipids as well as wettability of macroscopic surfaces of solid supported lipid films was investigated via apparent contact angle measurements and calculation of the apparent surface free energy of the films. The effects of relative humidity on the layer hydration and contact angle changes are also discussed. Finally, the effect of liposomes and enzymes (due to the hydrolysis reactions) on the hydrophobic/hydrophilic character of the film surfaces is overviewed.     

Photo-induced Janus effect of graphene oxide films

The effect of UV irradiation on the wettability of GO films, as well as the possibility of making a film with different properties of its surface, the Janus film, has been studied. The O/C ratio changes from 0.32 to 0.26 after 6 ​h of UV irradiation. The contact angle of water droplet wetting on an unirradiated surface is θ ​≈ ​35°. The contact angle reaches more than 95° on the irradiated surface, which means that a hydrophobic surface on a film can be obtained. The origin of amphiphilic properties of the GO film are associated with the photochemical reduction of GO.     

Wettability of carbon nanofiber layers on nickel foils

Carbon nanofiber (CNF) layers have been directly synthesized on nickel foils by chemical vapor deposition at 450°C using different H(2) concentrations and reaction times. The addition of 5% H(2) produces thicker, rougher and more porous CNF layers than when 1% H(2) is used. The roughness and porosity increases with reaction time when 5%, 10% or 20% H(2) are used; however, this effect is less pronounced when 1% H(2) is used. CNFs are 50-55 nm in diameter and have a fishbone type structure. We have studied the influence of CNF layer thickness, porosity and surface roughness on the interaction with water by measuring the contact angle. The water wetting properties of the samples are more significantly influenced by the CNF layer thickness than both surface roughness and porosity. When the CNF layer is thicker than ca. 20 μm, the surface is hydrophobic and the contact angle increases with surface roughness and porosity. When the CNF layer is thinner than ca. 20 μm, the surface is hydrophilic and the contact angle decreases with increasing surface roughness and porosity. This behavior is attributed to penetration of water, making contact with the hydrophilic C layer between the CNF layer and the foil.     

水溶性聚合物和两亲聚合物——10.两亲聚合物PAMC_(16)S的自组装有序膜

用自组装技术在金(纯金和经阳极氧化的金)表面上获得了新型两亲聚合物PAMC_(16)S的有序膜。用接触角测试,XPS谱和电化学分析等方法对自组装膜进行了表征。根据膜表面的润湿性,金表面的自组装膜是疏水的,亲水的磺酸基团连于金表面,而疏水的碳氢链从表面伸展出。XPS实验结果支持金表面上单层膜的疏水结构。聚合物单层膜复盖的金电极起到含有针孔缺陷的阻膈型电极的作用。单层膜在法拉第反应中显示很强的吸附稳定性,说明聚合物LB膜在潜在应用中有其特有的特点。     

纳米结构表面浸润性质的分子动力学研究

采用分子动力学方法研究了氩纳米液滴在铂金属及其模型固体表面的浸润现象,获得了液滴在平滑表面和三角纳米结构阵列表面的接触角和展布特性.研究表明,液滴与壁面的势能作用较强时,液滴与纳米结构表面为均匀浸润,但是由于迟滞效应,接触角受表面纳米结构的影响不明显;势能作用较弱时,纳米结构间隙中存在类似蒸汽的低密度相,液滴与纳米结构表面为非均匀浸润,接触角受纳米结构的影响而增大;表面纳米结构可以使表面具有超疏水性.     

Control over wettability of polyethylene glycol surfaces using capillary lithography

We demonstrate that wettability of poly(ethylene glycol) (PEG) surfaces can be controlled using nanostructures with various geometrical features. Capillary lithography was used to fabricate PEG nanostructures using a new ultraviolet (UV) curable mold consisting of functionalized polyurethane with acrylate group (MINS101m, Minuta Tech.). Two distinct wetting states were observed depending of the height of nanostructures. At relatively lower heights (< 300 nm for 150 nm pillars with 500 nm spacing), the initial contact angle of water was less than 80 degrees and the water droplet easily invaded into the surface grooves, leading to a reduced contact angle at equilibrium (Wenzel state). At relatively higher heights (> 400 nm for 150 nm pillars with 500 nm spacing), on the other hand, the nanostructured PEG surface showed hydrophobic nature and no significant change in contact angle was observed with time (Cassie state). The presence of two wetting states was also confirmed by dynamic wetting properties and contact-angle hysteresis. The wetting transition from hydrophilic (bare PEG surface) to hydrophobic (PEG nanostructures) was described by the Cassie-Baxter equation assuming that enhanced hydrophobicity is due to the heterogeneous wetting mediated by an air pocket on the surface. The measured contact angles in the Cassie state were increased with increasing air fraction, in agreement with the theoretical prediction.