Investigating the effects of solid surfaces on ice nucleation

Understanding the role played by solid surfaces in ice nucleation is a significant step toward designing anti-icing surfaces. However, the uncontrollable impurities in water and surface heterogeneities remain a great challenge for elucidating the effects of surfaces on ice nucleation. Via a designed process of evaporation, condensation, and subsequent ice formation in a closed cell, we investigate the ice nucleation of ensembles of condensed water microdroplets on flat, solid surfaces with completely different wettabilities. The water microdroplets formed on flat, solid surfaces by an evaporation and condensation process exclude the uncontrollable impurities in water, and the effects of surface heterogeneities can be minimized through studying the freezing of ensembles of separate and independent water microdroplets. It is found that the normalized surface ice nucleation rate on a hydrophilic surface is about 1 order of magnitude lower than that on a hydrophobic surface. This is ascribed to the difference in the viscosity of interfacial water and the surface roughness.     

Lateral Force Microscopy Study of the Friction between Silica Surfaces

The friction between a single silica glass sphere and a flat silica glass surface has been investigated using lateral force microscopy. Two types of silica surface were investigated, one fully hydroxylated and the other partially dehydroxlated. These samples have markedly different wetting properties and are known as hydrophilic and hydrophobic silica, respectively. The lateral friction force as a function of applied normal load has been collected for five different-sized spheres for both surface types. Analysis of the friction versus load data indicates that the hydrophilic surfaces have a molecularly smooth contact. For the hydrophobic surfaces, it is not clear whether the friction-load response is caused by a smooth or an asperity-dominated contact zone. Copyright 2000 Academic Press.     

Liquid–paper interactions during liquid drop impact and recoil on paper surfaces

The spreading and recoiling of water drops on several flat and macroscopically smooth model surfaces and on sized paper surfaces were studied over a range of drop impaction velocities using a high-speed CCD camera. The water drop spreading and recoiling results on several model hydrophobic and hydrophilic surfaces were found to be in agreement with observations reported in the literature. The maximum drop spreading diameter for those model surfaces at impact was found to be dependent upon the initial drop kinetic energy and the degree of hydrophobicity/hydrophilicity of the surface. The extent of the maximum drop recoiling was found to be much weaker for hydrophilic substrates than for hydrophobic substrates. Sized papers, however, showed an interesting switch of behaviour in the process of water drop impaction. They behave like a hydrophobic substrate when a water drop impacts on it, but like a hydrophilic substrate when water drop recoils. Although the contact angle between water and hydrophilic or hydrophobic non-porous surfaces changes from advancing to receding as reported in literature, the change of contact angle during water impact on paper surface is unique in that the level of sizing was found to have a smaller than expected influence on the degree of recoil. Atomic force microscopy (AFM) was used to probe fibres on a sized filter paper surface under water. The AFM data showed that water interacted strongly with the fibre even though the paper was heavily sized. Implications of this phenomenon were discussed in the context of inkjet print quality and of the surface conditions of sized papers. Results of this study are very useful in the understanding of inkjet ink droplet impaction on paper surfaces which sets the initial condition for ink penetration into paper after impaction.     

Interfacial water on hydrophobic surfaces recognized by ions and molecules

Recent spectrophotometric and molecular dynamics simulation studies have shown that the physicochemical properties and structures of water in the vicinity of hydrophobic surfaces differ from those of the bulk water. However, the interfacial water acting as a separation medium on hydrophobic surfaces has never been detected and quantified experimentally. In this study, we show that small inorganic ions and organic molecules differentiate the interfacial water formed on the surfaces of octadecyl-bonded (C(18)) silica particles from the bulk water and the chemical separation of these solutes in aqueous media with hydrophobic materials can be interpreted with a consistent mechanism, partition between the bulk water phase and the interfacial water formed on the hydrophobic surface. Thermal transition behaviour of the interfacial water incorporated in the nanopores of the C(18) silica materials and the solubility parameter of the water calculated from the distribution coefficients of organic compounds have indicated that the interfacial water may have a structure of disrupted hydrogen bonding. The thickness of the interfacial water or the limit of distance from the hydrophobic surface at which molecules and ions can sense the surface was estimated to be 1.25 ± 0.13 nm from the volume of the interfacial water obtained by a liquid chromatographic method and the surface area, suggesting that the hydrophobic effect may extend beyond the first solvation shell of water molecules directly surrounding the surfaces.     

Robust hydrophobic surfaces displaying different surface roughness scales while maintaining the same wettability

A range of surfaces coated with spherical silica particles, covering the size range from nanometer to micrometer, have been produced using Langmuir-Blodgett (LB) deposition. The particles were characterized both in suspension and in the Langmuir trough to optimize the surface preparation procedure. By limiting the particle aggregation and surface layer failures during the preparation steps, well-defined monolayers with a close-packed structure have been obtained for all particle sizes. Thus, this procedure led to structured surfaces with a characteristic variation in the amplitude and spatial roughness parameters. In order to obtain robust surfaces, a sintering protocol and an AFM-based wear test to determine the stability of the deposited surface layer were employed. Hydrophobization of the LB films followed by water contact angle measurements showed, for all tested particle sizes, the same increase in contact angle compared to the contact angle of a flat hydrophobic surface. This indicates nearly hexagonal packing and gives evidence for nearly complete surface wetting of the surface features.     

Beyond the lotus effect: roughness influences on wetting over a wide surface-energy range

To enhance our understanding of liquids in contact with rough surfaces, a systematic study has been carried out in which water contact angle measurements were performed on a wide variety of rough surfaces with precisely controlled surface chemistry. Surface morphologies consisted of sandblasted glass slides as well as replicas of acid-etched, sandblasted titanium, lotus leaves, and photolithographically manufactured golf-tee shaped micropillars (GTMs). The GTMs display an extraordinarily stable, Cassie-type hydrophobicity, even in the presence of hydrophilic surface chemistry. Due to pinning effects, contact angles on hydrophilic rough surfaces are shifted to more hydrophobic values, unless roughness or surface energy are such that capillary forces become significant, leading to complete wetting. The observed hydrophobicity is thus not consistent with the well-known Wenzel equation. We have shown that the pinning strength of a surface is independent of the surface chemistry, provided that neither capillary forces nor air enclosure are involved. In addition, pinning strength can be described by the axis intercept of the cosine-cosine plot of contact angles for rough versus flat surfaces with the same surface chemistries.     

Modification of the glass surface property in PDMS-glass hybrid microfluidic devices

This paper presents a simple method to change the hydrophilic nature of the glass surface in a poly(dimethylsiloxane) (PDMS)-glass hybrid microfluidic device to hydrophobic by an extra-heating step during the fabrication process. Glass substrates bonded to a native or oxygen plasma-treated PDMS chip having microchambers (12.5 mm diameter, 110 μm height) were heated at 200°C for 3 h, and then the hydrophobicity of the glass surfaces on the substrate was evaluated by measuring the contact angle of water. By the extra-heating process, the glass surfaces became hydrophobic, and its contact angle was around 109°, which is nearly the same as native PDMS surfaces. To demonstrate the usefulness of this surface modification method, a PDMS-glass hybrid microfluidic device equipped with microcapillary vent structures for pneumatic manipulation of droplets was fabricated. The feasibility of the microcapillary vent structures on the device with the hydrophobic glass surfaces are confirmed in practical use through leakage tests of the vent structures and liquid handling for the electrophoretic separation of DNA molecules.     

Fabrication of flexible gold films with periodic sub-micrometer roughness and their wettability control by modification of SAM

Flexible honeycomb gold films supported by polymer sheets are fabricated by using polystyrene particle monolayers. The surfaces of the flexible gold films are covered with self-assembled monolayers (SAMs) of hydrophobic or hydrophilic thiol compounds, and the wettability of the modified surface is evaluated by measurements of the contact angles of water droplets. The contact angle of the film covered with hydrophobic SAM is ca. 150 degrees, which is greater than the value of 112 degrees for a flat gold surface, while the values for hydrophilic SAM are below 10 degrees.     

特殊浸润性表面的液滴凝结

以铝片为基底, 经电化学腐蚀和沸水处理制备了多级微纳米结构; 通过气相沉积和涂油分别制备了超疏水表面、 疏水超润滑(slippery)表面和亲水slippery表面; 探究了表面不同的特殊浸润性(超亲水、 超疏水、 疏水slippery和亲水slippery)对液滴凝结的影响. 结果表明, 超亲水表面的液滴凝结属于膜状冷凝, 超疏水表面和slippery表面的液滴凝结均属于滴状冷凝. 超疏水表面液滴合并时, 合并的液滴会不定向弹离表面. 疏水slippery表面和亲水slippery表面由于表面浸润性的不同导致液滴成核密度和液滴合并的差异, 亲水slippery表面凝结液滴的最大体积远大于疏水slippery表面凝结液滴的最大体积. 4种表面的雾气收集效率由大到小依次为亲水slippery表面>疏水slippery表面>超亲水表面>超疏水表面.     

Defect induced asymmetric pit formation on hydroxyapatite

Defect sites on bone minerals play a critical role in bone remodeling processes. We investigated single crystal hydroxyapatite (100) surfaces bearing crystal defects under acidic dissolution conditions using real-time in situ atomic force microscopy. At defect sites, surface structure-dependent asymmetric hexagonal etch pits were formed, which dominated the overall dissolution rate. Meanwhile, dissolution from the flat terraces proceeded by stochastic formation of flat bottom etch pits. The resulting pit shapes were intrinsically dictated by the HAP crystal structure. Computational modeling also predicted different step energies associated with different facets of the asymmetric etch pits. Our microscopic observations of HAP dissolution are significant for understanding the effects of local surface structure on the bone mineral remodeling process and provide useful insights for the design of novel therapies for treating osteoporosis and dental caries.     

超疏水低粘着铜表面制备及其防覆冰性能

用喷砂处理在铜片表面形成微米级丘陵状凹坑,再用表面氧化处理在铜片表面制备菊花花瓣状CuO纳米片.通过喷砂-表面氧化处理在铜片表面成功构建了微米-纳米复合结构,这种表面氟化后与水滴的接触角高达161°,滚动角低至1°,显示出优异的超疏水性和很低的粘着性.低温下,这种表面与水滴间的热量交换较小,水滴不易凝结,有效地提高了抗结霜性.抗结霜性良好的超疏水铜有望在热交换器或低温运行设备等领域获得应用,这种简便的超疏水铜表面的制备方法也给其它工程材料超疏水表面的工业化制备提供了一个思路.     

Wetting of nanogrooved polymer surfaces

Molecular dynamics simulations were used to study the wetting of nanogrooved PE and PVC polymer surfaces. The contact angles, equilibrium states, and equilibrium shapes of two nanosized water droplets were analyzed on surfaces with 1D-arranged periodic roughness of various dimensions. The composite solid-liquid contact, which is preferred in practical applications and in which a droplet rests on top of the surface asperities, was observed on the roughest PE surfaces, whereas water filled the similar but slightly deeper grooves on PVC surfaces. The transition from the wetted to composite contact regime occurred when the contact angle with a flat surface reached the value at which the apparent Wenzel and Cassie contact angles are equal. Droplets on grooved PE surfaces with the composite contact exhibited contact angles in agreement with Cassie's equation, but the increase in hydrophobicity on smoother surfaces with the wetted contact was less than expected from Wenzel's equation. The difference between the simulated and theoretical values decreased as the dimensions of the surface grooves increased. Only a slight increase or even a slight decrease in the contact angles was observed on the grooved PVC surfaces, owing to the less hydrophobic nature of the flat PVC surface. On both polymers, the nanodroplet assumed a spherical shape in the composite contact. Only minor anisotropy was observed in the wetted contact on PE surfaces, whereas even a highly anisotropic shape was seen on the grooved PVC surfaces. The contact angle in the direction of the grooves was smaller than that in the perpendicular direction, and the difference between the two angles decreased with the increasing size of the water droplet.     

Molecular dynamics simulation of water near nanostructured hydrophobic surfaces: interfacial energies.

We present results from molecular dynamics simulations of water near structured hydrophobic surfaces. The surface structures reported herein are a planar alkane crystal as a reference and crystals with a hole and a protrusion of approximately 2.5 nm diameter and 0.5 nm depth or height. All indicators show that surface structuring increases the hydrophobicity: The water density is reduced near the structure elements, and the number of residual contacts between water and the surface decreases by about 40 % with respect to the planar surface. Thermodynamic integration shows that the interfacial energy of the structured surfaces is about 7 mJ m(-2) higher for structured surfaces than for the planar surface. The hydrophobicity increases by a similar amount for the hole and the protrusion geometries compared to the planar surface.     

Mercury adsorption on gold surfaces employed in the sampling and determination of vaporous mercury: a scanning tunneling microscopy study

To clarify the mechanism of mercury adsorption on gold surfaces thin epitaxial gold films have been exposed to trace amounts of gaseous mercury under laboratory conditions for different periods of time. The changes in the surface morphology of the thin films caused by the exposure have been studied by scanning tunneling microscopy (STM). The evolution of the surface structures with time has been also investigated, in the course of a few days after the exposure. The adsorption of mercury on the gold surfaces has caused drastic changes in the morphology of the surfaces. Pits and islands of 2 to 30 nm in diameter have appeared on the surface, their size and density per unit area depending on the amount of exposure to mercury. The formation of pits and islands followed a certain path of events.     

Mercury adsorption on gold surfaces employed in the sampling and determination of vaporous mercury: a scanning tunneling microscopy study

To clarify the mechanism of mercury adsorption on gold surfaces thin epitaxial gold films have been exposed to trace amounts of gaseous mercury under laboratory conditions for different periods of time. The changes in the surface morphology of the thin films caused by the exposure have been studied by scanning tunneling microscopy (STM). The evolution of the surface structures with time has been also investigated, in the course of a few days after the exposure. The adsorption of mercury on the gold surfaces has caused drastic changes in the morphology of the surfaces. Pits and islands of 2 to 30 nm in diameter have appeared on the surface, their size and density per unit area depending on the amount of exposure to mercury. The formation of pits and islands followed a certain path of events.     

Fabrication of biomimetic superhydrophobic surfaces by a simple flame treatment method

A simple flame treatment method was explored to construct micro/nanostructures on a surface and then fabricate a biomimetic superhydrophobic surface at a relatively low cost. SiO₂‐containing polydimethylsiloxane (PDMS) was used as a substrate. The PDMS replicas with various micropatterned surfaces were fabricated using grass leaf, sand paper, and PET sheet with parallel groove geometry as templates via PDMS replica molding. The PDMS replica surfaces with micron structures and the surface of a flat PDMS sheet as a control sample were further treated by flame. The fabricated surfaces were characterized by scanning electron microscopy and water contact angle measurements. The effect of surface microstructures on the transparency of PDMS was also investigated. The studies indicate that the fine nanoscale structures can be produced on the surfaces of PDMS replicas and a flat PDMS sheet by a flame treatment method, and that the hierarchical surface roughness can be adjusted and controlled by varying the flame treatment time. The flame‐treated surfaces of PDMS replicas and a flat PDMS sheet possess superhydrophobicity and an ultra‐low sliding angle reaching a limiting value of 1°, and the anisotropic wettability of the PDMS replica surface with oriented microgroove structures can be greatly suppressed via flame treatment. The visible light transmittance of the flame‐treated flat PDMS surface decreases with prolonged flame treatment times. Copyright © 2016 John Wiley & Sons, Ltd.     

Self-assembly of class II hydrophobins on polar surfaces

Hydrophobins are structural proteins produced by filamentous fungi that are amphiphilic and function through self-assembling into structures such as membranes. They have diverse roles in the growth and development of fungi, for example in adhesion to substrates, for reducing surface tension to allow aerial growth, in forming protective coatings on spores and other structures. Hydrophobin membranes at the air-water interface and on hydrophobic solids are well studied, but understanding how hydrophobins can bind to a polar surface to make it more hydrophobic has remained unresolved. Here we have studied different class II hydrophobins for their ability to bind to polar surfaces that were immersed in buffer solution. We show here that the binding under some conditions results in a significant increase of water contact angle (WCA) on some surfaces. The highest contact angles were obtained on cationic surfaces where the hydrophobin HFBI has an average WCA of 62.6° at pH 9.0, HFBII an average of 69.0° at pH 8.0, and HFBIII had an average WCA of 61.9° at pH 8.0. The binding of the hydrophobins to the positively charged surface was shown to depend on both pH and ionic strength. The results are significant for understanding the mechanism for formation of structures such as the surface of mycelia or fungal spore coatings as well as for possible technical applications.     

Roughness and ordering at the interface of oxidized polystyrene and water

For the first time, atomistically detailed molecular dynamics calculations revealed molecular ordering of the water-oxidized atactic polystyrene (aPS) interface. Both ordering of the water molecules and the phenyl rings occur. In addition, the natural roughness of the surface has been simulated and compared to experimental values. The composition of the simulated aPS films is based on spin-coated aPS films that have been oxidized and characterized experimentally. The aPS surfaces are oxidized with ultraviolet-ozone radiation and have been characterized by XPS, AFM, and water contact angle measurements. XPS measurements show that the oxygen content in the sample increases rapidly with exposure and reaches saturation near 24 at. % of oxygen. The molecular dynamics simulations show smoothening of an hydrophobic aPS surface upon transition from vacuum to water. The smoothening decreases with increasing hydrophilicity. The calculations reveal ordering of oxidized phenyl rings for aPS surfaces in water. The order increases with increasing hydrophilicity. Additionally, we investigated the water structure near the aPS-water interface as a function of the surface hydrophilicity. With increasing hydrophilicity, the density of water at the aPS-water interface increases. The water density profile is steeper in the presence of hydrophobic aPS. The water shows an ordered layer near both the hydrophobic and hydrophilic surfaces; the position of this layer shifts toward the interface with increasing hydrophilicity.     

Effect of Surface Depressions on Wetting and Interactions between Hydrophobic Pore Array Surfaces

The surface structure is known to significantly affect the long-range capillary forces between hydrophobic surfaces in aqueous solutions. It is, however, not clear how small depressions in the surface will affect the interaction. To clarify this, we have used the AFM colloidal probe technique to measure interactions between hydrophobic microstructured pore array surfaces and a hydrophobic colloidal probe. The pore array surfaces were designed to display two different pore spacings, 1.4 and 4.0 μm, each with four different pore depths ranging from 0.2 to 12.0 μm. Water contact angles measured on the pore array surfaces are lower than expected from the Cassie-Baxter and Wenzel models and not affected by the pore depth. This suggests that the position of the three-phase contact line, and not the interactions underneath the droplet, determines the contact angle. Confocal Raman microscopy was used to investigate whether water penetrates into the pores. This is of importance for capillary forces where both the movement of the three-phase contact line and the situation at the solid/liquid interface influence the stability of bridging cavities. By analyzing the shape of the force curves, we distinguish whether the cavity between the probe and the surfaces was formed on a flat part of the surface or in close proximity to a pore. The pore depth and pore spacing were both found to statistically influence the distance at which cavities form as surfaces approach each other and the distance at which cavities rupture during retraction.