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.     

Microscopic wetting of self-assembled monolayers with different surfaces: a combined molecular dynamics and quantum mechanics study

Molecular dynamics simulations are used to study the micronature of the organization of water molecules on the flat surface of well-ordered self-assembled monolayers (SAMs) of 18-carbon alkanethiolate chains bound to a silicon (111) substrate. Six different headgroups (-CH(3), -C═C, -OCH(3), -CN, -NH(2), -COOH) are used to tune the character of the surface from hydrophobic to hydrophilic, while the level of hydration is consistent on all six SAM surfaces. Quantum mechanics calculations are employed to optimize each alkyl chain of the different SAMs with one water molecule and to investigate changes in the configuration of each headgroup under hydration. We report the changes of the structure of the six SAMs with different surfaces in the presence of water, and the area of the wetted surface of each SAM, depending on the terminal group. Our results suggest that a corrugated and hydrophobic surface will be formed if the headgroups of SAM surface are not able to form H-bonds either with water molecules or between adjacent groups. In contrast, the formation of hydrogen bonds not only among polar heads but also between polar heads and water may enhance the SAM surface hydrophilicity and corrugation. We explicitly discuss the micromechanisms for the hydration of three hydrophilic SAM (CN-, NH(2)- and COOH-terminated) surfaces, which is helpful to superhydrophilic surface design of SAM in biomimetic materials.     

Several surfaces with special wettability: Influence on spreading and motion of W/O emulsion droplets

Physical and chemical modifications were made on the surface of the aluminum sheet to change the surface properties and superhydrophobic–hydrophilic wettability gradient surface was made on the perspex surface by using microstructure-pattering technique and self-assembled-monolayer method. By using high-speed video camera system and optical tensiometer, this paper discusses the influence of special surfaces with different wettability on spreading and motion of water, oil, and W/O emulsion droplets both experimentally and theoretically. In addition, the paper also discusses the influence of the superhydrophobic–hydrophilic wettability gradient on fluidity of W/O emulsion droplets and the coalescence process of droplets. The results showed that the contact angle of W/O emulsion droplets on the modified surfaces was related to the water and oil distribution at the three-phase line. On the wettability gradient surface, the droplet moved spontaneously when the droplet was located at the junction of the gradient. A quasi-steady theoretical model was used to analyze the driving and resistant forces acting on a droplet to improve the understanding of the self-transport behavior of the droplets.     

Nanosecond imaging of microboiling behavior on pulsed-heated au films modified with hydrophilic and hydrophobic self-assembled monolayers

Fast transient microboiling has been characterized on modified gold microheaters using a novel laser strobe microscopy technique. Microheater surfaces of different hydrophobicity were prepared using self-assembled monolayers of hexadecane thiol (hydrophobic) and 16-mercaptohexadecanol (hydrophilic) as well as the naturally hydrophilic bare gold surface. The microheater was immersed in a pool of water, and a 5-micros voltage pulse to the heater was applied, causing superheating of the water and nucleation of a vapor bubble on the heater surface. Light from a pulsed Nd:Yag laser was configured to illuminate and image the sample through a microscope assembly. The timing of the short duration (7.5 ns) laser flash was varied with respect to the voltage pulse applied to the heater to create a series of images illuminated by the flash of the laser. These images were correlated with the transient resistance change of the heater both during and after the voltage pulse. It was found that hydrophobic surfaces produced a bubble that nucleated at an earlier time, grew more slowly to a smaller maximum size, and collapsed more rapidly than bubbles formed on hydrophilic surfaces.     

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.     

Wetting and absorption of water drops on Nafion films

Water drops on Nafion films caused the surface to switch from being hydrophobic to being hydrophilic. Contact angle hysteresis of >70 degrees between advancing and receding values were obtained by the Wilhelmy plate technique. Sessile drop measurements were consistent with the advancing contact angle; the sessile drop contact angle was 108 degrees . Water drop adhesion, as measured by the detachment angle on an inclined plane, showed much stronger water adhesion on Nafion than Teflon. Sessile water and methanol drops caused dry Nafion films to deflect. The flexure went through a maximum with time. Flexure increased with contact area of the drop, but was insensitive to the film thickness. Methanol drops spread more on Nafion and caused larger film flexure than water. The results suggest that the Nafion surface was initially hydrophobic but water and methanol drops caused hydrophilic sulfonic acid domains to be drawn to the Nafion surface. Local swelling of the film beneath the water drop caused the film to buckle. The maximum flexure is suggested to result from motion of a water swelling front through the Nafion film.     

Study of temperature-responsibility on the surfaces of a thermo-responsive polymer modified stationary phase

We investigated a thermo-sensitive polymer, poly(N-isopropylacrylamide) (PNIPAAm), which is the basis of an HPLC stationary phase. We prepared a PNIPAAm terminally-modified surface. In this study, we investigated the effect of PNIPAAm on the surface of a stationary phase on separation based on changes of the retention time with the temperature step gradient. As the temperature changed the surface property of the stationary phase switched from hydrophilic to hydrophobic. The retention on the polymer-modified stationary phase remarkably changed upon changing the temperature. Using a column packed with PNIPAAm-modified silica, the separation of steroids was carried out by changing the temperature. With increasing temperature, an increased interaction between solutes and PNIPAAm-grafted surfaces of the stationary phases was observed. A temperature-dependent resolution of steroids was achieved using only water as a mobile phase. The PNIPAAm-modified surface of the stationary phase exhibited temperature-controlled hydrophilic-hydrophobic changes. The drastic and reversible surface hydrophilic-hydrophobic property alteration for PNIPAAm terminally-grafted surfaces should be due to rapid changes in the polymer hydration state around the polymer's transition temperature. A solvent gradient elution-like effect could be achieved with a single mobile phase by programmed temperature changes during chromatographic runs. This system should be highly useful to control the function and property of the stationary phase for HPLC only by changing the temperature with an aqueous solvent.     

The effect of surface wettability on induction and growth of neurites from the PC-12 cell on a polymer surface

Surface properties of polymeric devices that are used to regenerate nervous damage are a point to be considered for axon regeneration in nerve system. In our previous studies, we prepared a wettability gradient on polyethylene (PE) surfaces using a corona discharge treatment from a knife-type electrode whose power increases gradually along the sample length. The PE surfaces were oxidized gradually with increasing power. The effect of surface wettability on the different types of cells has an important role for cell adhesion and proliferation. The purpose of this study is to investigate neurite formation on polymer surfaces with different wettability. Induction and growth of neurites from the rat pheochromocytoma (PC-12) cells attached on the polymer surfaces with different hydrophilicity were investigated using the wettability gradient PE surfaces prepared by a corona discharge treatment. Neurites were investigated for number and length of neurites in terms of surface wettability. It was observed that neurite formation of PC-12 cells was increased more onto the positions with moderate hydrophilicity of the wettability gradient surface than onto the more hydrophobic or hydrophilic positions. From those results, it could be assumed that initial adhesion of PC-12 cells was caused by more calf serum (CS) protein than nerve growth factor (NGF), whereas the neurite formation of PC-12 cells was caused by more NGF than CS protein. It follows from what has been said thus far that PC-12 cells are a differentiated neuronal phenotype with a long neurite at around the position 2.5 cm (water contact angle of about 55 deg). In conclusion, surface wettability plays an important role for neurite formation on the polymer surfaces for axon regeneration.     

Non-invasive vibrational SFG spectroscopy reveals that bacterial adhesion can alter the conformation of grafted "brush" chains on SAM

Understanding bacterial adhesion on a surface is a crucial step to design new materials with improved properties or to control biofilm formation and eradication. Sum Frequency Generation (SFG) vibrational spectroscopy has been employed to study in situ the conformational response of a self-assembled monolayer (SAM) of octadecanethiol (ODT) on a gold film to the adhesion of hydrophilic and hydrophobic ovococcoid model bacteria. The present work highlights vibrational SFG spectroscopy as a powerful and unique non-invasive biophysical technique to probe and control bacteria interaction with ordered surfaces. Indeed, the SFG vibrational spectral changes reveal different ODT SAM conformations in air and upon exposure to aqueous solution or bacterial adhesion. Furthermore, this effect depends on the bacterial cell surface properties. The SFG spectral modeling demonstrates that hydrophobic bacteria flatten the ODT SAM alkyl chain terminal part, whereas the hydrophilic ones raise this ODT SAM terminal part. Microorganism-induced alteration of grafted chains can thus affect the desired interfacial functionality, a result that should be considered for the design of new reactive materials.     

Influence of nanobubbles on the adsorption of nanoparticles

A quartz crystal microbalance was used to study the influence of nanobubbles on the adsorption of polystyrene nanoparticles onto surfaces coated with gold, or coated with dodecanethiol or mercaptoundecanoic acid self-assembled monolayers (SAMs). Adsorption of the nanoparticles onto the surface causes the resonant frequency of the quartz crystal to decrease. We found that particles were adsorbed onto the gold-coated quartz crystal in air-rich water, but not in degassed water. This finding supports the long-standing hypothesis that nanobubbles play a key role in the long-range attractive force between hydrophobic surfaces in aqueous solutions. When the experiments were conducted using quartz crystals coated with a hydrophobic dodecanethiol SAM, the nanoparticles were adsorbed onto the surface even in degassed water due to the short-range hydrophobic interactions between the nanoparticles and the dodecanethiol molecules. In contrast, the nanoparticles were adsorbed to a lesser degree onto the hydrophilic mercaptoundecanoic acid-coated crystals due to electrostatic repulsive forces.     

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.     

Contact angle kinetics of human albumin solutions at solid surfaces

Contact angle kinetics of sessile drops of albumin solution on hydrophilic acetal and hydrophobic FC 721 surfaces were measured using axisymmetric drop shape analysis. Young's equation is used to calculate the solid/liquid interfacial tension from measured contact angles and surface tensions as a function of time. The change in solid/liquid interfacial tension is a result of protein adsorption. It indicates that at the hydrophilic acetal surface the albumin molecules, interact only weakly, whereas the interaction with the hydrophobic FC 721 surface is quite strong.     

Assembly of nanoparticles at the contact line of a drying droplet under the influence of a dipped tip

The manipulation of colloidal nanoparticles (NPs) in a drying droplet has critical importance not only for several industrial applications but also their assembly into patterns on surfaces. The influence of a tip with hydrophilic or hydrophobic surfaces dipped into a drying droplet on hydrophilic or hydrophobic surfaces on the behavior of 98 nm latex NPs was investigated. The formation of concentric rings on hydrophilic glass surfaces regardless of the surface chemistry of the dipped tip was observed. On the other hand, no pattern formation on hydrophobic surfaces was observed with the insertion of the tip. With a hydrophilic tip, the concentric rings were formed due to stick-slip motion of the solvent contact line resulting from competition between pinning and capillary forces while the capillary effect was not effective until the surface of the tip was changed by adherent NPs making the tip surface available for water adherence with a hydrophobic tip, which results in the pulling of droplet towards the tip. It is also found that the tip thickness and suspension concentration significantly influences the formation of concentric rings on surfaces. This simple procedure can be used to influence the distribution or assembly of NPs in the droplet area.     

Mechanical stabilization effect of water on a membrane-like system

The penetration resistance of a prototypical model-membrane system (HS-(CH2)11-OH self-assembled monolayer (SAM) on Au(111)) to the tip of an atomic force microscope (AFM) is investigated in the presence of different solvents. The compressibility (i.e., height vs tip load) of the HS-(CH2)11-OH SAM is studied differentially, with respect to a reference structure. The reference consists of hydrophobic alkylthiol molecules (HS-(CH2)17-CH3) embedded as nanosized patches into the hydrophilic SAM by nanografting, an AFM-assisted nanolithography technique. We find that the penetration resistance of the hydrophilic SAM depends on the nature of the solvent and is much higher in the presence of water than in 2-butanol. In contrast, no solvent-dependent effect is observed in the case of hydrophobic SAMs. We argue that the mechanical resistance of the hydroxyl-terminated SAM is a consequence of the structural order of the solvent-SAM interface, as suggested by our molecular dynamics simulations. The simulations show that in the presence of 2-butanol the polar head groups of the HS-(CH2)11-OH SAM, which bind only weakly to the solvent molecules, try to bind to each other, disrupting the local order at the interface. On the contrary, in the presence of water the polar head groups bind preferentially to the solvent that, in turn, mediates the release of the surface strain, leading to a more ordered interface. We suggest that the mechanical stabilization effect induced by water may be responsible for the stability of even more complex, real membrane systems.     

A unique behavior of water drops induced by low-density polyethylene surface with a sharp wettability transition

A low-density polyethylene (LDPE) surface with a sharp wettability gradient and high hysteresis was prepared, on which a unique behavior of water drops was found. The water contact angle of one water drop on the less hydrophobic region was larger than that on the more hydrophobic end, which was much different from the general phenomenon. The unique behavior is believed to be induced by the high hysteresis of the LDPE surface and the sharp change in wettability. The driving and hysteresis forces acting on the water drops were calculated and analyzed in detail. The reasons resulting to such a unique phenomenon were further explained.     

Chemical stability of nonwetting, low adhesion self-assembled monolayer films formed by perfluoroalkylsilanization of copper

A self-assembled monolayer (SAM) has been produced by reaction of 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) with an oxidized copper (Cu) substrate and investigated by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, and contact angle measurement. FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. The perfluoroalkyl SAM on Cu is found to be extremely hydrophobic, yielding sessile drop static contact angles of more than 130 degrees for pure water and a "surface energy" (which is proportional to the Zisman critical surface tension for a Cu surface with 0 rms roughness) of 14.5 mJm2(nMm). Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH=12, 60 degrees C) solutions for at least 30 min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70 min at 60 degrees C or 50 min at 80 degrees C. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for antiwetting, low adhesion surfaces or dropwise condensation on heat exchange surfaces.     

Fluorocarbon Surfactant Polymers: Effect of Perfluorocarbon Branch Density on Surface Active Properties

We describe a series of fluorocarbon surfactant polymers designed for modifying fluorocarbon surfaces such as poly(tetrafluoroethylene). Novel fluorocarbon surfactant polymers poly(N-vinyldextranaldonamide-co-N-vinylperfluoroundecanamide), in which hydrophilic dextran oligosaccharides and hydrophobic perfluoroundecanoyl groups were incorporated sequentially onto a poly(vinylamine) backbone, were synthesized and characterized by FT-IR, NMR, and XPS spectroscopy. By adjusting the feed ratio of dextran to fluorocarbon branches, surfactant polymers with different hydrophilic/hydrophobic balances were prepared. The surface activity of the surfactants at the air/water interface was demonstrated by significant reductions in water surface tension. Surfactant adsorption and adhesion at the solid PTFE/aqueous interface were examined under well-defined dynamic flow conditions, using a rotating disk system. The surface activity at the air/water interface and adhesion stability on PTFE under an applied shear stress both increase with increasing density of fluorocarbon branches on the polymer backbone. The results show that stable surfactant adhesion on PTFE can be achieved by adjusting the hydrophilic dextran to hydrophobic fluorocarbon branch ratio.     

Switching and structuring of binary reactive polymer brush layers

Switchable binary polymer brushes grafted to Si-wafers were prepared from hydrophilic and hydrophobic polymer components. When exposed to solvents, either the hydrophobic or the hydrophilic component extends in to the liquid phase, depending on the polarity of the solvent. The hydrophilic component was poly-2-vinylpyridine; the hydrophobic component was made photocrosslinkable in that a polystyrene copolymer containing a photodimerizing chromophore was used. In this system surfaces differing in water contact angle between 60° and 100° can be produced by variation of the solvent. The chromophore was phenylindene, which forms crosslinks upon direct UV-irradiation. Therefore, the polystyrene component can be fixed in the extended or collapsed state. It will be shown that by irradiation through an appropriate mask, surfaces can be structured and the structures fixed. In both the systems structural patterns differing in surface properties were produced and fixed photochemically.     

Polypeptide friction and adhesion on hydrophobic and hydrophilic surfaces: a molecular dynamics case study

Using all-atomistic MD simulations including explicit water, the mobility and adhesion of a mildly hydrophobic single polypeptide chain adsorbed on hydrophobic and hydrophilic diamond surfaces is investigated by application of lateral and vertical pulling forces. Forced motion on the hydrophilic surface exhibits stick-slip due to breaking and reformation of hydrogen bonds; in contrast, on the hydrophobic surface, the motion is smooth. By carefully tuning the driving force magnitude, the linear-response regime is reached on a hydrophobic surface and equilibrium values for mobility and adhesive strength are obtained. On the hydrophilic surface, on the other hand, slow hydrogen-bond kinetics prevents equilibration and only upper bounds for adhesion force and mobility can be estimated. Whereas the desorption force is rather comparable on the two surfaces and differs at most by a factor of 2, the mobility on the hydrophilic surface is at least 30-fold reduced compared to the hydrophobic one. A simple model based on a single particle diffusing in a corrugated potential landscape suggests that cooperativity is rather limited and that the small mobility on a hydrophilic surface can be rationalized in terms of incoherently moving monomers. The experimentally well-known peptide mobility in bulk water is quantitatively reproduced in our simulations, which serves as a sensitive test on our methodology employed.     

Nanodrop on a nanorough solid surface: density functional theory considerations

The density distributions and contact angles of liquid nanodrops on nanorough solid surfaces are determined on the basis of a nonlocal density functional theory. Two kinds of roughness, chemical and physical, are examined. The former considers the substrate as a sequence of two kinds of semi-infinite vertical plates of equal thicknesses but of different natures with different strengths for the liquid-solid interactions. The physical roughness involves an ordered set of pillars on a flat homogeneous surface. Both hydrophobic and hydrophilic surfaces were considered. For the chemical roughness, the contact angle which the drop makes with the flat surface increases when the strength of the liquid-solid interaction for one kind of plates decreases with respect to the fixed value of the other kind of plates. Such a behavior is in agreement with the Cassie-Baxter expression derived from macroscopic considerations. For the physical roughness on a hydrophobic surface, the contact angle which a drop makes with the plane containing the tops of the pillars increases with increasing roughness. Such a behavior is consistent with the Wenzel formula developed for macroscopic drops. For hydrophilic surfaces, as the roughness increases the contact angle first increases, in contradiction with the Wenzel formula, which predicts for hydrophilic surfaces a decrease of the contact angle with increasing roughness. However, a further increase in roughness changes nonmonotonously the contact angle, and at some roughness, the drop disappears and only a liquid film is present on the surface. It was also found that the contact angle has a periodic dependence on the volume of the drop.