Rough Hydrophobic Surfaces Research Articles

Model and experimental studies for contact angles of surfactant solutions on rough and smooth hydrophobic surfaces

Despite the practical need, no models exist to predict contact angles or wetting mode of surfactant solutions on rough hydrophobic or superhydrophobic surfaces. Using Gibbs' adsorption equation and a literature isotherm, a new model is constructed based on the Wenzel and Cassie equations. Experimental data for aqueous solutions of sodium dodecyl sulfate (SDS) contact angles on smooth Teflon surfaces are fit to estimate values for the adsorption coefficients in the model. Using these coefficients, model predictions for contact angles as a function of topological f (Cassie) and r (Wenzel) factors and SDS concentration are made for different intrinsic contact angles. The model is also used to design/tune surface responses. It is found that: (1) predictions compare favorably to data for SDS solutions on five superhydrophobic surfaces. Further, the model predictions can determine which wetting mode (Wenzel or Cassie) occurred in each experiment. The unpenetrated or partially penetrated Cassie mode was the most common, suggesting that surfactants inhibit the penetration of liquids into rough hydrophobic surfaces. (2) The Wenzel roughness factor, r, amplifies the effect of surfactant adsorption, leading to larger changes in contact angles and promoting total wetting. (3) The Cassie solid area fraction, f, attenuates the lowering of contact angles on rough surfaces. (4) The amplification/attenuation is understood to be due to increased/decreased solid-liquid contact-area.

Molecular Dynamics Simulation Study of Interaction between Model Rough Hydrophobic Surfaces

Molecular Dynamics Simulation Study of Interaction between Model Rough Hydrophobic Surfaces

Is the Cassie−Baxter Formula Relevant?

The utility of the Cassie-Baxter formula to predict the apparent contact angle of a drop on rough hydrophobic surfaces has been questioned recently. To resolve this issue, experimental and numerical data for advancing and receding contact angles are reported. In all cases considered it is seen that contact angles follow the overall trend of the Cassie-Baxter formula, except for the advancing front on pillar type roughness. It is shown that deviations from the Cassie-Baxter angle have a one-to-one correlation with microscopic distortions of the contact line with respect to its configuration in the Cassie-Baxter state.

Freezing Behavior of a Water Droplet on a Rough Hydrophobic Surface Coated with a Short-chained Fluoroalkylsilane

Abstract A highly hydrophobic surface with nanoscale roughness was prepared by coating with a short-chained fluoroalkylsilane. The freezing behavior of a water droplet on the surface was then investigated. Freezing initiated in the vicinity of the three-phase contact line, producing a sharpened onion-like top on the droplet. The result of the freezing ratio at each time and the volume ratio at each height demonstrates the possibility that freezing advanced linearly in a vertical direction.

Effect of Dew Condensation on the Wettability of Rough Hydrophobic Surfaces Coated with Two Different Silanes

Dew condensation effects on the wettability of rough and smooth coatings of two fluoroalkylsilanes (FAS3 and FAS17) were investigated by controlling the temperature. Contact angles of the coatings decreased concomitantly with decreasing surface temperature. Inflection points in the temperature dependence of contact angles were observed at the dew point. They were attributable to the change of the interfacial free energy of the solid-gas interface by water adsorption. The contact angle decrease suggested a mode transition from Cassie to Wenzel on the rough surface, and resulted from the surface wettability change and the increase of the condensation amount of water. The contact angle change by increasing temperature from -6 degrees C revealed that the Wenzel mode is more stable than Cassie's mode.

Evaporation-Triggered Wetting Transition for Water Droplets upon Hydrophobic Microstructures

When placed on rough hydrophobic surfaces, water droplets of diameter larger than a few millimeters can easily form pearls, as they are in the Cassie-Baxter state with air pockets trapped underneath the droplet. Intriguingly, a natural evaporating process can drive such a Fakir drop into a completely wetting (Wenzel) state. Our microscopic observations with simultaneous side and bottom views of evaporating droplets upon transparent hydrophobic microstructures elucidate the water-filling dynamics and suggest the mechanism of this evaporation-triggered transition. For the present material the wetting transition occurs when the water droplet size decreases to a few hundreds of micrometers in radius. We present a general global energy argument which estimates the interfacial energies depending on the drop size and can account for the critical radius for the transition.

Water adsorption on hydrophilic and hydrophobic self-assembled monolayers as proxies for atmospheric surfaces. A grand canonical Monte Carlo simulation study

Grand canonical Monte Carlo simulations are used to determine water adsorption on prototypical organic surfaces as a function of relative humidity at 300 K. Three model surfaces formed by well-ordered self-assembled monolayers (SAMs) of alkanethiolate chains on gold are investigated: (i) a smooth hydrophobic surface of methyl-terminated C(7)-CH(3) SAM; (ii) a rough hydrophobic surface of randomly mixed two-component SAM, composed of equal fractions of C(5)-CH(3) and C(7)-CH(3) chains (C(5)/C(7)-CH(3) SAM); and (iii) a smooth hydrophilic surface of carboxyl-terminated C(7)-COOH SAM. The all atom CHARMM22 force field is used for the SAM chains together with the SPC/E model for water. No noticeable water adsorption is observed on the smooth hydrophobic surface up to saturation. The mild surface roughness introduced by the uneven chain length of the two components constituting the C(5)/C(7)-CH(3) SAM has no significant effect on the surface hydrophobicity, and the rough hydrophobic surface also remains dry up to the point when water condensation occurs. In contrast, water readily adsorbs onto the hydrophilic surface by forming hydrogen bonds with the COOH groups of the substrate. In addition, hydrogen bonding with pre-adsorbed water molecules contributes to the mechanism of water uptake. Under low humidity conditions, water is present on the hydrophilic surface as individual molecules or small water clusters and, with increasing relative humidity, the surface coverage grows continuously beyond a monolayer formation. The adsorbed water film is observed to be rather inhomogeneous with patches of bare surface exposed. The amount of water constituting a stable adsorption layer prior to condensation is estimated to consist of about 2-5 molecular layers. Detailed analysis of the simulation results is used to obtain important insights into the structure and energetics of water adsorbed on highly oxidized organic surfaces exposed to ambient air of increasing relative humidity.

Wetting Transition Characteristics on Microstructured Hydrophobic Surfaces

Hydrophobicity and wetting transition behavior of water droplets were investigated on microstructured hydrophobic rough surfaces with pillar arrays, fabricated by self-replication with hydrophobic polydimethylsiloxane(PDMS) together with the use of CNC machine. The surfaces consist of microscale pillars(diameter: 105 μm, height: 150 μm) with varying spacing-to-diameter ratio (s⁄d) ranging from ∼1.0 to ∼3.3. A de-ionized(DI) water droplet of 4.3 μl was placed on hydrophobic surfaces and contact angles(CA) were measured by the digital image processing algorithm. A wetting transition from the Cassie state to the Wenzel state was demonstrated depending on the values of s⁄d, from ∼1.81 to ∼2.95. In the transition regime, a partial penetration of liquid meniscus which moves downward in the groove formed by four pillar posts was observed. It was also found that the contact angle prediction using the Cassie-Baxter equation showed fairly good agreement with experimental data, whereas in the transition regime, the rapid decrease in CA was found.

Underwater Sustainability of the “Cassie” State of Wetting

A rough hydrophobic surface when immersed in water can result in a "Cassie" state of wetting in which the water is in contact with both the solid surface and the entrapped air. The sustainability of the entrapped air on such surfaces is important for underwater applications such as reduction of flow resistance in microchannels and drag reduction of submerged bodies such as hydrofoils. We utilize an optical technique based on total internal reflection of light at the water-air interface to quantify the spatial distribution of trapped air on such a surface and its variation with immersion time. With this technique, we evaluate the sustainability of the Cassie state on hydrophobic surfaces with four different kinds of textures. The textures studied are regular arrays of pillars, ridges, and holes that were created in silicon by a wet etching technique, and also a texture of random craters that was obtained through electrodischarge machining of aluminum. These surfaces were rendered hydrophobic with a self-assembled layer of fluorooctyl trichlorosilane. Depending on the texture, the size and shape of the trapped air pockets were found to vary. However, irrespective of the texture, both the size and the number of air pockets were found to decrease with time gradually and eventually disappear, suggesting that the sustainability of the "Cassie" state is finite for all the microstructures studied. This is possibly due to diffusion of air from the trapped air pockets into the water. The time scale for disappearance of air pockets was found to depend on the kind of microstructure and the hydrostatic pressure at the water-air interface. For the surface with a regular array of pillars, the air pockets were found to be in the form of a thin layer perched on top of the pillars with a large lateral extent compared to the spacing between pillars. For other surfaces studied, the air pockets are smaller and are of the same order as the characteristic length scale of the texture. Measurements for the surface with holes indicate that the time for air-pocket disappearance reduces as the hydrostatic pressure is increased.

Nanodesign of superhydrophobic surfaces

When deposited on a hydrophobic rough surface, a small water drop looks like a small pearl. In this study we investigate the conditions to observe such a phenomenon when the roughness of the substrate, of fractal nature, consists of nanofeatures obtained by the ion track etching technique. The surface roughness was characterized by two parameters: the fractal dimension Df and the aspect ratio AR. Both were extracted from the analysis of atomic force microscopy images and were directly correlated with the etching time. Df is found in the interval of 2.46–2.69, while AR varies from 0.5 to ∼15. We show that for the highest Df values the water contact angles on these surfaces can exceed 150°, while the hysteresis—the difference between the advancing and receding contact angles—is reduced to 4–5°. Superhydrophobic surfaces can thus be obtained and this property seems well controlled by the fractal dimension, which is itself controlled by the ion track etching process. Furthermore, the experimental results are well described by the wetting theory, and it is shown that superhydrophobicity of these surfaces results from a single-scale roughness of nanometric size.

How Wetting Hysteresis Influences Ice Adhesion Strength on Superhydrophobic Surfaces

In this work, we measured the adhesion strength of artificially created glaze ice (similar to accreted in nature) on rough fluoropolymer-based hydrophobic surfaces with different contact angle (CA) and wetting hysteresis. The previously reported direct correlation between ice repellency and CA on superhydrophobic surfaces is shown to be only valid for surfaces with low wetting hysteresis. Another correlation was found between wetting hysteresis and ice adhesion strength on rough surfaces with similar chemistry.

Modified titanium surfaces promote accelerated osteogenic differentiation of mesenchymal stromal cells in vitro

Titanium (Ti) is the material of choice for dental and orthopaedic implants due to its highly biocompatible nature. Modification of the implant surface, either topographically (as roughness) or chemically, can promote accelerated osteogenesis in vivo and greatly increase bone-implant contact and bonding strength. In this paper, we sought to characterise the cellular and molecular responses of human bone marrow-derived mesenchymal stromal cells (hMSCs) to two modified Ti surfaces: a rough hydrophobic surface that was sand-blasted and acid-etched (SLA) and an SLA surface of the same roughness that was chemically modified to have high wettability/hydrophilicity (SLActive). A smooth polished (SMO) Ti surface was used as a control. Whilst no differences in initial cell attachment to any of the surfaces were observed, we found that hMSCs cultured on the rough surfaces underwent a decrease in cell number early in culture, yet simultaneously expressed higher levels of the osteogenic markers SPP1, RUNX2 and BSP. Furthermore, deposits of calcified matrix were observed at earlier time points on both SLA and SLActive surfaces compared to SMO and this correlated with increased expression of the osteogenic promoter WNT5A in response to the rough surfaces. Osteogenic responses to SLActive were moderately better than the hydrophobic SLA surface and gene expression studies indicate that WNT5A activation may be responsible for this increased osteogenic differentiation.

EFFECT OF SURFACE ROUGHNESS ON THE FABRICATION OF ELECTROWETTING DISPLAY CELLS AND ITS ELECTRO-OPTIC SWITCHING BEHAVIOR

Electrowetting is a new class of reflective display based on electric field controlled movement of oil/water interface across a hydrophobic layer. The focus of this paper is to fabricate electrowetting cells on a rough hydrophobic surface and to study its effect on kinetics of electrowetting. The surface roughening found effective in two ways in the design and operation of the electrowetting device: (i) It enhances the coating of photoresist (PR) on the hydrophobic surface, which is normally difficult due to low surface energy of Teflon and (ii) the roughness changes the contact angle of the liquid (oil), which in turn changes the electro-optic switching behavior of the device. The kinetics of optical switch was checked by calculating theoretically the white area fraction (WA%), which is a measure of optical switching in electrowetting display by changing the roughness of the hydrophobic surface. The present study showed that the optical performance found to increase with the increase of roughness of the hydrophobic surface.

Microchannels Constructed on Rough Hydrophobic Surfaces

AbstractA microchannel was constructed between two glass slides, taking advantage of their surface properties. The channel geometry was defined by a line that was previously printed on the slide surface using a highly water‐soluble liquid [2‐(2‐ethoxyethoxy)ethanol] as the ink. Water, which acted as the working fluid flowed along this line. Although the channel did not have any sidewalls, the water was fixed along the printed line due to the large contact‐angle hysteresis of the slide surface whose properties were rough and hydrophobic. Such roughness was more advantageous over smoothness due to the large contact‐angle hysteresis of water and the good wettability of the ink. Using a syringe pump, the water was able to continuously flow through a 1 mm wide and 0.13 mm deep channel without flooding.

Nanodroplet impact and sliding on structured polymer surfaces

A comprehensive understanding of the wetting dynamics of rough hydrophobic surfaces is necessary for the optimization of practical applications. Molecular dynamics simulations have been used to study the impact and sliding of a nanosized water droplet on nanostructured polyethylene (PE) and poly(vinyl chloride) (PVC) polymer surfaces. The impact velocity on collision with pillar surfaces mainly influences the maximal deformation of the drop from spherical and its intrusion depth between the pillars. There is no effect on the observed equilibrium state, with the exception of the most hydrophobic PE surface, but the equilibrium shape of a droplet at the Wenzel state may be asymmetrical. A bounce of the water droplet from the most hydrophobic PE surface with smaller pillars is observed at intermediate velocity. A bounce occurs at a lower impact velocity if the collision angle is decreased or the mass of the droplet is increased. The friction against sliding was higher on the PVC surfaces than on the PE surfaces due to the less hydrophobic nature of the corresponding polymer and clear pinning of the receding contact line. The sliding distances on the PVC pillar and grooved surfaces were all short and within a small range, whereas on the surfaces the differences were more substantial. The highest friction was observed on the grooved surface for sliding orthogonal to the grooves and the lowest friction was observed on the pillar surface with the smallest pillars. The friction increased with the size of the pillars due to the decreased hydrophobicity and increased resisting force of the pillar edges. The collisions with the pillar edges decreased the sliding distance on the more hydrophobic pillar surface such that it was equal to that on the grooved surface in the groove direction.

Nanodroplets on rough hydrophilic and hydrophobic surfaces

We present results of Molecular Dynamics (MD) calculations on the behavior of liquid nanodroplets on rough hydrophobic and hydrophilic solid surfaces. On hydrophobic surfaces, the contact angle for nanodroplets depends strongly on the root-mean-square roughness amplitude, but it is nearly independent of the fractal dimension of the surface. Since increasing the fractal dimension increases the short-wavelength roughness, while the long-wavelength roughness is almost unchanged, we conclude that for hydrophobic interactions the short-wavelength (atomistic) roughness is not very important. We show that the nanodroplet is in a Cassie-like state. For rough hydrophobic surfaces, there is no contact angle hysteresis due to strong thermal fluctuations, which occur at the liquid-solid interface on the nanoscale. On hydrophilic surfaces, however, there is strong contact angle hysteresis due to higher energy barrier. These findings may be very important for the development of artificially biomimetic superhydrophobic surfaces.

Meniscus and viscous forces during separation of hydrophilic and hydrophobic smooth/rough surfaces with symmetric and asymmetric contact angles

Adhesive or repulsive forces contributed by both meniscus and viscous forces can be significant and become one of the main reliability issues when the contacting surfaces are ultra smooth, and the normal load is small, as is common for micro/nano devices. In this study, both meniscus and viscous forces during separation for smooth and rough hydrophilic and hydrophobic surfaces are studied. The effects of separation distance, initial meniscus height, separation time, contact angle and roughness are presented. Meniscus force decreases with an increase of separation distance, whereas the viscous force has an opposite trend. Both forces decrease with an increase of initial meniscus height. An increase of separation time, initial meniscus height or a decrease of contact angle leads to an increase of critical meniscus area at which both forces are equivalent. An increase in contact angle leads to a decrease of attractive meniscus force but an increase of repulsive meniscus force (attractive or repulsive dependent on hydrophilic or hydrophobic surface, respectively). Contact angle has a limited effect on the viscous force. For asymmetric contact angles, the magnitude of the meniscus force and the critical meniscus area are in between the values for the two angles. An increase in the number of surface asperities (roughness) leads to an increase of meniscus force; however, its effect on viscous force is trivial. A slightly attractive force is observed for the hydrophobic surface during the end stage of separation though the magnitude is small. The study provides a fundamental understanding of the physics of the separation process and it can be useful for control of the forces in nanotechnology applications.

Growth Dynamics of Water Drops on a Square-Pattern Rough Hydrophobic Surface

Condensation on rough or superhydrophobic substrates can induce wetting behavior that is quite different from that of deposited or impinging drops. We investigate the growth dynamics of water drops in a well-controlled condensation chamber on a model rough hydrophobic surface made of square pillars. After having followed growth laws similar to those observed on flat surfaces, a transition to an air-pocket-like state occurred because of the bridging of the drops between the pillars. Another transition to the more stable Wenzel state is later ensured by a noticeable pillar self-drying process. Condensation ends up in a few large drops in a mixed Wenzel penetration regime. The drops are fed by neighboring channels and the adjacent pillars stay almost dry, a remarkable and seemingly general property of rough hydrophobic substrates.

Drying transition of confined water

Long-range hydrophobic interactions operating underwater are important in the mediation of many natural and synthetic phenomena, such as protein folding, adhesion and colloid stability. Here we show that rough hydrophobic surfaces can experience attractive forces over distances more than 30 times greater than any reported previously, owing to the spontaneous evaporation of the intervening, confined water. Our finding highlights the importance of surface roughness in the interaction of extended structures in water, which has so far been largely overlooked.

Directing Droplets Using Microstructured Surfaces

Systematic variation of microscale structures has been employed to create a rough superhydrophobic surface with a contact angle gradient. Droplets are propelled down these gradients, overcoming contact angle hysteresis using energy supplied by mechanical vibration. The rough hydrophobic surfaces have been designed to maintain air traps beneath the droplet by stabilizing its Fakir state. Dimensions and spacing of the microfabricated pillars in silicon control the solid-liquid contact area and are varied to create a gradient in the apparent contact angle. This work introduces the solid-liquid contact area fraction as a new control variable in any scheme of manipulating droplets, presenting theory, fabricated structures, and experimental results that validate the approach.