Effects of contact angle hysteresis on ice adhesion and growth on superhydrophobic surfaces under dynamic flow conditions

In this paper, the icephobic properties of superhydrophobic surfaces are investigated under dynamic flow conditions using a closed-loop low-temperature wind tunnel. Superhydrophobic surfaces were prepared by coating aluminum and steel substrate plates with nano-structured hydrophobic particles. The superhydrophobic plates, along with uncoated controls, were exposed to a wind tunnel air flow of 12 m/s and ?7 °C with deviations of ±1 m/s and ±2.5 °C, respectively, containing micrometer-sized (～50 μm in diameter) water droplets. The ice formation and accretion were observed by CCD cameras. Results show that the superhydrophobic coatings significantly delay ice formation and accretion even under the dynamic flow condition of highly energetic impingement of accelerated supercooled water droplets. It is found that there is a time scale for this phenomenon (delay in ice formation) which has a clear correlation with contact angle hysteresis and the length scale of the surface roughness of the superhydrophobic surface samples, being the highest for the plate with the lowest contact angle hysteresis and finest surface roughness. The results suggest that the key for designing icephobic surfaces under the hydrodynamic pressure of impinging droplets is to retain a non-wetting superhydrophobic state with low contact angle hysteresis, rather than to only have a high apparent contact angle (conventionally referred to as a “static” contact angle).     

The mechanics of contact and adhesion of periodically rough surfaces

An analytical model based on the Johnson–Kendall–Roberts (JKR) theory of adhesion was used to study the contact mechanics and adhesion of periodically rough surfaces. The relation of the applied load to the contact area and the work of adhesion W was found in closed form for arbitrary surface profiles. Our analysis showed that when the parameter [where α* is a numerical constant of order one, β is the aspect ratio of a typical surface profile (or asperity), and ρ is the number of asperities per unit length], the surfaces will jump into contact with each other with no applied load, and the contact area will continue to expand until the two surfaces are in full contact. The theory was then extended to the non‐JKR regime in which the region where the surface forces act is no longer confined to a small region near the contact zone. Exact solution was also obtained for this case. An exact analysis of the effect of entrapped air on the mechanics of adhesion and contact was also enacted. The results showed that interaction between asperities should be taken into consideration in contact‐mechanics models of adhesion or friction. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1195–1214, 2001     

Thermodynamics of capillary adhesion between rough surfaces

According to the Dupré equation, the work of adhesion is equal to the surface energy difference in the separated versus the joined materials minus an interfacial energy term. However, if a liquid is at the interface between two solid materials, evaporation or condensation takes place under equilibrium conditions. The resulting matter exchange is accompanied by heat flow, and can reduce or increase the work of adhesion. Accounting for the energies requires an open-system control volume analysis based on the first law of thermodynamics. Depending on whether evaporation or condensation occurs during separation, a work term that is negative or positive must be added to the surface energy term to calculate the work of adhesion. We develop and apply this energy balance to several different interface geometries and compare the work of adhesion to the surface energy created. The model geometries include a sphere on a flat with limiting approximations and also with an exact solution, a circular disc, and a combination of these representing a rough interface. For the sphere on a flat, the work of adhesion is one half the surface energy created if equilibrium is maintained during the pull-off process.     

Determining the contact angle between liquids and cylindrical surfaces

One of the simplest methods of measuring the quantities for estimating the adhesion properties of materials (i.e., the adhesion work, the surface energy, and the interfacial tension between certain liquids and a surface) requires the determination of the contact angle between the liquid and the surface. In the case of plane surfaces the determination of the drop dimensions makes it possible to calculate the contact angle by the sessile drop method, but in the case of cylindrical surfaces (such as the monofilaments), several methods were developed to improve the accuracy of the contact angle measurements. This paper presents a comprehensive method for precise evaluation of the contact angle between liquid drops and monofilaments by establishing a differential equation describing the drop contour. This equation makes it possible to accurately compute the contact angle using the dimensions of the drop. A comparison of the values of the contact angle calculated by our method and those obtained by other approaches is made. We applied our method in the case of polyamide-6 monofilaments treated using dielectric barrier discharge, knowing their medical applications in surgical sutures.     

Residence time, loading force, pH, and ionic strength affect adhesion forces between colloids and biopolymer-coated surfaces

Exopolymers are thought to influence bacterial adhesion to surfaces, but the time-dependent nature of molecular-scale interactions of biopolymers with a surface are poorly understood. In this study, the adhesion forces between two proteins and a polysaccharide [Bovine serum albumin (BSA), lysozyme, or dextran] and colloids (uncoated or BSA-coated carboxylated latex microspheres) were analyzed using colloid probe atomic force microscopy (AFM). Increasing the residence time of an uncoated or BSA-coated microsphere on a surface consistently increased the adhesion force measured during retraction of the colloid from the surface, demonstrating the important contribution of polymer rearrangement to increased adhesion force. Increasing the force applied on the colloid (loading force) also increased the adhesion force. For example, at a lower loading force of approximately 0.6 nN there was little adhesion (less than -0.47 nN) measured between a microsphere and the BSA surface for an exposure time up to 10 s. Increasing the loading force to 5.4 nN increased the adhesion force to -4.1 nN for an uncoated microsphere to a BSA surface and to as much as -7.5 nN for a BSA-coated microsphere to a BSA-coated glass surface for a residence time of 10 s. Adhesion forces between colloids and biopolymer surfaces decreased inversely with pH over a pH range of 4.5-10.6, suggesting that hydrogen bonding and a reduction of electrostatic repulsion were dominant mechanisms of adhesion in lower pH solutions. Larger adhesion forces were observed at low (1 mM) versus high ionic strength (100 mM), consistent with previous AFM findings. These results show the importance of polymers for colloid adhesion to surfaces by demonstrating that adhesion forces increase with applied force and detention time, and that changes in the adhesion forces reflect changes in solution chemistry.     

Interaction between silica nanoparticles in binary liquid mixtures: the effect of polarity on adhesion

In order to explore the relationship between selective liquid sorption and the stability of dispersed silica particles, we carried out studies in ethanol–cyclohexane binary mixtures as well as in partially miscible 1-butanol–water mixtures. In ethanol–cyclohexane, adsorption excess isotherms were determined on hydrophilic and hydrophobic aerosil particles. The volume and the thickness of the adsorption layer were derived from the isotherms. Knowing the layer thickness and Hamaker constants, interparticle interaction potentials were calculated at various mixture compositions. At low ethanol concentration, where hydrophilic surfaces are considerably enriched in ethanol, interparticle interaction is enhanced and the high shear stress calculated from rheological measurements indicates the development of a three-dimensional network of aggregated particles. In contrast, hydrophobic aerosil particles in ethanol–cyclohexane approach each other without ensuing aggregation because interparticle interactions are weak, a fact well demonstrated by rheological measurements. It was also established that interactions between silica particles with hydrophilic surfaces are weak in butanol–water mixtures. Since water is preferentially adsorbed on the surface of hydrophilic particles to the azeotropic composition (\( x_{\rm{1}}^{\rm{a}} \)=0.62), within this wide composition range the Hamaker constant of the interfacial layer is identical with that of water.     

Hydrophobic forces and hydrogen bonds in the adhesion between retinoid-coated surfaces

Interactions between hydrophobic chains of lipid monolayers and interactions between hydrophilic headgroups of lipid bilayers (with or without a molecular recognition step) are now well documented, especially for commonly used lipids. Here, we report force measurements between a new class of fluorinated lipid layers whose headgroups (synthetic ligands of retinoid receptors) display a very unusual polar/apolar character and can interact via a combination of hydrophobic forces and hydrogen bonds. Although these two interactions produce adhesion and are therefore not easily distinguishable, we show that it is possible to extract both contributions unambiguously. Experiments are performed both in pure water, where the adhesion is a combination of hydrophobic forces and hydrogen bonds, and in Tris buffer, where the hydrophobic effect is the dominant short-range attractive force. The contribution of hydrophobic forces scaled down to molecular interactions is deduced from force versus distance profiles, and the same value is found independently in pure water and Tris buffer, about 1 kBT. We also show that retinoid lipid layers attract each other through a very long-range (100 nm) exponential force, which is insensitive to the pH and the salinity. The origin of this long-range attraction is discussed on the basis of previously proposed mechanisms.     

Material transfer and polarity reversal in contact charging

In touch: the outcome of contact electrification between dielectrics depends not only on the transfer of charge but also on the transfer of material. Although only minute quantities of materials are being exchanged during contact, they can reverse the polarity of dielectrics. The reported results corroborate the mosaic model and suggest that the observations are because of the mechanical softness/hardness of the materials.     

Use of the JKR model for calculating adhesion between rough surfaces

A simple method for using the JKR model to determine interfacial adhesion between two ideal rough surfaces is demonstrated for individual asperity-asperity and asperity-flat contacts both in air and in water. The model takes into account the effect of a modified contact area at separation due to viscoelastic effects. The equilibrium version of the model significantly underestimates the measured adhesion, whereas the viscoelastic version of the model is much closer to the measured data. The asperity-flat geometry used with the viscoelastic version of the model seems to fit the experimental results best. This was thought to be due to the unlikely occurrence of direct asperity-asperity contacts. Instead, it would seem that the asperities have a far higher chance of fitting between each other on opposing surfaces, leading to correspondingly higher pull-off forces measured on separation. Many possible extensions to the roughness model described here may be made, allowing a much-improved understanding of the contact mechanics between two rough surfaces.     

Coatings of polyethylene glycol for suppressing adhesion between solid microspheres and flat surfaces

This article describes the development and the examination of surface coatings that suppress the adhesion between glass surfaces and polymer microspheres. Superparamagnetic doping allowed for exerting magnetic forces on the microbeads. The carboxyl functionalization of the polymer provided the means for coating the beads with polyethylene glycol (PEG) with different molecular weight. Under gravitational force, the microbeads settled on glass surfaces with similar polymer coatings. We examined the efficacy of removing the beads from the glass surfaces by applying a pulling force of ~1.2 pN. The percent beads remaining on the surface after applying the pulling force for approximately 5 s served as an indication of the adhesion propensity. Coating of PEG with molecular weight ranging between 3 and 10 kDa was essential for suppressing the adhesion. For the particular substrates, surface chemistry and aqueous media we used, coatings of 5 kDa manifested optimal suppression of adhesion: that is, only 3% of the microbeads remained on the surface after applying the pulling magnetic force. When either the glass or the beads were not PEGylated, the adhesion between them was substantial. Addition of a noncharged surfactant, TWEEN, above its critical micelle concentrations (CMCs) suppressed the adhesion between noncoated substrates. The extent of this surfactant-induced improvement of the adhesion suppression, however, did not exceed the quality of preventing the adhesion that we attained by PEGylating both substrates. In addition, the use of surfactants did not significantly improve the suppression of bead-surface adhesion when both substrates were PEGylated. These findings suggest that such surfactant additives tend to be redundant and that covalently grafted coatings of PEGs with selected chain lengths provide sufficient suppression of nonspecific interfacial interactions.     

Effect of surface polarity on water contact angle and interfacial hydration structure

We perform molecular dynamics simulations of water in the presence of hydrophobic/hydrophilic walls at T = 300 K and P = 0 GPa. For the hydrophilic walls, we use a hydroxylated silica model introduced in previous simulations [Lee, S. H.; Rossky, P. J. J. Chem. Phys. 1994, 100, 3334. Giovambattista, N.; Rossky, P. J.; Debenedetti, P. G.; Phys. Rev. E 2006, 73, 041604.]. By rescaling the physical partial atomic charges by a parameter 0 相似文献   

Conformal adhesion enhancement on biomimetic microstructured surfaces

Inspired by the superior adhesive ability of the gecko foot pad, we report an experimental study of conformal adhesion of a soft elastomer thin film on biomimetic micropatterned surfaces (micropillars), showing a remarkable adhesion enhancement due to the surface patterning. The adhesion of a low-surface-energy poly(dimethylsiloxane) tape to a SU-8 micropatterned surface was found be able to increase by 550-fold as the aspect ratio increases from 0 to 6. The dependency of the adhesion enhancement on the aspect ratio is highly nonlinear. A series of peeling experiment coupled with optical interference imaging were performed to investigate the adhesion enhancement as a function of the height of the micropillars and the associated delamination mechanisms. Local elastic energy dissipation, side-wall friction, and plastic deformations were analyzed and discussed in terms of their contributions to the adhesion enhancement. We conclude that the local adhesion and friction events of pulling micropillars out of the embedded polymer film play a primary role in the observed adhesion enhancement. The technical implications of this local friction-based adhesion enhancement mechanism were discussed for the effective assembly of similar or dissimilar material components at small scales. The combined use of the micro/nanostructured surfaces with the van der Waals interactions seem to be a potentially more universal solution than the conventional adhesive bonding technology, which depends on the chemical and viscoelastic properties of the materials.     

Particle adhesion force distributions on rough surfaces

The effect of roughness on adhesion force distribution was studied in the gas phase. Spherical gold particles with diameters between 5 and 20 microm were generated in a flame process and glued onto atomic force microscope (AFM) cantilevers directly after. Nanostructured substrates with defined roughness were produced by a dip-coating process. The geometry of the adhering partners was determined by AFM imaging, and the adhesion force was measured with the AFM. Depending on the roughness of the particles and the substrates, three types of distribution functions can be identified; two of them can be explained with a simple model. The obtained adhesion force distributions not only agree with those experimentally recorded in previous studies of commercially important powders (e.g., alumina, toner, and gold on different substrates) but also agree with distributions reported in the literature.     

Nonequilibrium effects in diffusion of interacting particles on vicinal surfaces

We study the influence of nonequilibrium conditions on the collective diffusion of interacting particles on vicinal surfaces. To this end, we perform Monte Carlo simulations of a lattice-gas model of an ideal stepped surface, where adatoms have nearest-neighbor attractive or repulsive interactions. Applying the Boltzmann-Matano method to spreading density profiles of the adatoms allows the definition of an effective, time-dependent collective diffusion coefficient D(C) (t)(theta) for all coverages theta. In the case of diffusion across the steps and strong binding at lower step edges we observe three stages in the behavior of the corresponding D(xx,C) (t)(theta). At early times when the adatoms have not yet crossed the steps, D(xx,C) (t)(theta) is influenced by the presence of steps only weakly. At intermediate times, where the adatoms have crossed several steps, there are sharp peaks at coverages theta<1L and theta>1-1L, where L is the terrace width. These peaks are due to different rates of relaxation of the density at successive terraces. At late stages of spreading, these peaks vanish and D(xx,C) (t)(theta) crosses over to its equilibrium value, where for strong step edge binding there is a maximum at theta=1L. In the case of diffusion in direction along the steps the nonequilibrium effects in D(yy,C) (t)(theta) are much weaker, and are apparent only when diffusion along ledges is strongly suppressed or enhanced.     

Testing the polarity and adsorptivity of nondeactivated GC capillary surfaces

Split injection of 1-pentanol headspace on to raw or treated fused silica tubing yields information on the characteristics of its surface (silanol concentration, polarity, adsorptivity). Fused silica tubing from three sources was compared. The effect of various leaching and etching procedures used for column preparation was studied, as was the stability of uncoated fused silica precolumns towards water and some organic solvents.     

Effect of three-phase contact line topology on dynamic contact angles on heterogeneous surfaces

Cassie-Baxter theory has traditionally been used to study liquid drops in contact with microstructured surfaces. The Cassie-Baxter theory arises from a minimization of the global Gibbs free energy of the system but does not account for the topology of the three-phase contact line. We experimentally compare two situations differing only in the microstructure of the roughness, which causes differences in contact line topology. We report that the contact angle is independent of area void fraction for surfaces with microcavities, which correspond to situations when the advancing contact line is continuous. This result is in contrast with Cassie-Baxter theory, which uses area void fraction as the determining parameter, regardless of the type of roughness.     

Advancing contact lines on chemically patterned surfaces

We report an experimental investigation on advancing contact lines of large drops spreading on chemically patterned surfaces. The model substrates were prepared using microphotolithography allowing precise control of the position and the size of the wettability patterns. Experiments were performed exploring different surface geometries: from ordered to disordered fields of defects and from low to high surface densities. The shape of the contact line between two isolated defects was investigated as a function of the distance. Portions of the contact line on the defects and on the matrix were studied during spreading experiments and were related to the apparent contact angles measured from the final thickness of the drops. A modified Cassie equation based on the line fraction of defects is proposed.     

Modeling receding contact lines on superhydrophobic surfaces

We use mesoscale simulations to study the depinning of a receding contact line on a superhydrophobic surface patterned by a regular array of posts. For the simulations to be feasible, we introduce a novel geometry where a column of liquid dewets a capillary bounded by a superhydrophobic plane that faces a smooth hydrophilic wall of variable contact angle. We present results for the dependence of the depinning angle on the shape and spacing of the posts and discuss the form of the meniscus at depinning. We find, in agreement with ref 17 , that the local post concentration is a primary factor in controlling the depinning angle and show that the numerical results agree well with recent experiments. We also present two examples of metastable pinned configurations where the posts are partially wet.