Vapour adsorption and contact angles on hydrophobic solid surfaces

To test the effects of vapour adsorption on contact angle measurements, contact angles of high-vapour-pressure liquids and low-vapour-pressure liquids on a hydrophobic solid surface (FC721) were measured by using the axisymmetric drop shape analysis-profile (ADSA-P) technique. Details of the surface preparation and the experiments are presented. By plotting the experimental data in terms of _1v cos vs. _1v, this study shows that the vapour adsorption on a fluorocarbon surface, FC721, is negligible.     

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.     

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).     

Impurity effects at hydrophobic surfaces

The effective charge of hydrophobic surfaces and in particular of the air–water interface is a crucial parameter for electrochemistry, colloidal chemistry and interfacial science, but different experiments give conflicting estimates. Zeta-potential and disjoining-pressure measurements point to a strongly negative surface charge, often interpreted as being due to adsorbing hydroxide ions. In contrast, surface tension measurements of acids and bases suggest the hydronium ion to be surface active, in agreement with some surface-specific non-linear spectroscopy results. The air–electrolyte interfacial tension exhibits a characteristic minimum at millimolar electrolyte concentration for all salts, the so-called Jones–Ray effect, which points to competitive adsorption mechanisms present in dilute electrolyte solutions. We show that all these puzzling experimental findings can be explained by the presence of trace amounts of surface-active charged impurities, most likely anionic surfactants.     

Novel self-organization of polymer particles on hydrophobic solid surfaces through hydrophobic interaction

A novel technique of particle monolayer fabrication based on hydrophobic interactions in aqueous systems is described in this paper. When alkylated glass plates modified with various silane coupling agents were immersed in aqueous dispersions of submicron-sized polystyrene particles of cationic or anionic surface charges, cationic particle monolayers containing active ester groups were effectively formed at the plate surfaces, whereas no anionic particles were self-organized on the plate surfaces. The coverage of the plates with cationic particles and the morphology of the monolayers varied with the hydrophobicities of the particles and plates as well as with the ionic strength of the medium and temperature. For less hydrophobic methylated glass surfaces modified with methyltriethoxysilane, cationic particles were self-organized at relatively regular intervals, whereas they were self-organized in the form of aggregates for the more hydrophobic octadecylated glass plates treated with n-octadecyltriethoxysilane. Closely packed monolayers were fabricated by adjusting ionic strength and temperature. Fluorescence labelling of cationic particle monolayers was successfully accomplished by the reaction of remaining active ester groups on the monolayers with a fluorescence probe containing amino groups. Cationic particle monolayers were physically stabilized by heating above the glass transition temperature (T _g) of the particles.     

Adsorptive modification of hydrophobic solid surfaces by mixed surfactant solutions

We studied the reciprocal influence of a nonionic surfactant (triton X-305) and a cationic surfactant (tetradecyltrimethylammonium bromide; TTAB) on their adsorption from aqueous solution on hydrophobic glass, interfacial tension at the solution/solid interface, composition of the mixed adsorption layer, and interaction parameters between surfactant molecules in mixed adsorption layers.     

Stick-slip of the three-phase line in measurements of dynamic contact angles

Contact angles of a series of n-alkanes (i.e., n-heptane to n-hexadecane) are studied on two functionalized maleimide copolymers (i.e., poly(ethene-alt-N-(4-(perfluoroheptylcarbonyl)aminobutyl)maleimide) (ETMF) and poly(octadecene-alt-N-(4-(perfluoroheptylcarbonyl)aminobutyl)maleimide) (ODMF)). On the homogeneous ETMF films, all liquids show a smooth motion of the three-phase line. In contrast, on ODMF surfaces that are found to consist of mainly fluorocarbons and small patches of hydrocarbons, short-chain n-alkanes show a stick-slip pattern. By increasing the chain length of the probe liquids, stick-slip is reduced significantly. The phenomenon is discussed in the framework of the Cassie equation. It is found that the upper limit of contact angles in the stick-slip pattern is given by the advancing angle that would be obtained on the pure fluorocarbon surface, whereas the lower limit of the stick-slip pattern is given by the Cassie angle.     

Models of adsorption at a line of three-phase contact

Two model density distributions at a line of three-phase contact for which the adsorptions are readily calculated are analyzed. One of them provides a numerical illustration of a recently found surprising fact about the thermodynamics of adsorption at such contact lines. A form of the line analogue of the Gibbs adsorption equation is conjectured, and it is noted that the conjecture is in principle testable by computer simulation and by experiment.     

Microscale thermoviscosity and evaporation at the three-phase contact zone

A microscale model of wetting at the three-phase contact zone that incorporates the thermoviscosity effect under nonisothermal and evaporation conditions is presented. The thermoviscosity effect is shown to change the content of both governing equations and boundary conditions. The differential equation of the liquid-vapor interface profile is expressed in terms of previously defined dimensionless groups and the new thermoviscosity change factor D(s). The temperature-dependent viscosity eta(T), and capillary number C(*) are defined as a product of eta and C and of 1-D(s)Theta(I), respectively. Model outputs show that increase of D(s) decreases the wave length and amplitude of the solution profile as well as the film thickness and slope. In the tested cases of water, nitrogen, and helium, increase of D(s) extends the physically feasible range of contact angle and wall temperature versus fluid velocity. Under rewetting conditions, the effect of increased D(s) is to shift the allowable range of wall temperatures toward smaller values, concurrent with increasing the feasible values of corresponding quench velocities. The capacity of the dimensionless groups, C, Ctheta(2)/F, N, and A, to change the liquid-vapor interface profile is diminished by D(s), the capillary number C and the Hamaker constant being most and least sensitive in this respect.     

Mobility of single DNA chain under electric field during its transient contact with solid surfaces

The motion of DNA chain under electric field when it is in transient contact with the solid surfaces in aqueous solution was studied by single molecule fluorescence microscopy at the total internal reflection geometry (TIRFM). In situ observation discovered that single λ-DNA chains driven by electric field made transient contact with the solid surface and made hitting–sliding–leaving-like motion along the surface. By varying the surface chemistry, from the negative-charged silanol group-rich surface to positive-charged amino group-rich surface, as well as hydrophobic surfaces, the dependence of DNA mobility on the surface–DNA interaction was studied. The results show that a dependence of the mobility of DNA on the surface polarity with respect to DNA itself. The study on different surfaces rich of silanol, amide, amino, and methyl groups show a sequence of DNA mobility of silanol > amide > amino. The mobility of DNA on methyl terminated surface was found to be similar to that on amino surface. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2541–2546, 2009     

Foams under dynamic conditions

This review has been focused on the importance of dynamic effects in foam formation and stability. It has been demonstrated that as foams are always formed under dynamic conditions so the equilibrium adsorption coverage's will usually not yet be attained. This fact may have a pronounced effect on the magnitude of the forces stabilizing the foam films. It has been underlined that more attention should be focused on the conditions of the foams' formation and existence because the mutual importance of the different types of the foam stabilizing forces can vary significantly depending on the stage of foam life and the conditions of its existence. Thus, none of these forces can solely determine the properties of the varying foam systems.     

Protein interactions with solid surfaces following contact with plasma and blood

Two aspects of blood protein interactions with solid surfaces are discussed. The first is competitive adsorption among the many proteins in the blood. The general factors which determine the composition of the adsorbed layer in any multicomponent protein system are considered and then related to current knowledge of competitive adsorption in blood. The latter pertains largely to the so-called Vroman effect whereby proteins are adsorbed and displaced from the surface in an ordered sequence. Secondly the possible transformation of adsorbed enzyme precursors into active enzymes by the agency of the surface is discussed. The example of the plasminogen-plasmin system is used to illustrate this discussion.     

On the role of contact line tension and 2D defects in the formation of the water depletion layer on hydrophobic surfaces

It is demonstrated that formation of nano-voids in the depletion liquid layer on the hydrophobic surfaces may be due to the phenomenon of the contact line tension. The mean radius of 2D circular void is calculated. It coincides with characteristic dimensions of nano-voids in depletion liquid layers on the hydrophobic surfaces reported experimentally.     

Metallisation of gel surfaces under ambient conditions

A room temperature method to coat a non-conducting gel phase with a metal is described, which uses galvanic displacement. Electrolytes are dissolved in the gel phase to allow metal deposition from an immiscible liquid electrolyte solution. Conformal deposition was achieved by imprinting the gel, followed by galvanic displacement of gold.     

The dynamic contact angle I. Dependence of the receding contact angle on velocity in the surfactant-containing three-phase system

Spontaneous three-phase contact (tpc) motion is investigated in order to determine the dependence of the static contact angle on tpc velocity in surfactant-containing systems after recession. To interpret the experimental results, the molecular-kinetic sitechanging theory and the hydrodynamic theory were considered. It is shown that, especially at very high tpc velocities, the experimental results are not thoroughly described by these theories. The deviations are explained as a surfactant transfer from the liquid/gas to the solid/gas interface which, under insufficient afterdiffusion, leads to an increase in surface tension and to a changed surface rheology. This mechanism could be governed by a model.     

Leakage behaviour of elastomer seals under dynamic unloading conditions at low temperatures

In technical applications, static seals are sometimes also subjected to dynamic loadings. Therefore, the leakage behaviour under dynamic conditions has to be evaluated as well. For this purpose, FKM elastomer seals have been tested by using newly designed equipment that allows for rapid partial release of the seal and simultaneous leakage rate measurement at a wide range of test temperatures. Furthermore, material characterisation was done by using Dynamic Mechanical Analysis, Differential Scanning Calorimetry and Compression Set. It was shown that, under static conditions, the leakage rate increased significantly during cooling at temperatures around 18 K lower than the glass transition range. On reheating, the seal's functionality was restored in the high temperature region of the glass rubber transition. In the subsequent dynamic release tests, that comprised a reduction of the seal compression within 1 s from 25% to 23%, increased leakage rates were observed in the high temperature region of the glass transition range. It was shown that the temperature that is critical for increased leakage is significantly lower under static conditions compared to dynamic conditions. The obtained leakage rates for static tests and dynamic release tests at different temperatures were analysed with reference to results of the material characterisation.