Contact angle measurement on rough surfaces

A new method for the measurement of apparent contact angles at the global energy minimum on real surfaces has been developed. The method consists of vibrating the surface, taking top-view pictures of the drop, monitoring the drop roundness, and calculating the contact angle from the drop diameter and weight. The use of the new method has been demonstrated for various rough surfaces, all having the same surface chemistry. In order to establish the optimal vibration conditions, the proper ranges for the system parameters (i.e., drop volume, vibration time, frequency of vibration, and amplitude of vibration) were determined. The reliability of the method has been demonstrated by the fact that the ideal contact angles of all surfaces, as calculated from the Wenzel equation using the measured apparent contact angles, came out to be practically identical. This ideal contact angle has been compared with three methods of calculation from values of advancing and receding contact angles.     

Contact angle relaxation on low energy surfaces

The spontaneous relaxation of the water—vapour interface, in contact with the “low energy” solids poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA), has been investigated after forced advancing and receding movement. A tensiometric apparatus has been used to probe the three-phase contact zone during relaxation for periods of up to 24 h. The measured force—time trace differs from that which might be anticipated, due to extraneous phenomena such as bulk evaporation/condensation/absorption. It is clear that even for a pure low viscosity liquid such as water, an imbalance in interfacial energies in the neighbourhood of the three-phase contact line (TPCL) exists for extended periods. Measurements have been made at both high and low water vapour pressures. In the advancing case, the TPCL is pinned and equilibration occurs via an essentially evaporative mechanism. In the receding case, the TPCL is mobile and the approach to equilibrium, which also occurs by an evaporative mechanism, is much slower. Indeed our results lead us to question whether equilibrium in the receding case is experimentally accessible. Contact angle hysteresis was found to be significantly smaller in magnitude than that typically measured within seconds or a few minutes of the cessation of forced TPCL movement.     

Contact angle hysteresis on regular pillar-like hydrophobic surfaces

A series of pillar-like patterned silicon wafers with different pillar sizes and spacing are fabricated by photolithography and further modified by a self-assembled fluorosilanated monolayer. The dynamic contact angles of water on these surfaces are carefully measured and found to be consistent with the theoretical predictions of the Cassie model and the Wenzel model. When a water drop is at the Wenzel state, its contact angle hysteresis increases along with an increase in the surface roughness. While the surface roughness is further raised beyond its transition roughness (from the Wenzel state to the Cassie state), the contact angle hysteresis (or receding contact angle) discontinuously drops (or jumps) to a lower (or higher) value. When a water drop is at the Cassie state, its contact angle hysteresis strongly depends on the solid fraction and has nothing to do with the surface roughness. Even for a superhydrophobic surface, the contact angle hysteresis may still exhibit a value as high as 41 degrees for the solid fraction of 0.563.     

Isotope exchange kinetics at heterogeneous solid surfaces (solid-liquid interfaces)

A system of equations describing isotope exchange kinetics at heterogeneous solid surfaces (solid-liquid interfaces) is studied numerically. The theoretical kinetic curves, characterizing the isotope exchange, are calculated for different discrete distributions of the isotope exchange rate constant.

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Isotopenaustauschkinetik an heterogenen Festkörperoberflächen (Fest-flüssig Grenzflächen)

Zusammenfassung Ein die Kinetik des Isotopenaustausches an heterogenen Festkörperflächen (fest-flüssig Grenzflächen) beschreibendes Gleichungssystem wird einer numerischen Auswertung unterzogen. Die theoretischen kinetischen Kurven des Isotopenaustausches werden für verschiedene diskontinuierliche Verteilungen der Isotopenaustausch-Geschwindigkeitskonstante berechnet.

     

Contact angle interpretation in terms of solid surface tension

Recent experimental (low-rate) dynamic contact angles for 14 solid surfaces are interpreted in terms of their solid surface tensions. Universality of these experimental contact angle patterns is illustrated; other reasons that can cause data to deviate from the patterns are discussed. It is found that surface tension component approaches do not reflect physical reality. Assuming solid surface tension is constant for one and the same solid surface, experimental contact angle patterns are employed to deduce a functional relationship to be used in conjunction with the Young equation to determine solid surface tensions. The explicit form of such a relation is obtained by modifying Berthelot’s rule together with experimental data; essentially constant solid surface tension values are obtained, independent of liquid surface tension and molecular structure. A new combining rule is also derived based on an expression similar to one used in molecular theory; such a combining rule should allow a better understanding of the molecular interactions between unlike solid–liquid pairs.     

Contact angle hysteresis of cylindrical drops on chemically heterogeneous striped surfaces

Contact angle hysteresis of a macroscopic droplet on a heterogeneous but flat substrate is studied using the interface displacement model. First, the apparent contact angle of a droplet on a heterogeneous surface under the condition of constant volume is considered. By assuming a cylindrical liquid-vapor surface (meniscus) and minimizing the total free energy, we derive an equation for the apparent contact angle, which is similar but different from the well-known Cassie's law. Next, using this modified Cassie's law as a guide to predict the behavior of a droplet on a heterogeneous striped surface, we examine several scenarios of contact angle hysteresis using a periodically striped surface model. By changing the volume of the droplet, we predict a sudden jump of the droplet edge, and a continuous change of the apparent contact angle at the edge of two stripes. Our results suggest that as drop volume is increased (advancing contact lines), the predominant drop configuration observed is the one whose contact angle is large; whereas, decreasing drop volume from a large value (receding contact lines) yields drop configuration that predominantly exhibit the smaller contact angle.     

Computer simulation of adsorption kinetics of surfactants on solid surfaces

Adsorption kinetics of surfactants on solid surfaces has been studied by using computer simulation. Both bulk surfactant concentration and diffusion region are explicitly integrated in our model. Depending on the head-surface interaction, our simulation results indicate that there exist two different kinetic modes in adsorption process of surfactants on solid surfaces. One is the four-regime mode and the other is step-wise mode. For the strongly attractive head-surface interaction, four distinct regimes of surfactant adsorption are found: a diffusion-controlled regime, a self-assembly controlled regime, an intermediate coverage regime and a saturated regime. In particular, the adsorption in second regime displays a power-law time dependence with an exponent unrelated to bulk concentrations and diffusion coefficients. While for the weaker adsorption surfaces, the step-wise mode is found. The mode includes a low-coverage nucleation regime and the saturated regime after a sudden aggregation of surfactants on the substrates which occurs stochastically. Besides the head-surface interaction, in this work, the effects of surfactant diffusivity, bulk concentration, the length of diffusion zone and surfactant architecture on the adsorption kinetics are also considered. The simulated adsorption kinetics is compared qualitatively with experimental results.     

Formal kinetics of nonlinear photochemical reactions in solid solutions

Analytic expressions are derived for the rate constants of some two-quantum photochemical reactions. The limits of application of the approximations are discussed. It is shown that the quantum yield in two-photon sensitization (second photon absorbed by a molecule in a triplet state) is independent of the sensitizer when the substrate concentration is high. The concept of quantum yield for a nonlinear reaction is discussed.We are indebted to V. E. Kholmogorov for guidance in this work and to our colleagues for discussion of the results.     

Contact angle of micro- and nanoparticles at fluid interfaces

The contact angle of particles attached to fluid interfaces plays a key role in many scientific and technological aspects of particle-laden layers. In spite of the recognized importance, the laws that govern this property are still poorly understood. The main problem associated with the study of this property is that multiple variables are involved in the wetting process of particles by fluid interfaces. Such variables are associated with the chemical nature of both the particles and the fluid phases, and with the particle’s size. Understanding of the different aspects controlling the contact angle of particles is a physico-chemical challenge, and is very important because of the many technological aspects in which particle laden interfaces are involved. This review discusses the current status and the aspects to be dealt with in the near future in the study of the contact angle of particles attached to fluid interfaces.     

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.     

Studies of the wetting kinetics of liquid drops on solid surfaces

The viscosity _L and the surface tension _L of the liquid as well as the equilibrium contact angle _e are essential parameters governing the wetting kinetics of liquids on solids. By means of a contact angle apparatus with video image digitization, the dynamic contact angle and the radiusr of the contact area of sessile drops on solid surfaces have simultaneously been determined in dependence on time after drop application between about 3·10^–2 s and long times.The measurements were performed with series of liquids: polydimethylsiloxanes with different molecular masses and solutions of polyisobutylene in decalin and polyacrylic acid in water, covering a wide range of concentrations. The liquids in each series have a constant surface tension, but viscosities ranging over about four orders of magnitude, allowing the influence of _L and _L to be studied independently. Solids such as glass, polyethylene and polytetrafluoroethylene were chosen so that the cases of complete wetting (spreading) and partial wetting ( _e) could be studied.The curves of cos andr/R ₀ vs. time for the different liquids of a series can be superimposed to a master curve by plotting them against _L·t _L·R ₀, whereR ₀ is the radius of the original drop. All these master curves coincide at small wetting times, with exception of the data for the polysiloxanes. That means that the early stage of the wetting process is determined only by the properties of the wetting liquid. The influence of the solid surface, characterized by the equilibrium contact angle _e becomes significant only at the end of the wetting process.Dedicated to Professor Dr. H. Willersinn on the occasion of his 65^th birthday     

Self-limited oxygen exchange kinetics at SnO2 surfaces

The oxygen exchange at SnO(2) surfaces strongly depends on surface termination, which is affected by the oxygen chemical potential. At low oxygen chemical potential, the surface adopts its reduced termination which allows oxygen exchange, while exchange is suppressed by the stoichiometric surface termination.     

Adsorption kinetics of surface-active substances from micellar solutions on solid phase

Summary The adsorption kinetics was studied of anion- and cation-active tensides on mineral surface from solutionsc _eq < CMC andc _eq CMC, and the adsorption mechanisms of ion exchange and ion pairing were discussed.In the range ofc _eq c _eb mono, the adsorption mechanism can be described using the Elovi-Zeldovi kinetic equations.In the rangec _eq CMC, the adsorption kinetics is more complicated. For very small values oft that lie beyond the possibility of measurements, the tenside molecules adsorb spontaneously, most probably as micelles, and then they desorb.As the measurements of _t (t) for the adsorption of H⁺ or OH^– have shown, the adsorption of tenside molecules in aqueous solutions occur in the presence of H⁺ or OH_– in the electric bilayer.The parallel course of both kinetics explains the anomalous behaviour in the range of the maximum, before the kinetic equilibrium is reached.

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Zusammenfassung Die Kinetik der Adsorption der anion- und kationaktiven Tenside auf der Mineraloberfläche aus LösungenC _eq < CM undC _eq CMC wurde untersucht und der Adsorptionsmechanismus des Ionenaustausches oder ion pairing diskutiert.Im BereichC _eq C _eq mono läßt sich der Adsorptionsmechanismus mit der kinetischen Gleichung nach Elovi-Zeldovi beschreiben.Im BereichC _eq CMC ist die Kinetik der Adsorption kompliziert. Für kleinet-Werte, die außerhalb der Meßmöglichkeiten liegen, kommt es zur spontanen Adsorption (wahrscheinlich in mizellarer Form) und danach folgender Desorption des Tensids.Wie die Messungen _t (t) für die Adsorption von H⁺ oder OH^– gezeigt haben, ist die Adsorption der Tensidmoleküle durch die Anwesenheit von H⁺ oder OH^– in der elektrischen Doppelschicht bedingt.Der parallele Verlauf beider Kinetiken erklärt das anomale Verhalten im Bereich des Maximums vor Erreichen des kinetischen Gleichgewichts.

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With 11 figures     

Neutral and charged polymer brushes at solid surfaces

Neutral and charged polymer brushes covalently attached to planar solid surfaces were generated by using self-assembled monolayers of an azo initiator and radical chain polymerization in situ. The brushes were characterized by FTIR-spectroscopy, optical waveguide-spectroscopy and Ellipsometry. Especially the film thicknesses of surface bound polyelectrolyte (PEL) monolayers were measured by optical waveguide spectroscopy (OWS) as a function of the humidity of the environment. The PEL brushes show strong increases in thickness as well as strong decrease of the refractive index of the surface attached layer due to water incorporation caused by the exposure to the humid environment. Additionally the behavior of neutral as well as charged brushes in contact with solvent was investigated by using multiple-angular-scans of ellipsometry in a total internal reflectance setup. The scaling behavior of the brush height as a function of the graft density of the attached polymer molecules was investigated for the neutral brush as well as for the PEL brush system.     

Synthetically useful oxidations at solid sodium permanganate surfaces

Solid NaMnO₄·H₂O is an efficient and selective oxidizing agent.     

Driving forces for protein adsorption at solid surfaces

Under most conditions proteins show a strong tendency to adsorb at interfaces. The general principles underlying the interaction between proteins and solid surfaces in an aqueous environment are discussed. These principles are illustrated by experimental results obtained with well-defined systems. The approach is mainly based on thermodynamic arguments.     

Diels-Alder chemistry at furan ring functionalized solid surfaces

A substrate-independent method for Diels-Alder chemistry at solid surfaces is described for the first time.     

Adsorption of bovine serum albumin at solid/aqueous interfaces

Adsorption of soluble serum proteins on hydrophilic and hydrophobic solid surfaces is important for biomaterials and chromatographic separations of proteins. The adsorption of bovine serum albumin (BSA) from aqueous solutions was studied with in situ ATR-IR spectroscopy, and with ex situ ATR-IR, ellipsometry, and water wettablity measurements. The results were used to quantitatively determine the adsorbed film thickness and surface density of BSA on hydrophilic silicon oxide/silicon surfaces, and on these surfaces covered with a hydrophobic lipid monolayer of dipalmitoylphosphatidylcholine (DPPC). The water contact angles were 5° for silicon oxide, 47° ± 1° for the DDPC monolayer, and 53° ± 1° for the BSA monolayers. At 25 °C, and with 0.01–1 wt% BSA in water, the surface densities range from Γ = 2.6–5.0 mg/m², and the film thicknesses range from d = 2.0–3.8 nm, on the assumption that the film is as dense as bulk protein. These results, and certain changes in the IR amide I and II bands of the protein, indicate that the protein adsorbs as a side-on monolayer, with some flattening due to unfolding or denaturation. The estimated -helical content for protein in buffer solutions is 15% higher than for solutions in water. The adsorption density reaches a steady-state value within 10 min for the lowest concentration, but does not appear to reach a steady-state value after 3 h f‘or the higher concentrations. Adsorption of BSA on a silicon oxide surface covered with a monolayer of DPPC leads to an adsorbed protein film of about half the thickness and surface density than on silicon oxide, but the same contact angle, indicating more protein unfolding on the hydrophobic than on the hydrophilic surface.