Study of Salt Effects on the Micelle-Monomer Exchange Process of Octyl-, Decyl-, and Dodecyltrimethylammonium Bromide in Aqueous Solutions by Means of Ultrasonic Relaxation Spectroscopy

Spreading of a tiny macroscopic droplet of a nonvolatile, completely wetting liquid over a flat solid is considered. A liquid in creeping is subjected to capillary forces and long-range molecular forces. The droplet may be surrounded with a precursor wetting film. This paper deals with the problem of determining of the microscopic parameter that influences the interface shape near the apparent line of wetting; this is regarded as the inverse problem in the hydrodynamics of wetting. If the system includes a precursor film, the microscopic parameter coincides with the maximum thickness of the film. A series of inverse equations for the microparameter is obtained, which relate it to, first, the current geometric parameters of the macroscopic drop part and, second, the spreading time. A method for determining how the microparameter depends on the wetting line speed is proposed. The theory expands the opportunity to perform macroscopic measurements and reveals additional parameters. The inverse relations may be used to experimentally study the growth of the maximum thickness of a precursor film during drop spreading. Copyright 2000 Academic Press.     

Pattern formation and dewetting in thin films of liquids showing complete macroscale wetting: from "pancakes"to "swiss cheese"

Based on the complete 3D numerical solutions of the nonlinear thin film equation, we address the problems of surface instability, dynamics, morphological diversity and evolution in unstable thin films of the liquids that display complete macroscale wetting. The twin constraints of complete macroscale wettability and nanoscale instability produce a variety of microscopic morphological phases approximating sharp crystal surfaces with flat tops resembling a mesa or a micro "pancake" or a slice of Swiss cheese. While the maximum thickness of flat regions is found to be independent of the initial film thickness, the precise lateral morphology of microdomains formed depends on the film thickness. As the film thickness is increased, the initial pathway of evolution changes from the formation of small spherical droplets, to long mesas (parapets) and islands, to circular holes, all of which eventually resolve by ripening into a collection of round pancakes at equilibrium. However, beyond a certain transition thickness, a novel metastable honeycombed morphology, resembling a membrane or a slice of Swiss cheese, is uncovered, which is produced by an abrupt "freezing" of the evolution during hole growth. In contrast, the spinodal dewetting in thin films of partially wettable systems always engenders spherical droplets at equilibrium. The equilibrium dewetted area from simulations, as well as from simple mass balance, is shown to decline linearly with the initial film thickness.     

Analysis of pseudopartial and partial wetting of various substrates by lead

Lead drops exhibit partial wetting on some substrates and pseudopartial wetting on others. In pseudopartial wetting, a film is in equilibrium with a capillary body with a nonzero contact angle. Using a free energy formulation appropriate for the experiments, we show the conditions under which minimization of the system energy is accurately achieved by minimizing the energy of the film alone. Using a set of simple surface energy isotherms, we explain the various wetting behaviors of lead. We contrast isotherms for autophobing systems and the metallic systems considered here.     

Interfacial tension and spreading coefficient for thin films

We present a modified mathematical expression for the interfacial tension of very thin films. At large thicknesses the modified expression converges to the classic mathematical expression. We use this modified expression to derive an equation for the spreading coefficient as a function of film thickness. The spreading coefficient equation is then used to calculate the equilibrium thickness of a wetting liquid film for a "pancake drop". Our predictions agree with experimental data. The study is subjected to systems with van der Waals interactions only.     

Monte Carlo simulation methods for computing the wetting and drying properties of model systems

We introduce general Monte Carlo simulation methods for determining the wetting and drying properties of model systems. We employ an interface-potential-based approach in which the interfacial properties of a system are related to the surface excess free energy of a thin fluid film in contact with a surface. Two versions of this approach are explored: a "spreading" method focused on the growth of a thin liquid film from a surface in a mother vapor and a "drying" method focused on the growth of a thin vapor film from a surface in a mother liquid. The former provides a direct measure of the spreading coefficient while the latter provides an analogous drying coefficient. When coupled with an independent measure of the liquid-vapor surface tension, these coefficients enable one to compute the contact angle. We also show how one can combine information gathered from application of the spreading and drying methods at a common state point to obtain direct measures of the contact angle and liquid-vapor surface tension. The computational strategies introduced here are applied to two model systems. One includes a monatomic Lennard-Jones fluid that interacts with a structureless substrate via a long-ranged substrate potential. The second model contains a monatomic Lennard-Jones fluid that interacts with an atomistically detailed substrate via a short-ranged potential. Expanded ensemble techniques are coupled with the interface potential approach to compile the temperature- and substrate strength-dependence of various interfacial properties for these systems. Overall, we find that the approach pursued here provides an efficient and precise means to calculate the wetting and drying properties of model systems.     

Liquid nanodroplets spreading on chemically patterned surfaces

Controlling the spatial distribution of liquid droplets on surfaces via surface energy patterning can be used to deliver material to specified regions via selective liquid/solid wetting. Although studies of the equilibrium shape of liquid droplets on heterogeneous substrates exist, much less is known about the corresponding wetting kinetics. Here we present large-scale atomistic simulations of liquid nanodroplets spreading on chemically patterned surfaces. Results are presented for lines of polymer liquid (droplets) on substrates consisting of alternating strips of wetting (equilibrium contact angle theta0 = 0 degrees) and nonwetting (theta0 approximately 90 degrees) material. Droplet spreading is compared for different wavelength lambda of the pattern and strength of surface interaction on the wetting strips. For small lambda, droplets partially spread on both the wetting and nonwetting regions of the substrate to attain a finite contact angle less than 90 degrees. In this case, the extent of spreading depends on the interaction strength in the wetting regions. A transition is observed such that, for large lambda, the droplet spreads only on the wetting region of the substrate by pulling material from nonwetting regions. In most cases, a precursor film spreads on the wetting portion of the substrate at a rate strongly dependent on the width of the wetting region.     

Diverse spreading behavior of binary polymer nanodroplets

Molecular dynamics simulations are used to study the spreading of binary polymer nanodroplets in a cylindrical geometry. The polymers, described by the bead-spring model, spread on a flat surface with a surface-coupled Langevin thermostat to mimic the effects of a corrugated surface. Each droplet consists of chains of length 10 or 100 monomers with approximately 350,000 monomers total. The qualitative features of the spreading dynamics are presented for differences in chain length, surface interaction strength, and composition. When the components of the droplet differ only in the surface interaction strength, the more strongly wetting component forms a monolayer film on the surface even when both materials are above or below the wetting transition. In the case where the only difference is the polymer chain length, the monolayer film beneath the droplet is composed of an equal amount of short chain and long chain monomers even when one component (the shorter chain length) is above the wetting transition and the other is not. The fraction of short and long chains in the precursor foot depends on whether both the short and the long chains are in the wetting regime. Diluting the concentration of the strongly wetting component in a mixture with a weakly wetting component decreases the rate of diffusion of the wetting material from the bulk to the surface and limits the spreading rate of the precursor foot, but the bulk spreading rate actually increases when both components are present. This may be due to the strongly wetting material pushing out the weakly wetting material as it moves toward the precursor foot.     

Wetting Film Dynamics

The spreading of a tiny macroscopic drop of a nonvolatile, completely wetting liquid over a flat solid is considered, assuming no gravitation. A liquid, in creeping, is subjected to capillary forces and van der Waals forces. This nonstationary and nonlinear problem in the dynamics of the wetting film from a droplet is studied using numerical modeling. The precursor wetting film motion is described by an evolution equation with conditions at the moving boundaries. The wetting line is regarded as an unknown boundary to be determined in the course of solution. A simplified equation for the wetting line dynamics is analyzed. The difference between the wetting line radius and a fixed (nonzero) radius is described by a diffusion time law. Results of numerical experiments show the simplified law of wetting to be valid over a wide range of spreading times (or a wide range of radii of the wetting line). Copyright 2000 Academic Press.     

Rupture of wetting films caused by nanobubbles

It is now widely accepted that nanometer sized bubbles, attached at a hydrophobic silica surface, can cause rupture of aqueous wetting films due to the so-called nucleation mechanism. But the knowledge of the existence of such nanobubbles does not give an answer to how the subprocesses of this rupture mechanism operate. The aim of this paper is to describe the steps of the rupture process in detail: (1) During drainage of the wetting film, the apex of the largest nanobubble comes to a distance from the wetting film surface, where surface forces are acting. (2) An aqueous "foam film" in nanoscale size is formed between the bubble and the wetting film surface; in this foam film different Derjaguin-Landau-Verwey-Overbeek (DLVO) forces are acting than in the surrounding wetting film. In the investigated system, hydrophobized silica/water/air, all DLVO forces in the wetting film are repulsive, whereas in the foam film the van der Waals force becomes attractive. (3) The surface forces over and around the apex of the nanobubble lead to a deformation of the film surfaces, which causes an additional capillary pressure in the foam film. An analysis of the pressure balance in the system shows that this additional capillary pressure can destabilize the foam film and leads to rupture of the foam film. (4) If the newly formed hole in the wetting film has a sufficient diameter, the whole wetting film is destabilized and the solid becomes dewetted. Experimental data of rupture thickness and lifetime of wetting films of pure electrolyte and surfactant solutions show that the stabilization of the foam film by surfactants has a crucial effect on the stability of the wetting film.     

Kinetics of wetting of liquid on a solid surface

To consider a sessile drop on an ideal solid surface in equilibrium with a vapor phase, the classic Young equation was given. The derivation of the Young equation was based on both the mechanics and the energy knowledge. According to the constant volume of the liquid in the wetting process of the liquid on a smooth and homogeneous solid surface and the low energy law, Young equation was ob-tained through the mathematic method in this paper. The previous work indicated that the contact angle θ was a function...     

To the theory of wetting

Young’s equation is considered as applied to describe the behavior of ideal systems in thermodynamic equilibrium with the classification of the solid bodies into bodies having low-energy and high-energy surfaces. This classification verifies the validity of categorizing real systems into wetting and nonwetting ones with the wetting boundary lying at the contact angle having a value of θ = 90° and allows the nonwetting systems to be represented by three ranges of manifestation of contact angles, namely: a nonwetting range with contact angles of θ > 106°, an equilibrium wetting range (74° < θ < 106°), and a nonequilibrium incomplete wetting range (θ < 74°).     

Dynamics of condensation of wetting layer in time-dependent Ginzburg-Landau model

The dynamics of liquid condensation on a substrate or within a capillary is studied when the wetting film grows via interface-limited growth. We use a phenomenological time-dependent Ginzburg-Landau (TDGL)-type model with long-range substrate potential. Using an order parameter, which does not directly represent the density, we can derive an analytic formula for the interfacial growth velocity that is directly related to the substrate potential. Using this analytic expression the growth of wetting film is shown to conform to a power-law-type growth, which is due to the presence of a long-range dispersion force.     

The condition of mechanical equilibrium on the surface of a nonuniform thin film

The condition of internal mechanical equilibrium of a curved surface layer is derived, and its application to practically important cases of incomplete formation of the surface layer (as is sometimes the case, for example, in thin films) is considered. The notion of a local disjoining pressure is introduced, and the equilibrium condition for a variable-thickness thin film is obtained; this condition is valid both in the absence and in the presence of external fields. The cases of a wedge-shaped film, cylindrical film, spherical film, and transition zone of a wetting film are analyzed.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 235–242.Original Russian Text Copyright © 2005 by Rusanov, Shchekin.     

Crystallization mechanisms in convective particle assembly

Colloidal particles are continuously assembled into crystalline particle coatings using convective fluid flows. Assembly takes place inside a meniscus on a wetting reservoir. The shape of the meniscus defines the profile of the convective flow and the motion of the particles. We use optical interference microscopy, particle image velocimetry, and particle tracking to analyze the particles' trajectory from the liquid reservoir to the film growth front and inside the deposited film as a function of temperature. Our results indicate a transition from assembly at a static film growth front at high deposition temperatures to assembly in a precursor film with high particle mobility at low deposition temperatures. A simple model that compares the convective drag on the particles to the thermal agitation explains this behavior. Convective assembly mechanisms exhibit a pronounced temperature dependency and require a temperature that provides sufficient evaporation. Capillary mechanisms are nearly temperature independent and govern assembly at lower temperatures. The model fits the experimental data with temperature and particle size as variable parameters and allows prediction of the transition temperatures. While the two mechanisms are markedly different, dried particle films from both assembly regimes exhibit hexagonal particle packings. We show that films assembled by convective mechanisms exhibit greater regularity than those assembled by capillary mechanisms.     

Theory of slope-dependent disjoining pressure with application to Lennard-Jones liquid films

A liquid film of thickness h<100 nm is subject to additional intermolecular forces, which are collectively called disjoining pressure Pi. Since Pi dominates at small film thicknesses, it determines the stability and wettability of thin films. Current theory derived for uniform films gives Pi=Pi(h). This solution has been applied recently to non-uniform films and becomes unbounded near a contact line as h-->0. Consequently, many different effects have been considered to eliminate or circumvent this singularity. We present a mean-field theory of Pi that depends on the slope h(x) as well as the height h of the film. When this theory is implemented for Lennard-Jones liquid films, the new Pi=Pi(h,h(x)) is bounded near a contact line as h-->0. Thus, the singularity in Pi(h) is artificial because it results from extending a theory beyond its range of validity. We also show that the new Pi can capture all three regimes of drop behavior (complete wetting, partial wetting, and pseudo-partial wetting) without altering the signs of the long and short-range interactions. We find that a drop with a precursor film is linearly stable.     

The application of thermodynamic perturbation theory to the calculation of excess free energy of small systems: 2. Excess free energy and disjoining pressure in the wetting layer of apolar liquid

Isotherms of disjoining pressure in the wetting film of apolar liquid on unmodified and modified solid surfaces were studied based on the thermodynamic perturbation theory. Specific calculations were performed for two systems: (1) the wetting film of decane on aluminum surface and (2) the wetting film of decane on aluminum surface modified by pentanol. It was shown that the results of calculation agree with experimental data.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 850–855.Original Russian Text Copyright © 2004 by Samsonov, Rumyantsev, Khashin.     

Signatures of non locality for short-ranged wetting at curved substrates

The binding potential for wetting near planes, spheres, and cylinders in systems with short-ranged forces is shown to have a universal geometrical structure. This arises from the nonlocal nature of the interfacial interactions and is exactly described by a recently proposed binding potential functional, which provides a systematic framework for studying wetting at arbitrarily shaped substrates. The corrections to the equilibrium wetting layer thickness induced by nonlocality are comparable to those arising from a Tolman length and lead to diverging terms in the total mass adsorption.     

Influence of Solid-liquid Interaction and Temperature on the Dynamic Dewetting of a Thin Polymer Film:A Molecular Dynamics Study

Coarse-grained molecular dynamics simulations were carried out to investigate the dewetting behavior of a polymer thin film on partial wetting solid surface at the early stage of the dewetting process. Spontaneous dewetting is initiated by removing a band of strip from both the ends of the liquid polymer film which has achieved equilibrium. The solid-liquid interaction and temperature were varied to show their influence on the dewetting dynamics during dewetting as well as the shape evolution of the liquid ...     

Fine Structure of Meniscus of a Wetting Liquid

Equilibrium of a capillary meniscus near a wetting film on a solid in a gravitational field is considered. Unlike previous studies, the present study proves that the fine meniscus structure in a gravitational field is a universal feature—it takes place in a wide variety of problems. In the general case, the capillary meniscus is at a certain distance from the wetting film and does not intersect it. The relation for the minimum distance from the arbitrary meniscus to the solid generalizes the Derjaguin formula for a flat slit. An equation that optimally approximates the meniscus with due account of the contribution of the meniscus/film transition region is derived. A refined solution to the problem of a meniscus on a vertical plate is derived within the perturbation theory. Both gravity and nonuniformity of the vertical static film above a capillary–gravitational meniscus do not affect the minimum distance (the influence is less than 0.0001). A general method for solving sophisticated problems of capillary equilibrium in gravitational field is proposed.     

Wetting films on a hydrophilic silica surface obtained from aqueous solutions of hydrophobically modified inulin polymeric surfactant

The thickness of wetting films on a hydrophilic silica surface was investigated using a microinterferometric technique. Aqueous solutions of hydrophobically modified inulin (INUTEC^®SP1) at various concentrations, in the presence or absence of NaCl or Na₂SO₄, were studied. The equilibrium film thickness (h _eq) showed a complex dependence on INUTEC^®SP1 concentration. At low electrolyte concentrations, h _eq decreased with an increase in INUTEC^®SP1 concentration, reaching a minimum at 10^?6 mol dm^?3. However, at high electrolyte concentrations, this dependence became less pronounced. At any given INUTEC^®SP1 concentration, the equilibrium film thickness decreased with an increase in electrolyte concentration as a result of the compression of the electrical double layer reaching a minimum value. After that, the film thickness showed a small decrease with further increase in electrolyte concentration. This indicates that the electrostatic component of disjoining pressure can be neglected, and the steric repulsion of the loops and tails of INUTEC^®SP1 determined the film thickness.