Coupling hydrophobic, dispersion, and electrostatic contributions in continuum solvent models

Recent studies of the hydration of micro- and nanoscale solutes have demonstrated a strong {\it coupling} between hydrophobic, dispersion and electrostatic contributions, a fact not accounted for in current implicit solvent models. We present a theoretical formalism which accounts for coupling by minimizing the Gibbs free energy with respect to a solvent volume exclusion function. The solvent accessible surface is output of our theory. Our method is illustrated with the hydration of alkane-assembled solutes on different length scales, and captures the strong sensitivity to the particular form of the solute-solvent interactions in agreement with recent computer simulations.Comment: 11 pages, 2 figure

Effective capillary interaction of spherical particles at fluid interfaces

We present a detailed analysis of the effective force between two smooth spherical colloids floating at a fluid interface due to deformations of the interface. The results hold in general and are applicable independently of the source of the deformation provided the capillary deformations are small so that a superposition approximation for the deformations is valid. We conclude that an effective long--ranged attraction is possible if the net force on the system does not vanish. Otherwise, the interaction is short--ranged and cannot be computed reliably based on the superposition approximation. As an application, we consider the case of like--charged, smooth nanoparticles and electrostatically induced capillary deformation. The resulting long--ranged capillary attraction can be easily tuned by a relatively small external electrostatic field, but it cannot explain recent experimental observations of attraction if these experimental systems were indeed isolated.Comment: 23 page

Analytical modeling of micelle growth. 2. Molecular thermodynamics of mixed aggregates and scission energy in wormlike micelles

Hypotheses: Quantitative molecular-thermodynamic theory of the growth of giant wormlike micelles in mixed nonionic surfactant solutions can be developed on the basis of a generalized model, which includes the classical phase separation and mass action models as special cases. The generalized model describes spherocylindrical micelles, which are simultaneously multicomponent and polydisperse in size. Theory: The model is based on explicit analytical expressions for the four components of the free energy of mixed nonionic micelles: interfacial-tension, headgroup-steric, chain-conformation components and free energy of mixing. The radii of the cylindrical part and the spherical endcaps, as well as the chemical composition of the endcaps, are determined by minimization of the free energy. Findings: In the case of multicomponent micelles, an additional term appears in the expression for the micelle growth parameter (scission free energy), which takes into account the fact that the micelle endcaps and cylindrical part have different compositions. The model accurately predicts the mean mass aggregation number of wormlike micelles in mixed nonionic surfactant solutions without using any adjustable parameters. The endcaps are enriched in the surfactant with smaller packing parameter that is better accommodated in regions of higher mean surface curvature. The model can be further extended to mixed solutions of nonionic, ionic and zwitterionic surfactants used in personal-care and house-hold detergency

A mesoscopic model for microscale hydrodynamics and interfacial phenomena: Slip, films, and contact angle hysteresis

We present a model based on the lattice Boltzmann equation that is suitable for the simulation of dynamic wetting. The model is capable of exhibiting fundamental interfacial phenomena such as weak adsorption of fluid on the solid substrate and the presence of a thin surface film within which a disjoining pressure acts. Dynamics in this surface film, tightly coupled with hydrodynamics in the fluid bulk, determine macroscopic properties of primary interest: the hydrodynamic slip; the equilibrium contact angle; and the static and dynamic hysteresis of the contact angles. The pseudo- potentials employed for fluid-solid interactions are composed of a repulsive core and an attractive tail that can be independently adjusted. This enables effective modification of the functional form of the disjoining pressure so that one can vary the static and dynamic hysteresis on surfaces that exhibit the same equilibrium contact angle. The modeled solid-fluid interface is diffuse, represented by a wall probability function which ultimately controls the momentum exchange between solid and fluid phases. This approach allows us to effectively vary the slip length for a given wettability (i.e. the static contact angle) of the solid substrate

Coupling nonpolar and polar solvation free energies in implicit solvent models

Recent studies on the solvation of atomistic and nanoscale solutes indicate that a strong coupling exists between the hydrophobic, dispersion, and electrostatic contributions to the solvation free energy, a facet not considered in current implicit solvent models. We suggest a theoretical formalism which accounts for coupling by minimizing the Gibbs free energy of the solvent with respect to a solvent volume exclusion function. The resulting differential equation is similar to the Laplace-Young equation for the geometrical description of capillary interfaces, but is extended to microscopic scales by explicitly considering curvature corrections as well as dispersion and electrostatic contributions. Unlike existing implicit solvent approaches, the solvent accessible surface is an output of our model. The presented formalism is illustrated on spherically or cylindrically symmetrical systems of neutral or charged solutes on different length scales. The results are in agreement with computer simulations and, most importantly, demonstrate that our method captures the strong sensitivity of solvent expulsion and dewetting to the particular form of the solvent-solute interactions.Comment: accpted in J. Chem. Phy

Direct measurements of the effects of salt and surfactant on interaction forces between colloidal particles at water-oil interfaces

The forces between colloidal particles at a decane-water interface, in the presence of low concentrations of a monovalent salt (NaCl) and of the surfactant sodium dodecylsulfate (SDS) in the aqueous subphase, have been studied using laser tweezers. In the absence of electrolyte and surfactant, particle interactions exhibit a long-range repulsion, yet the variation of the interaction for different particle pairs is found to be considerable. Averaging over several particle pairs was hence found to be necessary to obtain reliable assessment of the effects of salt and surfactant. It has previously been suggested that the repulsion is consistent with electrostatic interactions between a small number of dissociated charges in the oil phase, leading to a decay with distance to the power -4 and an absence of any effect of electrolyte concentration. However, the present work demonstrates that increasing the electrolyte concentration does yield, on average, a reduction of the magnitude of the interaction force with electrolyte concentration. This implies that charges on the water side also contribute significantly to the electrostatic interactions. An increase in the concentration of SDS leads to a similar decrease of the interaction force. Moreover the repulsion at fixed SDS concentrations decreases over longer times. Finally, measurements of three-body interactions provide insight into the anisotropic nature of the interactions. The unique time-dependent and anisotropic interactions between particles at the oil-water interface allow tailoring of the aggregation kinetics and structure of the suspension structure.Comment: Submitted to Langmui

Free energy of colloidal particles at the surface of sessile drops

The influence of finite system size on the free energy of a spherical particle floating at the surface of a sessile droplet is studied both analytically and numerically. In the special case that the contact angle at the substrate equals $\pi/2$ a capillary analogue of the method of images is applied in order to calculate small deformations of the droplet shape if an external force is applied to the particle. The type of boundary conditions for the droplet shape at the substrate determines the sign of the capillary monopole associated with the image particle. Therefore, the free energy of the particle, which is proportional to the interaction energy of the original particle with its image, can be of either sign, too. The analytic solutions, given by the Green's function of the capillary equation, are constructed such that the condition of the forces acting on the droplet being balanced and of the volume constraint are fulfilled. Besides the known phenomena of attraction of a particle to a free contact line and repulsion from a pinned one, we observe a local free energy minimum for the particle being located at the drop apex or at an intermediate angle, respectively. This peculiarity can be traced back to a non-monotonic behavior of the Green's function, which reflects the interplay between the deformations of the droplet shape and the volume constraint.Comment: 24 pages, 19 figure

Direct Observation of the Dynamics of Latex Particles Confined inside Thinning Water-Air Films

The dynamics of micrometer-size polystyrene latex particles confined in thinning foam films was investigated by microscopic interferometric observation. The behavior of the entrapped particles depends on the mobility of the film surfaces, the particle concentration, hydrophobicity, and rate of film formation. When the films were stabilized by sodium dodecyl sulfate, no entrapment of particles between the surfaces was possible. When protein was used as a stabilizer, a limited number of particles were caught inside the film area due to the decreased mobility of the interfaces. In this case, extraordinary long-ranged (>100 Ìm) capillary attraction leads to two-dimensional (2D) particle aggregation. A major change occurs when the microspheres are partially hydrophobized by the presence of cationic surfactant. After the foam films are opened and closed a few times, a layer of particles simultaneously adsorbed to the two interfaces is formed, which sterically inhibits any further film opening and thinning. The particles within this layer show an excellent 2D hexagonal ordering. The experimental data are relevant to the dynamics of defects in coating films, Pickering emulsions, and particle assembly into 2D arrays

Particles at oil–air surfaces : powdered oil, liquid oil marbles, and oil foam

The type of material stabilized by four kinds of fluorinated particles (sericite and bentonite platelet clays and spherical zinc oxide) in air–oil mixtures has been investigated. It depends on the particle wettability and the degree of shear. Upon vigorous agitation, oil dispersions are formed in all the oils containing relatively large bentonite particles and in oils of relatively low surface tension (γla < 26 mN m⁻¹) like dodecane, 20 cS silicone, and cyclomethicone containing the other fluorinated particles. Particle-stabilized oil foams were obtained in oils having γla > 26 mN m⁻¹ where the advancing air–oil–solid contact angle θ lies between ca. 90° and 120°. Gentle shaking, however, gives oil-in-air liquid marbles with all the oil–particle systems except for cases where θ is <60°. For oils of tension >24 mN m⁻¹ with omniphobic zinc oxide and sericite particles for which advancing θ ≥ 90°, dry oil powders consisting of oil drops in air which do not leak oil could be made upon gentle agitation up to a critical oil:particle ratio (COPR). Above the COPR, catastrophic phase inversion of the dry oil powders to air-in-oil foams was observed. When sheared on a substrate, the dry oil powders containing at least 60 wt % of oil release the encapsulated oil, making these materials attractive formulations in the cosmetic and food industries

Comprehension of demoulding mechanisms at the formwork/oil/concrete interface

The implementation of concrete and its association with a release agent influence the aesthetics of the concrete facings. The mineral oils tend to be replaced by vegetable formulations, to reduce the impact of the substances spilled in the environment. From a technical point of view, it is important to characterize the action of these new formulations at the interface concrete/oil/formwork. Two performing techniques have been used to study the physicochemical processes, the tribometry and electrochemical impedance spectroscopy. The correlation of the results obtained allowed to improve the understanding of the mechanisms involved at the interface mould/oil, in connection with the use of an acidifier in the formulation