Kinetics of Surfactant Adsorption at Fluid-Fluid Interfaces

We present a theory for the kinetics of surfactant adsorption at the interface between an aqueous solution and another fluid (air, oil) phase. The model relies on a free-energy formulation. It describes both the diffusive transport of surfactant molecules from the bulk solution to the interface, and the kinetics taking place at the interface itself. When applied to non-ionic surfactant systems, the theory recovers results of previous models, justify their assumptions and predicts a diffusion-limited adsorption, in accord with experiments. For salt-free ionic surfactant solutions, electrostatic interactions are shown to drastically affect the kinetics. The adsorption in this case is predicted to be kinetically limited, and the theory accounts for unusual experimental results obtained recently for the dynamic surface tension of such systems. Addition of salt to an ionic surfactant solution leads to screening of the electrostatic interactions and to a diffusion-limited adsorption. In addition, the free-energy formulation offers a general method for relating the dynamic surface tension to surface coverage without relying on equilibrium relations.Comment: 36 pages, latex, 10 figure

Self-Assembly in Mixtures of Polymers and Small Associating Molecules

The interaction between a flexible polymer in good solvent and smaller associating solute molecules such as amphiphiles (surfactants) is considered theoretically. Attractive correlations, induced in the polymer because of the interaction, compete with intra-chain repulsion and eventually drive a joint self-assembly of the two species, accompanied by partial collapse of the chain. Results of the analysis are found to be in good agreement with experiments on the onset of self-assembly in diverse polymer-surfactant systems. The threshold concentration for self-assembly in the mixed system (critical aggregation concentration, cac) is always lower than the one in the polymer-free solution (critical micelle concentration, cmc). Several self-assembly regimes are distinguished, depending on the effective interaction between the two species. For strong interaction, corresponding experimentally to oppositely charged species, the cac is much lower than the cmc. It increases with ionic strength and depends only weakly on polymer charge. For weak interaction, the cac is lower but comparable to the cmc, and the two are roughly proportional over a wide range of cmc values. Association of small molecules with amphiphilic polymers exhibiting intra-chain aggregation (polysoaps) is gradual, having no sharp onset.Comment: 21 pages, 5 figures, RevTex, the published version, see also cond-mat/990305

Phase Behavior of Polyelectrolyte-Surfactant Complexes at Planar Surfaces

We investigate theoretically the phase diagram of an insoluble charged surfactant monolayer in contact with a semi-dilute polyelectrolyte solution (of opposite charge). The polyelectrolytes are assumed to have long-range and attractive (electrostatic) interaction with the surfactant molecules. In addition, we introduce a short-range (chemical) interaction which is either attractive or repulsive. The surfactant monolayer can have a lateral phase separation between dilute and condensed phases. Three different regimes of the coupled system are investigated depending on system parameters. A regime where the polyelectrolyte is depleted due to short range repulsion from the surface, and two adsorption regimes, one being dominated by electrostatics, whereas the other by short range chemical attraction (similar to neutral polymers). When the polyelectrolyte is more attracted (or at least less repelled) by the surfactant molecules as compared with the bare water/air interface, it will shift upwards the surfactant critical temperature. For repulsive short-range interactions the effect is opposite. Finally, the addition of salt to the solution is found to increase the critical temperature for attractive surfaces, but does not show any significant effect for repulsive surfaces.Comment: 23 pages, 10 figure

Roughness-Induced Wetting

We investigate theoretically the possibility of a wetting transition induced by geometric roughness of a solid substrate for the case where the flat substrate does not show a wetting layer. Our approach makes use of a novel closed-form expression which relates the interaction between two sinusoidally modulated interfaces to the interaction between two flat interfaces. Within the harmonic approximation, we find that roughness-induced wetting is indeed possible if the substrate roughness, quantified by the substrate surface area, exceeds a certain threshold. In addition, the molecular interactions between the substrate and the wetting substance have to satisfy several conditions. These results are expressed in terms of a lower bound on the wetting potential for a flat substrate in order for roughness-induced wetting to occur. This lower bound has the following properties: A minimum is present at zero or very small separation between the two interfaces, as characteristic for the non-wetting situation in the flat case. Most importantly, the wetting potential needs to have a pronounced maximum at a separation comparable to the amplitude of the substrate roughness. These findings are in agreement with the experimental observation of roughness-induced surface premelting at a glass-ice interface as well as the calculation of the dispersion interaction for the corresponding glass-water-ice system.Comment: 17 pages, 8 figure

Diblock copolymer ordering induced by patterned surfaces

We use a Ginzburg-Landau free energy functional to investigate diblock copolymer morphologies when the copolymer melt interacts with one surface or is confined between two chemically patterned surfaces. For temperatures above the order-disorder transition a complete linear response description of the copolymer melt is given, in terms of an arbitrary two-dimensional surface pattern. The appearance of order in the direction parallel to the surface is found as a result of the order in the perpendicular direction. Below the order-disorder point and in a thin-film geometry, our procedure enables the analytic calculation of distorted perpendicular and tilted lamellar phases in the presence of uniform or modulated surface fields.Comment: 8 pages, 3 figures, to be published in Europhys. Let

Kinetics of Surfactant Adsorption at Fluid-Fluid Interfaces: Surfactant Mixtures

The adsorption at the interface between an aqueous solution of several surface-active agents and another fluid (air or oil) phase is addressed theoretically. We derive the kinetic equations from a variation of the interfacial free energy, solve them numerically and provide an analytic solution for the simple case of a linear adsorption isotherm. Calculating asymptotic solutions analytically, we find the characteristic time scales of the adsorption process and observe the behavior of the system at various temporal stages. In particular, we relate the kinetic behavior of the mixture to the properties of its individual constituents and find good agreement with experiments. In the case of kinetically limited adsorption, the mixture kinetics is found to be considerably different from that of the single-surfactant solutions because of strong coupling between the species.Comment: 19 pages, 7 figures, to be published in Langmui