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

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

Random Polyelectrolytes and Polyampholytes in Solution

The behavior of polyelectrolytes and polyampholytes in semi-dilute solutions is investigated theoretically. Various statistical charge distributions along the polyelectrolyte chains are considered: smeared, annealed, permuted and quenched. Annealed polyampholytes are also considered. Path integral formulation was used to derive mean field free energies for the different models. Self-consistent field equation is obtained for the polymer order parameter and a Poisson-Boltzmann like equation for the electrostatic potential. The random phase approximation is used to calculate the monomer-monomer structure factor S(q) for the different statistical charge distribution models. We show that in the annealed model, fluctuations of the the monomer charges contribute to the electrostatic screening in addition to the free ions in the solution. The strength of this screening depends on the variance of the monomer charge distribution and is especially important for polyampholytes in bad solvent conditions where the mesophase separation is enhanced. The ratio between the variance and the net average charge determines whether polyampholytes behave as polyelectrolytes or as neutral chains.Comment: 18 pages, 5 figures, submitted to Eur. Phys. J.

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