Validity of the scaling functional approach for polymer interfaces as a variational theory

We discuss the soundness of the scaling functional (SF) approach proposed by Aubouy Guiselin and Raphael (Macromolecules 29, 7261 (1996)) to describe polymeric interfaces. In particular, we demonstrate that this approach is a variational theory. We emphasis the role of SF theory as an important link between ground-state theories suitable to describe adsorbed layers, and "classical" theories for polymer brushes.Comment: 8 pages, 1 figure, to be published in Phys. Rev.

A simple approach for charge renormalization of highly charged macro-ions

We revisit the popular notion of effective or renormalized charge, which is a concept of central importance in the field of highly charged colloidal or polyelectrolyte solutions. Working at the level of a linear Debye-H\"uckel like theory only, we propose a simple, efficient and versatile method to predict the saturated amount of charge renormalization, which is however a non-linear effect arising at strong electrostatic coupling. The results are successfully tested against the numerical solutions of Poisson-Boltzmann theory for polyions of various shapes (planar, cylindrical and spherical), both in the infinite dilution limit or in confined geometry, with or without added electrolyte. Our approach, accurate for monovalent micro-ions in solvents like water, is finally confronted against experimental results, namely the crystallization of charged colloidal suspensions and the osmotic coefficient of B-DNA solutions

Analytical estimate of effective charges at saturation in Poisson-Boltzmann cell models

We propose a simple approximation scheme to compute the effective charge of highly charged colloids (spherical or cylindrical with infinite length). Within non-linear Poisson-Boltzmann theory, we start from an expression of the effective charge in the infinite dilution limit which is asymptotically valid for large salt concentrations; this result is then extended to finite colloidal concentration, approximating the salt partitioning effect which relates the salt content in the suspension to that of a dializing reservoir. This leads to an analytical expression of the effective charge as a function of colloid volume fraction and salt concentration. These results compare favorably with the effective charges {\em at saturation} (i.e. in the limit of large bare charge) computed numerically following the standard prescription proposed by Alexander {\it et al.} within the cell model.Comment: 5 pages, 2 figures, to appear in Journal of Physics : Condensed Matte

Inwardly curved polymer brushes : Concave is not like Convex

Inwardly curved polymer brushes are present in cylindrical and spherical micelles or in membranes tubes and vesicles decorated with anchored polymers, and influence their stability. We consider such polymer brushes in good solvent and show that previous works, based on a self-similar concentric structure of the brush, are physically inconsistent. We use scaling laws to derive very simply the leading term of the free energy in the high curvature limit, where the osmotic pressure is the relevant physical ingredient. We also derive the complete conformation at all curvatures using a self-consistent field approach. The free energy is computed therefrom using a local scaling description.Comment: Subm. to Eur. Phys. J. E., rev. version, 12 pages plus 9 figures, PACS : 36.20.Ey / 82.35.Gh / 82.70.-y. Figure 1 modified. In introduction, discussion added on concentration gradients near the edge of the brush. [email protected] [email protected] [email protected] [email protected]

Effective interactions and phase behaviour for a model clay suspension in an electrolyte

Since the early observation of nematic phases of disc-like clay colloids by Langmuir in 1938, the phase behaviour of such systems has resisted theoretical understanding. The main reason is that there is no satisfactory generalization for charged discs of the isotropic DLVO potential describing the effective interactions between a pair of spherical colloids in an electrolyte. In this contribution, we show how to construct such a pair potential, incorporating approximately both the non-linear effects of counter-ion condensation (charge renormalization) and the anisotropy of the charged platelets. The consequences on the phase behaviour of Laponite dispersions (thin discs of 30 nm diameter and 1 nm thickness) are discussed, and investigation into the mesostructure via Monte Carlo simulations are presented.Comment: LaTeX, 12 pages, 11 figure

Two-dimensional flows of foam: drag exerted on circular obstacles and dissipation

A Stokes experiment for foams is proposed. It consists in a two-dimensional flow of a foam, confined between a water subphase and a top plate, around a fixed circular obstacle. We present systematic measurements of the drag exerted by the flowing foam on the obstacle, \emph{versus} various separately controlled parameters: flow rate, bubble volume, solution viscosity, obstacle size and boundary conditions. We separate the drag into two contributions, an elastic one (yield drag) at vanishing flow rate, and a fluid one (viscous coefficient) increasing with flow rate. We quantify the influence of each control parameter on the drag. The results exhibit in particular a power-law dependence of the drag as a function of the solution viscosity and the flow rate with two different exponents. Moreover, we show that the drag decreases with bubble size, increases with obstacle size, and that the effect of boundary conditions is small. Measurements of the streamwise pressure gradient, associated to the dissipation along the flow of foam, are also presented: they show no dependence on the presence of an obstacle, and pressure gradient depends on flow rate, bubble volume and solution viscosity with three independent power laws.Comment: 23 pages, 13 figures, proceeding of Eufoam 2004 conferenc

Adsorption of polyelectrolytes from semi-dilute solutions on an oppositely charged surface

We propose a detailed description of the structure of the layer formed by polyelectrolyte chains adsorbed onto an oppositely charged surface in the semi-dilute regime. We combine the mean-field Poisson-Boltzmann-Edwards theory and the scaling functional theory to describe the variations of the monomer concentration, the electrostatic potential, and the local grafting density with the distance to the surface. For long polymers, we find that the effective charge of the decorated surface (surface plus adsorbed polyelectrolytes) can be much larger than the bare charge of the surface at low salt concentration, thus providing an experimental route to a "supercharging" type of effect.Comment: 14 pages, 6 figure

Effective interactions in the colloidal suspensions from HNC theory

The HNC Ornstein-Zernike integral equations are used to determine the properties of simple models of colloidal solutions where the colloids and ions are immersed in a solvent considered as a dielectric continuum and have a size ratio equal to 80 and a charge ratio varying between 1 and 4000. At an infinite dilution of colloids, the effective interactions between colloids and ions are determined for ionic concentrations ranging from 0.001 to 0.1 mol/l and compared to those derived from the Poisson-Boltzmann theory. At finite concentrations, we discuss on the basis of the HNC results the possibility of an unambiguous definition of the effective interactions between the colloidal molecules.Comment: 26 pages, 15 figure

Evidence of environmental strains on charge injection in silole based organic light emitting diodes

Using d. functional theory (DFT) computations, the authors demonstrated a substantial skeletal relaxation when the structure of 2,5-bis-[4-anthracene-9-yl-phenyl]-1,1-dimethyl-3,4-diphenyl-silole (BAS) is optimized in the gas-phase comparing with the mol. structure detd. from monocrystal x-ray diffraction. The origin of such a relaxation is explained by a strong environmental strains induced by the presence of anthracene entities. Also, the estn. of the frontier orbital levels showed that this structural relaxation affects mainly the LUMO that is lowered of 190 meV in the gas phase. To check if these theor. findings would be confirmed for thin films of BAS, the authors turned to UV photoemission spectroscopy and/or inverse photoemission spectroscopy and electrooptical measurements. The study of the c.d. or voltage and luminance or voltage characteristics of an ITO/PEDOT/BAS/Au device clearly demonstrated a very unusual temp.-dependent behavior. Using a thermally assisted tunnel transfer model, this behavior likely originated from the variation of the electronic affinity of the silole deriv. with the temp. The thermal agitation relaxes the mol. strains in thin films as it is shown when passing from the cryst. to the gas phase. The relaxation of the intramol. thus induces an increase of the electronic affinity and, as a consequence, the more efficient electron injection in org. light-emitting diodes

Exact asymptotic expansions for the cylindrical Poisson-Boltzmann equation

The mathematical theory of integrable Painleve/Toda type systems sheds new light on the behavior of solutions to the Poisson-Boltzmann equation for the potential due to a long rod-like macroion. We investigate here the case of symmetric electrolytes together with that of 1:2 and 2:1 salts. Short and large scale features are analyzed, with a particular emphasis on the low salinity regime. Analytical expansions are derived for several quantities relevant for polyelectrolytes theory, such as the Manning radius. In addition, accurate and practical expressions are worked out for the electrostatic potential, which improve upon previous work and cover the full range of radial distances