Polymer-mediated interactions of fluid membranes in a lyotropic lamellar phase: a small angle X-ray and neutron scattering study

Small angle X-ray and neutron scattering data on an effective three-component lamellar phase composed of water, a non adsorbing water-soluble polymer (polyvynilpyrolidone), fluid membranes, made from a mixture of a cationic surfactant (cetylpiridiumchloride) and a cosurfactant (hexanol), are presented for various membrane as well as polymer concentrations. The data are fitted with a recently proposed model which takes into account the geometry and the fluctuations of these periodic structures. This allows a quantitative study of the polymer contribution to the smectic compression modulus of the lamellar phase. Four different regimes of polymer confinement are expected. The associated variations in are compared to a recent theoretical model, which predicts the polymer-mediated contribution to the smectic compression modulus. Received 20 January 1998     

Bounded step superdiffusion in an oriented hexagonal phase

Fluorescence recovery after pattern photobleaching is used to measure the self-diffusion of surfactant molecules, along cylinders and perpendicular to their main axis in an oriented hexagonal lyotropic phase. Unexpectedly, while the motion along cylinders is diffusive, a superdiffusive behavior is observed in the direction perpendicular to the cylinder axis. Moreover, varying the lattice parameter, we found that the perpendicular diffusion time is governed only by the number of cylinders to cross, providing experimental evidence for superdiffusion with a bounded step length.     

Copolymer-induced stabilizing effect of highly swollen hexagonal mesophases

We show that small amounts of copolymer that decorate an oil/water interface can greatly enhance the stability of swollen surfactant hexagonal phases, comprising oil tubes regularly arranged in a water matrix. Both the radius of the tubes and the thickness of the aqueous channel between the tubes can be controlled independently over large ranges. Such soft composite materials offer a potential interest for the synthesis of mesoporous materials.     

Structural signature of a brittle-to-ductile transition in self-assembled networks

We study the nonlinear rheology of a novel class of transient networks, made of surfactant micelles of tunable morphology reversibly linked by block copolymers. We couple rheology and time-resolved structural measurements, using synchrotron radiation, to characterize the highly nonlinear viscoelastic regime. We propose the fluctuations of the degree of alignment of the micelles under shear as a probe to identify a fracture process. We show a clear signature of a brittle-to-ductile transition in transient gels, as the morphology of the micelles varies, and provide a parallel between the fracture of solids and the fracture under shear of viscoelastic fluids.     

Inwardly curved polymer brushes: concave is not like convex

The European Physical Journal E - Inwardly curved polymer brushes are present in cylindrical and spherical micelles or in membranes tubes and vesicles decorated with anchored polymers, and...     

Fractures in complex fluids: the case of transient networks

We present a comprehensive review of the current state of fracture phenomena in transient networks, a wide class of viscoelastic fluids. We will first define what is a fracture in a complex fluid and recall the main structural and rheological properties of transient networks. Secondly, we review experimental reports on fractures of transient networks in several configurations: shear-induced fractures, fractures in Hele–Shaw cells, and fracture in extensional geometries (filament-stretching rheometry and pendant drop experiments), including fracture propagation. The tentative extension of the concepts of brittleness and ductility to the fracture mechanisms in transient networks is also discussed. Finally, the different and apparently contradictory theoretical approaches developed to interpret fracture nucleation will be addressed and confronted to experimental results. Rationalized criteria to discriminate the relevance of these different models will be proposed.     

Unusual Interfacial Phase Behavior of Two Nonmiscible Liquids in a Cylindrical Test Tube: Equilibrium Shapes and Stability of Axisymmetric Liquid Bridges under Gravity

In this paper the unusual interfacial phase behavior of two nonmiscible fluids contained in a cylindrical glass test tube is reported. Water, which is the lighter phase, takes up the upper part of the tube, whereas the denser compound (a hydrofluorocarbon) is in the bottom. However, below some critical volume of water, the denser phase emerges at the air surface, by forming an axisymmetric liquid bridge through the aqueous phase. Above the critical condition, the formation of the bridge, the evolution of the shape of this bridge, and its final breakdown can be visually inspected after shaking the tube. The minority liquid (water) is dispersed in the majority phase (HCFC) as an unstable dispersion of droplets. Droplets rise to the air surface under the action of the buoyant force, and coalesce on the glass wall: this leads to the formation of a bridge (made from the dispersion in the middle of a hollow axisymmetric water drop), whose height increases and thickness decreases during the coalescence process, until it breaks down. Using a free energy analysis, we state the exact variational problem via its Euler-Lagrange equation. However, since this nonlinear differential equation cannot be solved analytically, a simplified "mean-field" approach is developed, which provides a comprehensive insight into the physical origin of these capillary bridges and their stability under gravity. Copyright 2000 Academic Press.     

Structure and rheological properties of model microemulsion networks filled with nanoparticles

Model microemulsion networks of oil droplets stabilized by non-ionic surfactant and telechelic polymer C18 -PEO(10k)- C18 have been studied for two droplet-to-polymer size ratios. The rheological properties of the networks have been measured as a function of network connectivity and can be described in terms of simple percolation laws. The network structure has been characterised by Small Angle Neutron Scattering (SANS). A Reverse Monte Carlo (RMC) approach is used to demonstrate the interplay of attraction and repulsion induced by the copolymer. These model networks are then used as matrix for the incorporation of silica nanoparticles (R = 10 nm), individual dispersion being checked by scattering. A strong impact on the rheological properties is found for silica volume fractions up to 9%. q(A-1).