Elastometry of deflated capsules elastic moduli from shape and wrinkle analysis

Elastic capsules, prepared from droplets or bubbles attached to a capillary (as in a pendant drop tensiometer), can be deflated by suction through the capillary. We study this deflation and show that a combined analysis of the shape and wrinkling characteristics enables us to determine the elastic properties in situ. Shape contours are analyzed and fitted using shape equations derived from nonlinear membrane-shell theory to give the elastic modulus, Poisson ratio and stress distribution of the membrane. We include wrinkles, which generically form upon deflation, within the shape analysis. Measuring the wavelength of wrinkles and using the calculated stress distribution gives the bending stiffness of the membrane. We illustrate this method on two very different capsule materials: polymerized octadecyltrichlorosilane (OTS) capsules and hydrophobin (HFBII) coated bubbles. Our results are in agreement with the available rheological data. For hydrophobin coated bubbles the method reveals an interesting nonlinear behavior consistent with the hydrophobin molecules having\ud a rigid core surrounded by a softer shell

Spatio-temporal dynamics of wormlike micelles under shear

Velocity profiles in a wormlike micelle solution (CTAB in D2O) are recorded using ultrasound every 2 s after a step-like shear rate into the shear-banding regime. The stress relaxation occurs over more than six hours and corresponds to the very slow nucleation and growth of the high-shear band. Moreover, oscillations of the interface position with a period of about 50 s are observed during the growth process. Strong wall slip, metastable states and transient nucleation of three-band flows are also reported and discussed in light of previous experiments and theoretical models.Comment: 4 pages, 5 figures, submitted to Phys.Rev.Let

Oscillations of a solid sphere falling through a wormlike micellar fluid

We present an experimental study of the motion of a solid sphere falling through a wormlike micellar fluid. While smaller or lighter spheres quickly reach a terminal velocity, larger or heavier spheres are found to oscillate in the direction of their falling motion. The onset of this instability correlates with a critical value of the velocity gradient scale $\Gamma_{c}\sim 1$ s$^{-1}$. We relate this condition to the known complex rheology of wormlike micellar fluids, and suggest that the unsteady motion of the sphere is caused by the formation and breaking of flow-induced structures.Comment: 4 pages, 4 figure

Velocity profiles in shear-banding wormlike micelles

Using Dynamic Light Scattering in heterodyne mode, we measure velocity profiles in a much studied system of wormlike micelles (CPCl/NaSal) known to exhibit both shear-banding and stress plateau behavior. Our data provide evidence for the simplest shear-banding scenario, according to which the effective viscosity drop in the system is due to the nucleation and growth of a highly sheared band in the gap, whose thickness linearly increases with the imposed shear rate. We discuss various details of the velocity profiles in all the regions of the flow curve and emphasize on the complex, non-Newtonian nature of the flow in the highly sheared band.Comment: 4 pages, 5 figures, submitted to Phys. Rev. Let

Ehrenfest relations at the glass transition: solution to an old paradox

In order to find out whether there exists a thermodynamic description of the glass phase, the Ehrenfest relations along the glass transition line are reconsidered. It is explained that the one involving the compressibility is always satisfied, and that the one involving the specific heat is principally incorrect. Thermodynamical relations are presented for non-ergodic systems with a one-level tree in phase space. They are derived for a spin glass model, checked for other models, and expected to apply, e.g., to glass forming liquids. The second Ehrenfest relation gets a contribution from the configurational entropy.Comment: 4 pages revtex, to appear in Phys. Rev. Let

Thermodynamic picture of the glassy state

A picture for thermodynamics of the glassy state is introduced. It assumes that one extra parameter, the effective temperature, is needed to describe the glassy state. This explains the classical paradoxes concerning the Ehrenfest relations and the Prigogine-Defay ratio. As a second part, the approach connects the response of macroscopic observables to a field change with their temporal fluctuations, and with the fluctuation-dissipation relation, in a generalized non-equilibrium way.Comment: Proceedings of the Conference "Unifying Concepts in Glass Physics", ICTP, Trieste, 15 - 18 September 199

Linear and nonlinear rheology of wormlike micelles

Several surfactant molecules self-assemble in solution to form long, cylindrical, flexible wormlike micelles. These micelles can be entangled with each other leading to viscoelastic phases. The rheological properties of such phases are very interesting and have been the subject of a large number of experimental and theoretical studies in recent years. We shall report on our recent work on the macrorheology, microrheology and nonlinear flow behaviour of dilute aqueous solutions of a surfactant CTAT (Cetyltrimethylammonium Tosilate). This system forms elongated micelles and exhibits strong viscoelasticity at low concentrations ($\sim$ 0.9 wt%) without the addition of electrolytes. Microrheology measurements of $G(\omega)$ have been done using diffusing wave spectroscopy which will be compared with the conventional frequency sweep measurements done using a cone and plate rheometer. The second part of the paper deals with the nonlinear rheology where the measured shear stress $\sigma$ is a nonmonotonic function of the shear rate $\dot{\gamma}$. In stress-controlled experiments, the shear stress shows a plateau for $\dot{\gamma}$ larger than some critical strain rate, similar to the earlier reports on CPyCl/NaSal system. Cates et al have proposed that the plateau is a signature of mechanical instability in the form of shear bands. We have carried out extensive experiments under controlled strain rate conditions, to study the time-dependence of shear stress. The measured time series of shear stress has been analysed in terms of correlation integrals and Lyapunov exponents to show unambiguously that the behaviour is typical of low dimensional dynamical systems.Comment: 15 pages, 10 eps figure

Structure factor of polymers interacting via a short range repulsive potential: application to hairy wormlike micelles

We use the Random Phase Approximation (RPA) to compute the structure factor, S(q), of a solution of chains interacting through a soft and short range repulsive potential V. Above a threshold polymer concentration, whose magnitude is essentially controlled by the range of the potential, S(q) exhibits a peak whose position depends on the concentration. We take advantage of the close analogy between polymers and wormlike micelles and apply our model, using a Gaussian function for V, to quantitatively analyze experimental small angle neutron scattering profiles of semi-dilute solutions of hairy wormlike micelles. These samples, which consist in surfactant self-assembled flexible cylinders decorated by amphiphilic copolymer, provide indeed an appropriate experimental model system to study the structure of sterically interacting polymer solutions

Vorticity Banding During the Lamellar-to-Onion Transition in a Lyotropic Surfactant Solution in Shear Flow

We report on the rheology of a lamellar lyotropic surfactant solution (SDS/dodecane/pentanol/water), and identify a discontinuous transition between two shear thinning regimes which correspond to the low stress lamellar phase and the more viscous shear induced multi-lamellar vesicle, or ``onion'' phase. We study in detail the flow curve, stress as a function of shear rate, during the transition region, and present evidence that the region consists of a shear banded phase where the material has macroscopically separated into bands of lamellae and onions stacked in the vorticity direction. We infer very slow and irregular transformations from lamellae to onions as the stress is increased through the two phase region, and identify distinct events consistent with the nucleation of small fractions of onions that coexist with sheared lamellae.Comment: 10 pages, 10 figure