397 research outputs found
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
s. 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
Coordination cage-based emulsifiers: templated formation of metal oxide microcapsules monitored by in situ LC-TEM
Metallo-supramolecular self-assembly has yielded a plethora of discrete nanosystems, many of which show competence in capturing guests and catalyzing chemical reactions. However, the potential of low-molecular bottom-up self-assemblies in the development of structured inorganic materials has rarely been methodically explored so far. Herein, we present a new type of metallo-supramolecular surfactant with the ability to stabilize non-aqueous emulsions for a significant period. The molecular design of the surfactant is based on a heteroleptic coordination cage (CGA-3; CGA=Cage-based Gemini Amphiphile), assembled from two pairs of organic building blocks, grouped around two Pd(II) cations. Shape-complementarity between the differently functionalized components generates discrete amphiphiles with a tailor-made polarity profile, able to stabilize non-aqueous emulsions, such as hexadecane-in-DMSO. These emulsions were used as a medium for the synthesis of spherical metal oxide microcapsules (titanium oxide, zirconium oxide, and niobium oxide) from soluble, water-sensitive alkoxide precursors by allowing a controlled dosage of water to the liquid-liquid phase boundary. Synthesized materials were analyzed by a combination of electron microscopic techniques. In situ liquid cell transmission electron microscopy (LC-TEM) was utilized for the first time to visualize the dynamics of the emulsion-templated formation of hollow inorganic titanium oxide and zirconium oxide microspheres
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 ( 0.9 wt%) without the addition of
electrolytes. Microrheology measurements of 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 is a nonmonotonic function of the shear rate . In
stress-controlled experiments, the shear stress shows a plateau for
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
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