Showing papers in "European Physical Journal E in 2008"

Wetting transitions on textured hydrophilic surfaces

Abstract: We consider the quasi-static energy of a drop on a textured hydrophilic surface, with taking the contact angle hysteresis (CAH) into account. We demonstrate how energy varies as the contact state changes from the Cassie state (in which air is trapped at the drop bottom) to the Wenzel state (in which liquid fills the texture at the drop bottom) assuming that the latter state nucleates from the center of the drop bottom. When the textured substrate is hydrophilic enough to allow spontaneous penetration of liquid film of the texture thickness, the present theory asserts that the drop develops into an experimentally observed state in which a drop looks like an egg fried without flipped over (sunny-side up) with a well-defined radius of “the egg yolk.” Otherwise, the final contact state of the drop becomes like a Wenzel state, but with the contact circle smaller than the original Wenzel state due to the CAH. We provide simple analytical estimations for the yolk radius of the “sunny-side-up” state and for the final radius of the contact circle of the pseudo-Wenzel state.

Ellipsoidal particles at fluid interfaces.

Abstract: For partially wetting, ellipsoidal colloids trapped at a fluid interface, their effective, interface-mediated interactions of capillary and fluctuation-induced type are analyzed For contact angles different from 90( degrees ) , static interface deformations arise which lead to anisotropic capillary forces that are substantial already for micrometer-sized particles The capillary problem is solved using an efficient perturbative treatment which allows a fast determination of the capillary interaction for all distances between and orientations of two particles Besides static capillary forces, fluctuation-induced forces caused by thermally excited capillary waves arise at fluid interfaces For the specific choice of a spatially fixed three-phase contact line, the asymptotic behavior of the fluctuation-induced force is determined analytically for both the close-distance and the long-distance regime and compared to numerical solutions

Discrete rearranging disordered patterns, part I: Robust statistical tools in two or three dimensions

Abstract: Discrete rearranging patterns include cellular patterns, for instance liquid foams, biological tissues, grains in polycrystals; assemblies of particles such as beads, granular materials, colloids, molecules, atoms; and interconnected networks. Such a pattern can be described as a list of links between neighbouring sites. Performing statistics on the links between neighbouring sites yields average quantities (hereafter "tools") as the result of direct measurements on images. These descriptive tools are flexible and suitable for various problems where quantitative measurements are required, whether in two or in three dimensions. Here, we present a coherent set of robust tools, in three steps. First, we revisit the definitions of three existing tools based on the texture matrix. Second, thanks to their more general definition, we embed these three tools in a self-consistent formalism, which includes three additional ones. Third, we show that the six tools together provide a direct correspondence between a small scale, where they quantify the discrete pattern's local distortion and rearrangements, and a large scale, where they help describe a material as a continuous medium. This enables to formulate elastic, plastic, fluid behaviours in a common, self-consistent modelling using continuous mechanics. Experiments, simulations and models can be expressed in the same language and directly compared. As an example, a companion paper (P. Marmottant, C. Raufaste, and F. Graner, this issue, 25 (2008) DOI 10.1140/epje/i2007-10300-7) provides an application to foam plasticity.

Simulating (electro)hydrodynamic effects in colloidal dispersions: Smoothed profile method

Abstract: Previously, we have proposed a direct simulation scheme for colloidal dispersions in a Newtonian solvent (Phys. Rev. E 71, 036707 (2005)). An improved formulation called the “Smoothed Profile (SP) method” is presented here in which simultaneous time-marching is used for the host fluid and colloids. The SP method is a direct numerical simulation of particulate flows and provides a coupling scheme between the continuum fluid dynamics and rigid-body dynamics through utilization of a smoothed profile for the colloidal particles. Moreover, the improved formulation includes an extension to incorporate multi-component fluids, allowing systems such as charged colloids in electrolyte solutions to be studied. The dynamics of the colloidal dispersions are solved with the same computational cost as required for solving non-particulate flows. Numerical results which assess the hydrodynamic interactions of colloidal dispersions are presented to validate the SP method. The SP method is not restricted to particular constitutive models of the host fluids and can hence be applied to colloidal dispersions in complex fluids.

Anisotropic colloids through non-trivial buckling.

Abstract: We present a study on buckling of colloidal particles, including experimental, theoretical and numerical developments. Oil-filled thin shells prepared by emulsion templating show buckling in mixtures of water and ethanol, due to dissolution of the core in the external medium. This leads to conformations with a single depression, either axisymmetric or polygonal depending on the geometrical features of the shells. These conformations could be theoretically and/or numerically reproduced in a model of homogeneous spherical thin shells with bending and stretching elasticity, submitted to an isotropic external pressure.

Size-dependent denaturing kinetics of bovine serum albumin adsorbed onto gold nanospheres

Abstract: We have used localized surface plasmon resonance (LSPR) to monitor the kinetics of thermal denaturing of bovine serum albumin (BSA) adsorbed onto gold nanospheres of size 5 nm-100 nm. The effect of the protein on the LSPR was monitored by visible extinction spectroscopy. The wavelength of the peak extinction (resonance) is affected by the conformation of the adsorbed protein layer, and as such can be used as a very sensitive probe of thermal denaturing that is specific to the adsorbed (as opposed to free) protein. The time dependence of the denaturing is measured in the temperature range 60 °C–70 °C, and the lifetimes are used to calculate an activation barrier for thermal denaturing. The results show that thermally activated denaturing of proteins adsorbed onto nanoparticles has a nanoparticle-size-dependent activation barrier, and this barrier increases for decreasing particle size. This may have important implications for other protein-nanoparticle interactions.

Influence of hydrodynamic interactions on lane formation in oppositely charged driven colloids

Abstract: The influence of hydrodynamic interactions on lane formation of oppositely charged driven colloidal suspensions is investigated using Brownian dynamics computer simulations performed on the Rotne-Prager level of the mobility tensor. Two cases are considered, namely sedimentation and electrophoresis. In the latter case the Oseen contribution to the mobility tensor is screened due to the opposite motion of counterions. The simulation results are compared to that resulting from simple Brownian dynamics where hydrodynamic interactions are neglected. For sedimentation, we find that hydrodynamic interactions strongly disfavor laning. In the steady state of lanes, a macroscopic phase separation of lanes is observed. This is in marked contrast to the simple Brownian case where a finite size of lanes was obtained in the steady state. For strong Coulomb interactions between the colloidal particles a lateral square lattice of oppositely driven lanes is stable similar to the simple Brownian dynamics. In an electric field, on the other hand, the behavior is found in qualitative and quantitative accordance with the case of neglected hydrodynamics.

Local crystalline order in a 2D colloidal glass former

Abstract: A mixture of two types of super-paramagnetic colloidal particles with long-range dipolar interaction is confined by gravity to a flat interface of a hanging water droplet The particles are observed by video microscopy and the dipolar interaction strength is controlled by an external magnetic field The local structure as obtained by pair correlation functions and bond order statistics is investigated as a function of system temperature and relative concentration Although the system has no long-range order and exhibits glassy dynamics, different types of stable crystallites coexist The local order of the globally disordered structure is explained by a small set of specific crystal structures The statistics of crystal unit cells show a continuous increase of local order with decreasing system temperature as well as a dependence on sample history and local composition

Local friction at a sliding interface between an elastomer and a rigid spherical probe.

Abstract: This paper reports on spatially resolved measurements of the shear stress distribution at a frictional interface between a flat rubber substrate and a glass lens. Silicone rubber specimens marked close to their surface by a colored pattern have been prepared in order to measure the surface displacement field induced by the steady-state friction of the spherical probe. The deconvolution of this displacement field then provides the actual shear stress distribution at the contact interface. When a smooth glass lens is used, a nearly constant shear stress is achieved within the contact. On the other hand, a bell-shaped shear stress distribution is obtained with rough lenses. These first results suggest that simple notions of real contact area and constant interface shear stress cannot account for the observed changes in local friction when roughness is varied.

Diffusing wave spectroscopy in Maxwellian fluids.

Abstract: We present a critical assessment of the diffusing wave spectroscopy (DWS) technique for obtaining the characteristic lengths and for measuring the loss and storage moduli of a reasonable well-known wormlike micelle (WM) system. For this purpose, we tracked the Brownian motion of particles using DWS embedded in a Maxwellian fluid constituted by a wormlike micellar solution made of cetyltrimethylammonium bromide (CTAB), sodium salicylate (NaSal), and water. We found that the motion of particles was governed by the viscosity of the solvent at short times and by the stress relaxation mechanisms of the giant micelles at longer times. From the time evolution of the mean square displacement of particles, we could obtain for the WM solution the cage size where each particle is harmonically bound at short times, the long-time diffusion coefficient, and experimental values for the exponent that accounts for the broad spectrum of relaxation times at the plateau onset time found in the (deltar2(t)) vs. time curves. In addition, from the (deltar2(t)) vs. time curves, we obtained G'(omega) and G"(omega) for the WM solutions. All the DWS microreological information allowed us to estimate the characteristic lengths of the WM network. We compare our DWS microrheological results and characteristic lengths with those obtained with mechanical rheometers at different NaSal/CTAB concentration ratios and temperatures.

Bacterium organizes hierarchical amorphous structure in microbial cellulose

Abstract: A pellicle, a gel film of microbial cellulose, is a supermolecular system containing 99% of water by weight, which is closely related to an amorphous structure in it. Using ultra-small-angle neutron scattering, in order to cover over a wide range of length scales from nm to 10μm, we examined the hierarchical amorphous structure in the microbial cellulose, which is synthesized by a bacterium (Acetobacter xylinum). The microbial cellulose swollen by water shows small-angle scattering that obeys a power law q -behavior according to q-α as a function of the magnitude of the scattering vector q . The power law, determined by scattering, is attributed to a mass fractal due to the distribution of the center of mass for the crystallite (microfibril) in amorphous cellulose swollen by water. As q increases, α takes the values of 2.5, 1, and 2.35, corresponding, respectively, to a gel network composed of bundles, a bundle composed of cellulose ribbons, and concentration fluctuations in a bundle. From the mass fractal q -behavior and its length scale limits, we evaluated a volume fraction of crystallite in microbial cellulose. It was found that 90% of the cellulose bundle is occupied by amorphous cellulose containing water.

Discrete rearranging disordered patterns, part II: 2D plasticity, elasticity and flow of a foam.

Abstract: The plastic flow of a foam results from bubble rearrangements. We study their occurrence in experiments where a foam is forced to flow in 2D: around an obstacle; through a narrow hole; or sheared between rotating disks. We describe their orientation and frequency using a topological matrix defined in the companion paper (F. Graner, B. Dollet, C. Raufaste, and P. Marmottant, this issue, 25 (2008) DOI 10.1140/epje/i2007-10298-8), which links them with continuous plasticity at large scale. We then suggest a phenomenological equation to predict the plastic strain rate: its orientation is determined from the foam's local elastic strain; and its rate is determined from the foam's local elongation rate. We obtain a good agreement with statistical measurements. This enables us to describe the foam as a continuous medium with fluid, elastic and plastic properties. We derive its constitutive equation, then test several of its terms and predictions.

Two-dimensional fluctuating vesicles in linear shear flow

Abstract: The stochastic motion of a two-dimensional vesicle in linear shear flow is studied at finite temperature. In the limit of small deformations from a circle, Langevin-type equations of motion are derived, which are highly nonlinear due to the constraint of constant perimeter length. These equations are solved in the low-temperature limit and using a mean-field approach, in which the length constraint is satisfied only on average. The constraint imposes non-trivial correlations between the lowest deformation modes at low temperature. We also simulate a vesicle in a hydrodynamic solvent by using the multi-particle collision dynamics technique, both in the quasi-circular regime and for larger deformations, and compare the stationary deformation correlation functions and the time autocorrelation functions with theoretical predictions. Good agreement between theory and simulations is obtained.

Nanodroplets on rough hydrophilic and hydrophobic surfaces

Abstract: We present results of Molecular Dynamics (MD) calculations on the behavior of liquid nanodroplets on rough hydrophobic and hydrophilic solid surfaces. On hydrophobic surfaces, the contact angle for nanodroplets depends strongly on the root-mean-square roughness amplitude, but it is nearly independent of the fractal dimension of the surface. Since increasing the fractal dimension increases the short-wavelength roughness, while the long-wavelength roughness is almost unchanged, we conclude that for hydrophobic interactions the short-wavelength (atomistic) roughness is not very important. We show that the nanodroplet is in a Cassie-like state. For rough hydrophobic surfaces, there is no contact angle hysteresis due to strong thermal fluctuations, which occur at the liquid-solid interface on the nanoscale. On hydrophilic surfaces, however, there is strong contact angle hysteresis due to higher energy barrier. These findings may be very important for the development of artificially biomimetic superhydrophobic surfaces.

An elasto-visco-plastic model for immortal foams or emulsions

Abstract: A variety of complex fluids consist in soft, round objects (foams, emulsions, assemblies of copolymer micelles or of multilamellar vesicles --- also known as onions). Their dense packing induces a slight deviation from their prefered circular or spherical shape. As a frustrated assembly of interacting bodies, such a material evolves from one conformation to another through a succession of discrete, topological events driven by finite external forces. As a result, the material exhibits a finite yield threshold. The individual objects usually evolve spontaneously (colloidal diffusion, object coalescence, molecular diffusion), and the material properties under low or vanishing stress may alter with time, a phenomenon known as aging. We neglect such effects to address the simpler behaviour of (uncommon) immortal fluids: we construct a minimal, fully tensorial, rheological model, equivalent to the (scalar) Bingham model. Importantly, the model consistently describes the ability of such soft materials to deform substantially in the elastic regime (be it compressible or not) before they undergo (incompressible) plastic creep --- or viscous flow under even higher stresses.

Tunable-slip boundaries for coarse-grained simulations of fluid flow.

Abstract: On the micro- and nanoscale, classical hydrodynamic boundary conditions such as the no-slip condition no longer apply. Instead, the flow profiles exhibit “slip“ at the surface, which is characterized by a finite slip length (partial slip). We present a new, systematic way of implementing partial-slip boundary conditions with arbitrary slip length in coarse-grained computer simulations. The main idea is to represent the complex microscopic interface structure by a spatially varying effective viscous force. An analytical equation for the resulting slip length can be derived for planar and for curved surfaces. The comparison with computer simulations of a DPD (dissipative particle dynamics) fluid shows that this expression is valid from full slip to no slip.

Coefficient of tangential restitution for viscoelastic spheres

Abstract: The collision of frictional granular particles may be described by an interaction force whose normal component is that of viscoelastic spheres while the tangential part is described by the model by Cundall and Strack (Geotechnique 29, 47 (1979)) being the most popular tangential collision model in Molecular Dynamics simulations. Albeit being a rather complicated model, governed by 5 phenomenological parameters and 2 independent initial conditions, we find that it is described by 3 independent parameters only. Surprisingly, in a wide range of parameters the corresponding coefficient of tangential restitution, et, is well described by the simple Coulomb law with a cut-off at et = 0. A more complex behavior of the coefficient of restitution as a function on the normal and tangential components of the impact velocity, g n and g t , including negative values of e n , is found only for very small ratio g t /g n . For the analysis presented here we neglect dissipation of the interaction in normal direction.

Single-particle thermal diffusion of charged colloids: Double-layer theory in a temperature gradient

Abstract: The double-layer contribution to the single-particle thermal diffusion coefficient of charged, spherical colloids with arbitrary double-layer thickness is calculated and compared to experiments. The calculation is based on an extension of the Debye-Huckel theory for the double-layer structure that includes a small temperature gradient. There are three forces that constitute the total thermophoretic force on a charged colloidal sphere due to the presence of its double layer: i) the force F W that results from the temperature dependence of the internal electrostatic energy W of the double layer, ii) the electric force F el with which the temperature-induced non-spherically symmetric double-layer potential acts on the surface charges of the colloidal sphere and iii) the solvent-friction force F sol on the surface of the colloidal sphere due to the solvent flow that is induced in the double layer because of its asymmetry. The force F W will be shown to reproduce predictions based on irreversible-thermodynamics considerations. The other two forces F el and F sol depend on the details of the temperature-gradient-induced asymmetry of the double-layer structure which cannot be included in an irreversible-thermodynamics treatment. Explicit expressions for the thermal diffusion coefficient are derived for arbitrary double-layer thickness, which complement the irreversible-thermodynamics result through the inclusion of the thermophoretic velocity resulting from the electric- and solvent-friction force.

Capillary filling with pseudo-potential binary Lattice-Boltzmann model

Abstract: We present a systematic study of capillary filling for a binary fluid by using a mesoscopic lattice Boltzmann model for immiscible fluids describing a diffusive interface moving at a given contact angle with respect to the walls. The phenomenological way to impose a given contact angle is analysed. Particular attention is given to the case of complete wetting, that is contact angle equal to zero. Numerical results yield quantitative agreement with the theoretical Washburn’s law, provided that the correct ratio of the dynamic viscosities between the two fluids is used. Finally, the presence of precursor films is experienced and it is shown that these films advance in time with a square-root law but with a different prefactor with respect to the bulk interface.

Three-sphere low-Reynolds-number swimmer with a cargo container

Abstract: A recently introduced model for an autonomous swimmer at low Reynolds number that is comprised of three spheres connected by two arms is considered when one of the spheres has a large radius. The Stokes hydrodynamic flow associated with the swimming strokes and net motion of this system can be studied analytically using the Stokes Green's function of a point force in front of a sphere of arbitrary radius R provided by Oseen. The swimming velocity is calculated, and shown to scale as 1/R3 with the radius of the sphere.

The large amplitude oscillatory strain response of aqueous foam: Strain localization and full stress Fourier spectrum

Abstract: We study the low frequency stress response of aqueous foams, subjected to oscillatory strain. As the strain amplitude is progressively increased starting from zero, the initially linear viscoelastic response becomes nonlinear as yielding sets in. To characterize this crossover from solid-like to liquid-like behaviour quantitatively, the full harmonic spectrum of the stress is measured. These results are compared to the soft glassy rheology model as well as to elastoplastic models. Moreover, to check for strain localization, we monitor the displacement profile of the bubbles at the free surface of the foam sample in a Couette cell using video microscopy. These observations indicate that strain localisation occurs close to the middle of the gap, but only at strain amplitudes well above the yield strain.

Effect of atmosphere on reductions in the glass transition of thin polystyrene films

Abstract: We have used nulling ellipsometry to measure the glass transition temperature, T g , of thin films of polystyrene in ambient, dry nitrogen, and vacuum environments. For all environments, the measured T g values decrease with decreasing film thickness in a way that is quantitatively similar to previously reported studies in ambient conditions. These results provide strong reinforcement of previous conclusions that such reduced T g values are an intrinsic property of the confined material. Furthermore, the results are in contrast to recent reports which suggest that the T g reductions measured by many researchers are the results of artifacts (i.e. degradation of the polymer due to annealing in ambient conditions, or moisture content).

Molecular Dynamics simulation of a polymer chain translocating through a nanoscopic pore: hydrodynamic interactions versus pore radius.

Abstract: The detection of linear polymers translocating through a nanoscopic pore is a promising idea for the development of new DNA analysis techniques. However, the physics of constrained macromolecules and the fluid that surrounds them at the nanoscopic scale is still not well understood. In fact, many theoretical models of polymer translocation neglect both excluded-volume and hydrodynamic effects. We use Molecular Dynamics simulations with explicit solvent to study the impact of hydrodynamic interactions on the translocation time of a polymer. The translocation time τ that we examine is the unbiased (no charge on the chain and no driving force) escape time of a polymer that is initially placed halfway through a pore perforated in a monolayer wall. In particular, we look at the effect of increasing the pore radius when only a small number of fluid particles can be located in the pore as the polymer undergoes translocation, and we compare our results to the theoretical predictions of Chuang et al. (Phys. Rev. E 65, 011802 (2001)). We observe that the scaling of the translocation time varies from τ ∼ N 11/5 to τ ∼ N 9/5 as the pore size increases (N is the number of monomers that goes up to 31 monomers). However, the scaling of the polymer relaxation time remains consistent with the 9/5 power law for all pore radii.

Simulation of charge reversal in salty environments: Giant overcharging?

Abstract: We have performed MD simulations of a highly charged colloid in a solution of 3:1 and additional 1:1 salt. The dependency of the colloid's inverted charge on the concentration of the additional 1:1 salt has been studied. Most theories predict, that the inverted charge increases when the concentration of monovalent salt grows, up to what is called giant overcharging, while experiments and simulational studies observe the opposite. Our simulations agree with the experimental findings and shed light onto the weaknesses of the theories.

On the study of local-stress rearrangements during quasi-static plastic shear of a model glass: do local-stress components contain enough information?

Abstract: We present a numerical study of the mechanical response of a 2D Lennard-Jones amorphous solid under steady quasi-static and athermal shear. We focus here on the evolution of local stress components. While the local stress is usually taken as an order parameter in the description of the rheological behaviour of complex fluids, and for plasticity in glasses, we show here that the knowledge of local stresses is not sufficient for a complete description of the plastic behaviour of our system. The distribution of local stresses can be approximately described as resulting from the sum of localized quadrupolar events with an exponential distribution of amplitudes. However, we show that the position of the center of the quadrupoles is not related to any special evolution of the local stress, but must be described by another variable.

Electrowetting --A versatile tool for controlling microdrop generation

Abstract: Integrating insulator-covered electrodes into a microfluidic flow focusing device (FFD) we demonstrate enhanced flexibility and control of the flow of two non-miscible liquids based on electrowetting (EW). In the parameters space, determined by liquid inlet pressures, we identify a specific region where drops can only be generated and addressed via EW. In this regime we show that the size distribution and the frequency of drop generation can be controlled by the applied voltage and the width of voltage pulses. Moreover it turns out that with EW the drop size and the frequency can be tuned independently. Finally we show that the same drop generation phenomena can also be observed in the presence of surfactants.

Thermal diffusion and bending kinetics in nematic elastomer cantilever

Abstract: Vertically aligned monodomain nematic liquid-crystal elastomers contract when heated. If a temperature gradient is applied across the width of such a cantilever, inhomogeneous strain distribution leads to bending motion. We modelled the kinetics of thermally induced bending in the limit of a long thin strip and the predicted time variation of curvature agreed quantitatively with experimental data from samples with a range of critical indices and nematic-isotropic transition temperatures. We also deduced a value for the thermal diffusion coefficient of the elastomer.

Morphological instabilities of polymer crystals

Abstract: We present experimental observations at comparatively low supercooling of morphology transitions from dendritic to faceted structures in polymer crystals growing in thin films of a poly-2-vinylpyridineblock-polyethyleneoxid copolymer. Our results are compared with theoretical concepts describing morphological instabilities of single crystals. Although these concepts originally were not developed for polymers, they allow to describe and interpret our experimental results quite well. In particular, the measured temperature dependence of the width W and frequency of dendritic side branches and the radius of curvature ρ of the growth tips of the crystals follow these concepts. We present preliminary evidence for the influence of polymer attachment kinetics and reorganisation processes behind the growth front. Polymer thin films provide valuable model systems for studying general concepts of crystallisation and allow to distinguish at which point the connectivity of the crystallising units within chain-like molecules starts to play a measurable role.

Dielectric and conductivity relaxation in mixtures of glycerol with LiCl.

Abstract: We report a thorough dielectric characterization of the α relaxation of glass-forming glycerol with varying additions of LiCl. Nine salt concentrations from 0.1 to 20mol% are investigated in a frequency range of 20Hz-3GHz and analyzed in the dielectric loss and modulus representation. Information on the dc conductivity, the dielectric relaxation time (from the loss) and the conductivity relaxation time (from the modulus) is provided. Overall, with increasing ion concentration, a transition from reorientationally to translationally dominated behavior is observed and the translational ion dynamics and the dipolar reorientational dynamics become successively coupled. This gives rise to the prospect that, by adding ions to dipolar glass formers, dielectric spectroscopy may directly couple to the translational degrees of freedom determining the glass transition, even in frequency regimes where usually strong decoupling is observed.

Bending modulus of lipid bilayers in a liquid-crystalline phase including an anomalous swelling regime estimated by neutron spin echo experiments

Abstract: Membrane fluctuations of dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) were investigated by neutron spin echo spectroscopy The intermediate structure factor was analyzed in terms of the model proposed by Zilman and Granek (Phys Rev Lett 77, 4788 (1996)), and the bending modulus of lipid bilayers was derived The hardening of a lipid bilayer upon approaching the main transition point in the anomalous swelling regime was observed, which naturally connects the bending modulus in the gel phase below the main transition temperature