arXiv subjects

Armand Ajdari

Publications and source records attributed to Armand Ajdari.

At least 19 recordsLinked to original sources

arXiv2009

Towards an understanding of induced-charge electrokinetics at large applied voltages in concentrated solutions

The venerable theory of electrokinetic phenomena rests on the hypothesis of a dilute solution of point-like ions near a weakly charged surface, whose potential relative to the bulk is of order the thermal voltage ($kT/e \approx 25$ mV at room temperature). In nonlinear electrokinetic phenomena, such as AC or induced-charge electro-osmosis (ACEO, ICEO) and induced-charge electrophoresis (ICEP), several Volts $\approx 100 kT/e$ are applied to polarizable surfaces in microscopic geometries, and the resulting electric fields and induced surface charges are large enough to violate the assumptions of the classical theory. In this article, we review the literature, highlight discrepancies between theory and experiment, introduce possible modifications of the theory, and analyze their consequences. We argue that, in response to a large applied voltage, the "compact layer" and "shear plane" effectively advance into the liquid, due to the crowding of counter-ions. Using simple continuum models, we predict two general trends, each enhanced by dielectric response: (i) ionic crowding against a blocking surface expands the diffuse double layer and thus decreases its differential capacitance, and (ii) a charge-induced viscosity increase near the surface reduces the electro-osmotic mobility. The first effect is able to predict high-frequency flow reversal in ACEO pumps, while the second may explain the decay of ICEO flow with increasing salt concentration. Through examples, such as ICEP of an uncharged metal sphere in an asymmetric electrolyte, we show that ICEO flows are ion-specific. Similar issues arise in nanofluidics (due to confinement) and ionic liquids (due to the lack of solvent), so the paper concludes with a general framework of modified electrokinetic equations for finite-sized ions.

physics.flu-dyn↗

arXiv2009

A kinetic theory of plastic flow in soft glassy materials

A kinetic model for the elasto-plastic dynamics of a flowing jammed material is proposed, which takes the form of a non-local -- Boltzmann-like -- kinetic equation for the stress distribution function. Coarse-graining this equation yields a non-local constitutive law for the flow, introducing as a key dynamic quantity the local rate of plastic events. This quantity, interpreted as a local fluidity, is spatially correlated, with a correlation length diverging in the quasi-static limit, i.e. close to yielding. We predict finite size effects in the flow behavior, as well as the absence of an intrinsic local flow curves. These features are supported by recent experimental and numerical observations.

cond-mat.soft↗

arXiv2009

Stochastic Low Reynolds Number Swimmers

As technological advances allow us to fabricate smaller autonomous self-propelled devices, it is clear that at some point directed propulsion could not come from pre-specified deterministic periodic deformation of the swimmer's body and we need to develop strategies to extract a net directed motion from a series of random transitions in the conformation space of the swimmer. We present a theoretical formulation to describe the "stochastic motor" that drives the motion of low Reynolds number swimmers based on this concept, and use it to study the propulsion of a simple low Reynolds number swimmer, namely, the three-sphere swimmer model. When the detailed-balanced is broken and the motor is driven out of equilibrium, it can propel the swimmer in the required direction. The formulation can be used to study optimal design strategies for molecular-scale low Reynolds number swimmers.

cond-mat.soft↗

arXiv2008

Modeling phase behavior for quantifying micro-pervaporation experiments

We present a theoretical model for the evolution of mixture concentrations in a micro-pervaporation device, similar to those recently presented experimentally. The described device makes use of the pervaporation of water through a thin PDMS membrane to build up a solute concentration profile inside a long microfluidic channel. We simplify the evolution of this profile in binary mixtures to a one-dimensional model which comprises two concentration-dependent coefficients. The model then provides a link between directly accessible experimental observations, such as the widths of dense phases or their growth velocity, and the underlying chemical potentials and phenomenological coefficients. It shall thus be useful for quantifying the thermodynamic and dynamic properties of dilute and dense binary mixtures.

cond-mat.soft↗

arXiv2008

Analytic results for the three-sphere swimmer at low Reynolds number

The simple model of a low Reynolds number swimmer made from three spheres that are connected by two arms is considered in its general form and analyzed. The swimming velocity, force--velocity response, power consumption, and efficiency of the swimmer are calculated both for general deformations and also for specific model prescriptions. The role of noise and coherence in the stroke cycle is also discussed.

cond-mat.soft↗

arXiv2007

Mechanical Response of a Small Swimmer Driven by Conformational Transitions

A conformation space kinetic model is constructed to drive the deformation cycle of a three-sphere swimmer to achieve propulsion at low Reynolds number. We analyze the effect of an external load on the performance of this kinetic swimmer, and show that it depends sensitively on where the force is exerted, so that there is no general force--velocity relation. We discuss how the conformational cycle of such swimmers should be designed to increase their performance in resisting forces applied at specific points.

cond-mat.soft↗

arXiv2007

Nonlinear Electrokinetics at large applied voltages

The classical theory of electrokinetic phenomena assumes a dilute solution of point-like ions in chemical equilibrium with a surface whose double-layer voltage is of order the thermal voltage, $k_BT/e = 25$ mV. In nonlinear ``induced-charge'' electrokinetic phenomena, such as AC electro-osmosis, several Volts $\approx 100 k_BT/e$ are applied to the double layer, so the theory breaks down and cannot explain many observed features. We argue that, under such a large voltage, counterions ``condense'' near the surface, even for dilute bulk solutions. Based on simple models, we predict that the double-layer capacitance decreases and the electro-osmotic mobility saturates at large voltages, due to steric repulsion and increased viscosity of the condensed layer, respectively. The former suffices to explain observed high frequency flow reversal in AC electro-osmosis; the latter leads to a salt concentration dependence of induced-charge flows comparable to experiments, although a complete theory is still lacking.

cond-mat.other↗

arXiv2007

Transverse transport of solutes between co-flowing pressure-driven streams for microfluidic studies of diffusion/reaction processes

We consider a situation commonly encountered in microfluidics: two streams of miscible liquids are brought at a junction to flow side by side within a microchannel, allowing solutes to diffuse from one stream to the other and possibly react. We focus on two model problems: (i) the transverse transport of a single solute from a stream into the adjacent one, (ii) the transport of the product of a diffusion-controlled chemical reaction between solutes originating from the two streams. Our description is made general through a non-dimensionalized formulation that incorporates both the parabolic Poiseuille velocity profile along the channel and thermal diffusion in the transverse direction. Numerical analysis over a wide range of the streamwise coordinate $x$ reveal different regimes. Close to the top and the bottom walls of the microchannel, the extent of the diffusive zone follows three distinct power law regimes as $x$ is increased, characterized respectively by the exponents 1/2, 1/3 and 1/2. Simple analytical arguments are proposed to account for these results.

cond-mat.soft↗

arXiv2007

Propulsion of a molecular machine by asymmetric distribution of reaction--products

A simple model for the reaction-driven propulsion of a small device is proposed as a model for (part of) a molecular machine in aqueous media. Motion of the device is driven by an asymmetric distribution of reaction products. The propulsive velocity of the device is calculated as well as the scale of the velocity fluctuations. The effects of hydrodynamic flow as well as a number of different scenarios for the kinetics of the reaction are addressed.

cond-mat.soft↗

arXiv2006

Steric effects in the dynamics of electrolytes at large applied voltages: II. Modified Poisson-Nernst-Planck equations

In situations involving large potentials or surface charges, the Poisson Boltzman(PB) equation has shortcomings because it neglects ion-ion interactions and steric effects. This has been widely recognized by the electrochemistry community, leading to the development of various alternative models resulting in different sets "modified PB equations", which have had at least qualitative success in predicting equilibrium ion distributions. On the other hand, the literature is scarce in terms of descriptions of concentration dynamics in these regimes. Here, adapting strategies developed to modify the PB equation, we propose a simple modification of the widely used Poisson-Nernst-Planck (PNP) equations for ionic transport, which at least qualitatively accounts for steric effects. We analyze numerical solutions of these MPNP equations on the model problem of the charging of a simple electrolyte cell, and compare the outcome to that of the standard PNP equations. Finally, we repeat the asymptotic analysis of Bazant, Thornton, and Ajdari(2004} for this new system of equations to further document the interest and limits of validity of the simpler equivalent electrical circuit models introduced in Part I for such problems.

physics.chem-ph↗

arXiv2006

Steric effects in the dynamics of electrolytes at large applied voltages: I. Double-layer charging

The classical Poisson-Boltzmann (PB) theory of electrolytes assumes a dilute solution of point charges with mean-field electrostatic forces. Even for very dilute solutions, however, it predicts absurdly large ion concentrations (exceeding close packing) for surface potentials of only a few tenths of a volt, which are often exceeded, e.g. in microfluidic pumps and electrochemical sensors. Since the 1950s, several modifications of the PB equation have been proposed to account for the finite size of ions in equilibrium, but in this two-part series, we consider steric effects on diffuse charge dynamics (in the absence of electro-osmotic flow). In this first part, we review the literature and analyze two simple models for the charging of a thin double layer, which must form a condensed layer of close-packed ions near the surface at high voltage. A surprising prediction is that the differential capacitance typically varies non-monotonically with the applied voltage, and thus so does the response time of an electrolytic system. In PB theory, the capacitance blows up exponentially with voltage, but steric effects actually cause it to decrease above a threshold voltage where ions become crowded near the surface. Other nonlinear effects in PB theory are also strongly suppressed by steric effects: The net salt adsorption by the double layers in response to the applied voltage is greatly reduced, and so is the tangential "surface conduction" in the diffuse layer, to the point that it can often be neglected compared to bulk conduction (small Dukhin number).

physics.chem-ph↗

arXiv2006

Microfluidic Exploration of the Phase Diagram of a Surfactant/Water Binary System

We investigate the behaviour of a binary surfactant solution (AOT/water) as it is progressively concentrated in microfluidic evaporators. We observe in time a succession of phase transitions from a dilute solution up to a dense state, which eventually grows and invades the microchannels. Analyzing these observations, we show that, with a few experiments and a limited amount of material, our microdevices permit a semi-quantitative screening of the equilibrium phase diagram as well as a few kinetic observations.

cond-mat.soft↗

arXiv2006

Giant amplification of interfacially driven transport by hydrodynamic slip: diffusio-osmosis and beyond

We demonstrate that "moderate" departures from the no-slip hydrodynamic boundary condition (hydrodynamic slip lengths in the nanometer range) can result in a very large enhancement - up to two orders of magnitude- of most interfacially driven transport phenomena. We study analytically and numerically the case of neutral solute diffusio-osmosis in a slab geometry to account for non-trivial couplings between interfacial structure and hydrodynamic slip. Possible outcomes are fast transport of particles in externally applied or self-generated gradient, and flow enhancement in nano- or micro-fluidic geometries.

cond-mat.soft↗

arXiv2006

Micro-evaporators for kinetic exploration of phase diagrams

We use pervaporation-based microfluidic devices to concentrate species in aqueous solutions with spatial and temporal control of the process. Using experiments and modelling, we quantitatively describe the advection-diffusion behavior of the concentration field of various solutions (electrolytes, colloids, etc) and demonstrate the potential of these devices as universal tools for the kinetic exploration of the phases and textures that form upon concentration.

cond-mat.soft↗

arXiv2004

Slow flows of yield stress fluids: complex spatio-temporal behaviour within a simple elasto-plastic model

A minimal athermal model for the flow of dense disordered materials is proposed, based on two generic ingredients: local plastic events occuring above a microscopic yield stress, and the non-local elastic release of the stress these events induce in the material. A complex spatio-temporal rheological behaviour results, with features in line with recent experimental observations. At low shear rates, macroscopic flow actually originates from collective correlated bursts of plastic events, taking place in dynamically generated fragile zones. The related correlation length diverges algebraically at small shear rates. In confined geometries bursts occur preferentially close to the walls yielding an intermittent form of flow localization.

cond-mat.soft↗

arXiv2004

Elastic consequences of a single plastic event : a step towards the microscopic modeling of the flow of yield stress fluids

With the eventual aim of describing flowing elasto-plastic materials, we focus on the elementary brick of such a flow, a plastic event, and compute the long-range perturbation it elastically induces in a medium submitted to a global shear strain. We characterize the effect of a nearby wall on this perturbation, and quantify the importance of finite size effects. Although for the sake of simplicity most of our explicit formulae deal with a 2D situation, our statements hold for 3D situations as well.

cond-mat.soft↗

arXiv2004

Diffuse-Charge Dynamics in Electrochemical Systems

The response of a model micro-electrochemical system to a time-dependent applied voltage is analyzed. The article begins with a fresh historical review including electrochemistry, colloidal science, and microfluidics. The model problem consists of a symmetric binary electrolyte between parallel-plate, blocking electrodes which suddenly apply a voltage. Compact Stern layers on the electrodes are also taken into account. The Nernst-Planck-Poisson equations are first linearized and solved by Laplace transforms for small voltages, and numerical solutions are obtained for large voltages. The ``weakly nonlinear'' limit of thin double layers is then analyzed by matched asymptotic expansions in the small parameter $ε= λ_D/L$, where $λ_D$ is the screening length and $L$ the electrode separation. At leading order, the system initially behaves like an RC circuit with a response time of $λ_D L / D$ (not $λ_D^2/D$), where $D$ is the ionic diffusivity, but nonlinearity violates this common picture and introduce multiple time scales. The charging process slows down, and neutral-salt adsorption by the diffuse part of the double layer couples to bulk diffusion at the time scale, $L^2/D$. In the ``strongly nonlinear'' regime (controlled by a dimensionless parameter resembling the Dukhin number), this effect produces bulk concentration gradients, and, at very large voltages, transient space charge. The article concludes with an overview of more general situations involving surface conduction, multi-component electrolytes, and Faradaic processes.

cond-mat.soft↗

arXiv2003

Effects of intermediate bound states in dynamic force spectroscopy

We revisit here some aspects of the interpretation of dynamic force spectroscopy experiments. The standard theory predicts a typical unbinding force $f^*$ linearly proportional to the logarithm of the loading rate $r$ when a single energetical barrier controls the unbinding process; for a more complex situation of $N$ barriers, it predicts at most $N$ linear segments for the $f^*$ vs. $\log(r)$ curve, each segment characterizing a different barrier. We here extend this existing picture using a refined approximation, we provide a more general analytical formula, and show that in principle up to $N(N+1)/2$ segments can show up experimentally. As a consequence the interpretation of data can be ambiguous, for the characteristics and even the number of barriers. A further possible outcome of a multiple-barrier landscape is a bimodal or multimodal distribution of the unbinding force at a given loading rate, a feature recently observed experimentally.

cond-mat.stat-mech↗