arXiv subjects

Martin Z. Bazant

Publications and source records attributed to Martin Z. Bazant.

At least 163 records · Page 9Linked to original sources

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

A stochastic flow rule for granular materials

There have been many attempts to derive continuum models for dense granular flow, but a general theory is still lacking. Here, we start with Mohr-Coulomb plasticity for quasi-2D granular materials to calculate (average) stresses and slip planes, but we propose a "stochastic flow rule" (SFR) to replace the principle of coaxiality in classical plasticity. The SFR takes into account two crucial features of granular materials - discreteness and randomness - via diffusing "spots" of local fluidization, which act as carriers of plasticity. We postulate that spots perform random walks biased along slip-lines with a drift direction determined by the stress imbalance upon a local switch from static to dynamic friction. In the continuum limit (based on a Fokker-Planck equation for the spot concentration), this simple model is able to predict a variety of granular flow profiles in flat-bottom silos, annular Couette cells, flowing heaps, and plate-dragging experiments -- with essentially no fitting parameters -- although it is only expected to function where material is at incipient failure and slip-lines are inadmissible. For special cases of admissible slip-lines, such as plate dragging under a heavy load or flow down an inclined plane, we postulate a transition to rate-dependent Bagnold rheology, where flow occurs by sliding shear planes. With different yield criteria, the SFR provides a general framework for multiscale modeling of plasticity in amorphous materials, cycling between continuum limit-state stress calculations, meso-scale spot random walks, and microscopic particle relaxation.

cond-mat.soft↗

arXiv2006

Nonlinear electrochemical relaxation around conductors

We analyze the simplest problem of electrochemical relaxation in more than one dimension - the response of an uncharged, ideally polarizable metallic sphere (or cylinder) in a symmetric, binary electrolyte to a uniform electric field. In order to go beyond the circuit approximation for thin double layers, our analysis is based on the Poisson-Nernst-Planck (PNP) equations of dilute solution theory. Unlike most previous studies, however, we focus on the nonlinear regime, where the applied voltage across the conductor is larger than the thermal voltage. In such strong electric fields, the classical model predicts that the double layer adsorbs enough ions to produce bulk concentration gradients and surface conduction. Our analysis begins with a general derivation of surface conservation laws in the thin double-layer limit, which provide effective boundary conditions on the quasi-neutral bulk. We solve the resulting nonlinear partial differential equations numerically for strong fields and also perform a time-dependent asymptotic analysis for weaker fields, where bulk diffusion and surface conduction arise as first-order corrections. We also derive various dimensionless parameters comparing surface to bulk transport processes, which generalize the Bikerman-Dukhin number. Our results have basic relevance for double-layer charging dynamics and nonlinear electrokinetics in the ubiquitous PNP approximation.

cond-mat.mtrl-sci↗

arXiv2006

Interfacial dynamics in transport-limited dissolution

Various model problems of ``transport-limited dissolution'' in two dimensions are analyzed using time-dependent conformal maps. For diffusion-limited dissolution (reverse Laplacian growth), several exact solutions are discussed for the smoothing of corrugated surfaces, including the continuous analogs of ``internal diffusion-limited aggregation'' and ``diffusion-limited erosion''. A class of non-Laplacian, transport-limited dissolution processes are also considered, which raise the general question of when and where a finite solid will disappear. In a case of dissolution by advection-diffusion, a tilted ellipse maintains its shape during collapse, as its center of mass drifts obliquely away from the background fluid flow, but other initial shapes have more complicated dynamics.

cond-mat.stat-mech↗

arXiv2006

Dynamics of Random Packings in Granular Flow

We present a multiscale simulation algorithm for amorphous materials, which we illustrate and validate in a canonical case of dense granular flow. Our algorithm is based on the recently proposed Spot Model, where particles in a dense random packing undergo chain-like collective displacements in response to diffusing "spots" of influence, carrying a slight excess of interstitial free volume. We reconstruct the microscopic dynamics of particles from the "coarse grained" dynamics of spots by introducing a localized particle relaxation step after each spot-induced block displacement, simply to enforce packing constraints with a (fairly arbitrary) soft-core repulsion. To test the model, we study to what extent it can describe the dynamics of up to 135,000 frictional, viscoelastic spheres in granular drainage simulated by the discrete-element method (DEM). With only five fitting parameters (the radius, volume, diffusivity, drift velocity, and injection rate of spots), we find that the spot simulations are able to largely reproduce not only the mean flow and diffusion, but also some subtle statistics of the flowing packings, such as spatial velocity correlations and many-body structural correlations. The spot simulations run over 100 times faster than DEM and demonstrate the possibility of multiscale modeling for amorphous materials, whenever a suitable model can be devised for the coarse-grained spot dynamics.

cond-mat.soft↗

arXiv2006

Analysis of Granular Flow in a Pebble-Bed Nuclear Reactor

Pebble-bed nuclear reactor technology, which is currently being revived around the world, raises fundamental questions about dense granular flow in silos. A typical reactor core is composed of graphite fuel pebbles, which drain very slowly in a continuous refueling process. Pebble flow is poorly understood and not easily accessible to experiments, and yet it has a major impact on reactor physics. To address this problem, we perform full-scale, discrete-element simulations in realistic geometries, with up to 440,000 frictional, viscoelastic 6cm-diameter spheres draining in a cylindrical vessel of diameter 3.5m and height 10m with bottom funnels angled at 30 degrees or 60 degrees. We also simulate a bidisperse core with a dynamic central column of smaller graphite moderator pebbles and show that little mixing occurs down to a 1:2 diameter ratio. We analyze the mean velocity, diffusion and mixing, local ordering and porosity (from Voronoi volumes), the residence-time distribution, and the effects of wall friction and discuss implications for reactor design and the basic physics of granular flow.

cond-mat.soft↗

arXiv2005

The Average Shape of Transport-Limited Aggregates

We study the relation between stochastic and continuous transport-limited growth models, which generalize conformal-mapping formulations of diffusion-limited aggregation (DLA) and viscous fingering, respectively. We derive a nonlinear integro-differential equation for the asymptotic shape (average conformal map) of stochastic aggregates, whose mean-field approximation is the corresponding continuous equation, where the interface moves at its local expected velocity. Our equation accurately describes advection-diffusion-limited aggregation (ADLA), and, due to nonlinear averaging over fluctuations, the average ADLA cluster is similar, but not identical, to an exact solution of the mean-field dynamics. Similar results should apply to all models in our class, thus explaining the known discrepancies between average DLA clusters and viscous fingers in a channel geometry.

cond-mat.stat-mech↗

arXiv2005

Steady advection-diffusion around finite absorbers in two-dimensional potential flows

We perform an exhaustive study of the simplest, nontrivial problem in advection-diffusion -- a finite absorber of arbitrary cross section in a steady two-dimensional potential flow of concentrated fluid. This classical problem has been studied extensively in the theory of solidification from a flowing melt, and it also arises in Advection-Diffusion-Limited Aggregation. In both cases, the fundamental object is the flux to a circular disk, obtained by conformal mapping from more complicated shapes. We construct the first accurate numerical solution using an efficient new method, which involves mapping to the interior of the disk and using a spectral method in polar coordinates. Our method also combines exact asymptotics and an adaptive mesh to handle boundary layers. Starting from a well-known integral equation in streamline coordinates, we also derive new, high-order asymptotic expansions for high and low Péclet numbers ($\Pe$). Remarkably, the `high' $\Pe$ expansion remains accurate even for such low $\Pe$ as $10^{-3}$. The two expansions overlap well near $\Pe = 0.1$, allowing the construction of an analytical connection formula that is uniformly accurate for all $\Pe$ and angles on the disk with a maximum relative error of 1.75%. We also obtain an analytical formula for the Nusselt number ($\Nu$) as a function of the Péclet number with a maximum relative error of 0.53% for all possible geometries. Because our finite-plate problem can be conformally mapped to other geometries, the general problem of two-dimensional advection-diffusion past an arbitrary finite absorber in a potential flow can be considered effectively solved.

cond-mat.soft↗

arXiv2005

Velocity profile of granular flows inside silos and hoppers

We measure the flow of granular materials inside a quasi-two dimensional silo as it drains and compare the data with some existing models. The particles inside the silo are imaged and tracked with unprecedented resolution in both space and time to obtain their velocity and diffusion properties. The data obtained by varying the orifice width and the hopper angle allows us to thoroughly test models of gravity driven flows inside these geometries. All of our measured velocity profiles are smooth and free of the shock-like discontinuities ("rupture zones") predicted by critical state soil mechanics. On the other hand, we find that the simple Kinematic Model accurately captures the mean velocity profile near the orifice, although it fails to describe the rapid transition to plug flow far away from the orifice. The measured diffusion length $b$, the only free parameter in the model, is not constant as usually assumed, but increases with both the height above the orifice and the angle of the hopper. We discuss improvements to the model to account for the differences. From our data, we also directly measure the diffusion of the particles and find it to be significantly less than predicted by the Void Model, which provides the classical microscopic derivation of the Kinematic Model in terms of diffusing voids in the packing. However, the experimental data is consistent with the recently proposed Spot Model, based on a simple mechanism for cooperative diffusion. Finally, we discuss the flow rate as a function of the orifice width and hopper angles. We find that the flow rate scales with the orifice size to the power of 1.5, consistent with dimensional analysis. Interestingly, the flow rate increases when the funnel angle is increased.

cond-mat.soft↗

arXiv2005

The Spot Model for random-packing dynamics

The diffusion and flow of amorphous materials, such as glasses and granular materials, has resisted a simple microscopic description, analogous to defect theories for crystals. Early models were based on either gas-like inelastic collisions or crystal-like vacancy diffusion, but here we propose a cooperative mechanism for dense random-packing dynamics, based on diffusing ``spots'' of interstitial free volume. Simulations with the Spot Model can efficiently generate realistic flowing packings, and yet the model is simple enough for mathematical analysis. Starting from a non-local stochastic differential equation, we derive continuum equations for tracer diffusion, given the dynamics of free volume (spots). Throughout the paper, we apply the model to granular drainage in a silo, and we also briefly discuss glassy relaxation. We conclude by discussing the prospects of spot-based multiscale modeling and simulation of amorphous materials.

cond-mat.stat-mech↗

arXiv2004

Conformal mapping methods for interfacial dynamics

The article provides a pedagogical review aimed at graduate students in materials science, physics, and applied mathematics, focusing on recent developments in the subject. Following a brief summary of concepts from complex analysis, the article begins with an overview of continuous conformal-map dynamics. This includes problems of interfacial motion driven by harmonic fields (such as viscous fingering and void electromigration), bi-harmonic fields (such as viscous sintering and elastic pore evolution), and non-harmonic, conformally invariant fields (such as growth by advection-diffusion and electro-deposition). The second part of the article is devoted to iterated conformal maps for analogous problems in stochastic interfacial dynamics (such as diffusion-limited aggregation, dielectric breakdown, brittle fracture, and advection-diffusion-limited aggregation). The third part notes that all of these models can be extended to curved surfaces by an auxilliary conformal mapping from the complex plane, such as stereographic projection to a sphere. The article concludes with an outlook for further research.

cond-mat.soft↗

arXiv2004

Current-Voltage Relations for Electrochemical Thin Films

The dc response of an electrochemical thin film, such as the separator in a micro-battery, is analyzed by solving the Poisson-Nernst-Planck equations, subject to boundary conditions appropriate for an electrolytic/galvanic cell. The model system consists of a binary electrolyte between parallel-plate electrodes, each possessing a compact Stern layer, which mediates Faradaic reactions with nonlinear Butler-Volmer kinetics. Analytical results are obtained by matched asymptotic expansions in the limit of thin double layers and compared with full numerical solutions. The analysis shows that (i) decreasing the system size relative to the Debye screening length decreases the voltage of the cell and allows currents higher than the classical diffusion-limited current; (ii) finite reaction rates lead to the important possibility of a reaction-limited current; (iii) the Stern-layer capacitance is critical for allowing the cell to achieve currents above the reaction-limited current; and (iv) all polarographic (current-voltage) curves tend to the same limit as reaction kinetics become fast. Dimensional analysis, however, shows that ``fast'' reactions tend to become ``slow'' with decreasing system size, so the nonlinear effects of surface polarization may dominate the dc response of thin films.

physics.chem-ph↗

arXiv2004

Electrochemical Thin Films At and Above the Classical Limiting Current

We study a model electrochemical thin film at dc currents exceeding the classical diffusion-limited value. The mathematical problem involves the steady Poisson-Nernst-Planck equations for a binary electrolyte with nonlinear boundary conditions for reaction kinetics and Stern-layer capacitance, as well as an integral constraint on the number of anions. At the limiting current, we find a nested boundary layer structure at the cathode, which is required by the reaction boundary condition. Above the limiting current, a depletion of anions generally characterizes the cathode side of the cell. In this regime, we derive leading-order asymptotic approximations for the (i) classical bulk space-charge layer and (ii) another, nested highly charged boundary layer at the cathode. The former involves an exact solution to the Nernst-Planck equations for a single, unscreened ionic species, which may apply more generally to Faradaic conduction through very thin insulating films. By matching expansions, we derive current-voltage relations well into the space-charge regime. Throughout our analysis, we emphasize the strong influence of the Stern-layer capacitance on cell behavior.

physics.chem-ph↗

arXiv2004

A Theory of Cooperative Diffusion in Dense Granular Flows

Dilute granular flows are routinely described by collisional kinetic theory, but dense flows require a fundamentally different approach, due to long-lasting, many-body contacts. In the case of silo drainage, many continuum models have been developed for the mean flow, but no realistic statistical theory is available. Here, we propose that particles undergo cooperative displacements in response to diffusing ``spots'' of free volume. The typical spot size is several particle diameters, so cages of nearest neighbors tend to remain intact over large distances. The spot hypothesis relates diffusion and cage-breaking to volume fluctuations and spatial velocity correlations, in agreement with new experimental data. It also predicts density waves caused by weak spot interactions. Spots enable fast, multiscale simulations of dense flows, in which a small, internal relaxation enforces packing constraints during spot-induced motion. In the continuum limit of the model, tracer diffusion is described by a new stochastic differential equation, where the drift velocity and diffusion tensor are coupled non-locally to the spot density. The same mathematical formalism may also find applications to glassy relaxation, as a compelling alternative to void (or hole) random walks.

cond-mat.stat-mech↗

arXiv2004

Induced-Charge Electro-Osmosis

We describe the general phenomenon of `induced-charge electro-osmosis' (ICEO) -- the nonlinear electro-osmotic slip that occurs when an applied field acts on the ionic charge it {\sl induces} around a polarizable surface. Motivated by a simple physical picture, we calculate ICEO flows around conducting cylinders in steady (DC), oscillatory (AC), and suddenly-applied electric fields. This picture, and these systems, represent perhaps the clearest example of nonlinear electrokinetic phenomena. We complement and verify this physically-motivated approach using a matched asymptotic expansion to the electrokinetic equations in the thin double-layer and low potential limits. ICEO slip velocities vary like $u_s \propto E_0^2 L$, where $E_0$ is the field strength and $L$ is a geometric length scale, and are set up on a time scale $τ_c = λ_D L/D$, where $λ_D$ is the screening length and $D$ is the ionic diffusion constant. We propose and analyze ICEO microfluidic pumps and mixers that operate without moving parts under low applied potentials. Similar flows around metallic colloids with fixed total charge have been described in the Russian literature (largely unnoticed in the West). ICEO flows around conductors with fixed potential, on the other hand, have no colloidal analog and offer further possibilities for microfluidic applications.

physics.flu-dyn↗

arXiv2004

Induced-charge Electrokinetic Phenomena: Theory and Microfluidic Applications

We give a general, physical description of ``induced-charge electro-osmosis'' (ICEO), the nonlinear electrokinetic slip at a polarizable surface, in the context of some new techniques for microfluidic pumping and mixing. ICEO generalizes ``AC electro-osmosis'' at micro-electrode arrays to various dielectric and conducting structures in weak DC or AC electric fields. The basic effect produces micro-vortices to enhance mixing in microfluidic devices, while various broken symmetries -- controlled potential, irregular shape, non-uniform surface properties, and field gradients -- can be exploited to produce streaming flows. Although we emphasize the qualitative picture of ICEO, we also briefly describe the mathematical theory (for thin double layers and weak fields) and apply it to a metal cylinder with a dielectric coating in a suddenly applied DC field.

physics.flu-dyn↗

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

Diffusion and mixing in gravity-driven dense granular flows

We study the transport properties of particles draining from a silo using imaging and direct particle tracking. The particle displacements show a universal transition from super-diffusion to normal diffusion, as a function of the distance fallen, independent of the flow speed. In the super-diffusive (but sub-ballistic) regime, which occurs before a particle falls through its diameter, the displacements have fat-tailed and anisotropic distributions. In the diffusive regime, we observe very slow cage breaking and Peclet numbers of order 100, contrary to the only previous microscopic model (based on diffusing voids). Overall, our experiments show that diffusion and mixing are dominated by geometry, consistent with fluctuating contact networks but not thermal collisions, as in normal fluids.

cond-mat.soft↗