Analysis of diffuse-layer effects on time-dependent interfacial kinetics

We investigate the subtle effects of the diffuse charged layer on interfacial kinetics by solving the governing equations for ion transport (Nernst–Planck) with realistic boundary conditions representing reaction kinetics (Butler–Volmer) and compact-layer capacitance (Stern) in the asymptotic limit =λ_D/L→0, where λ_D is the Debye screening length and L is the distance between the working and counter electrodes. Using the methods of singular perturbation theory, we derive the leading-order steady-state response to a nonzero applied current in the case of the oxidation of a neutral species into cations, without any supporting electrolyte. In certain parameter regimes, the theory predicts a reaction-limited current smaller than the classical diffusion-limited current; this over potential effect is not due to ohmic drop effects in the bulk of the cell but rather to antagonist processes involved in the surface charge transfer and diffuse layer charging respectively. We demonstrate that the charging of diffuse charge, since it is intimately coupled to the surface reaction and cannot be considered independently, plays a fundamental role in nonequilibrium surface reactions when the transport of one of the reacting species is coupled to the total interfacial response of the compact and diffuse layers.     

Imbricate continuum and progressive fracturing of concrete and geomaterials

Meccanica - After giving an overview of the recent results at Northwestern University on mathematical models for fracturing heterogeneous materials, the lecture addresses the problem of a continuum...     

Theoretical prediction of fast 3D AC electro-osmotic pumps

AC electro-osmotic (ACEO) pumps in microfluidics currently involve planar electrode arrays, but recent work on the underlying phenomenon of induced-charge electro-osmosis (ICEO) suggests that three-dimensional (3D) geometries may be exploited to achieve faster flows. In this paper, we present some new design principles for periodic 3D ACEO pumps, such as the "fluid conveyor belt" of ICEO flow over a stepped electrode array. Numerical simulations of these designs (using the standard low-voltage model) predict flow rates almost twenty times faster than existing planar ACEO pumps, for the same applied voltage and minimum feature size. These pumps may enable new portable or implantable lab-on-a-chip devices, since rather fast (mm s(-1)), tuneable flows should be attainable with battery voltages (<10 V).     

Average shape of transport-limited aggregates

We study the relation between stochastic and continuous transport-limited growth models. We derive a nonlinear integro-differential equation for the average shape of stochastic aggregates, whose mean-field approximation is the corresponding continuous equation. Focusing on the advection-diffusion-limited aggregation (ADLA) model, we show that the average shape of the stochastic growth is similar, but not identical, to the corresponding continuous dynamics. Similar results should apply to DLA, thus explaining the known discrepancies between average DLA shapes and viscous fingers in a channel geometry.     

Corrections to the Central Limit Theorem for Heavy-tailed Probability Densities

Classical Edgeworth expansions provide asymptotic correction terms to the Central Limit Theorem (CLT) up to an order that depends on the number of moments available. In this paper, we provide subsequent correction terms beyond those given by a standard Edgeworth expansion in the general case of regularly varying distributions with diverging moments (beyond the second). The subsequent terms can be expressed in a simple closed form in terms of certain special functions (Dawson’s integral and parabolic cylinder functions), and there are qualitative differences depending on whether the number of moments available is even, odd, or not an integer, and whether the distributions are symmetric or not. If the increments have an even number of moments, then additional logarithmic corrections must also be incorporated in the expansion parameter. An interesting feature of our correction terms for the CLT is that they become dominant outside the central region and blend naturally with known large-deviation asymptotics when these are applied formally to the spatial scales of the CLT.     

Unified nano-mechanics based probabilistic theory of quasibrittle and brittle structures: I. Strength, static crack growth, lifetime and scaling

Engineering structures must be designed for an extremely low failure probability such as 10⁻⁶, which is beyond the means of direct verification by histogram testing. This is not a problem for brittle or ductile materials because the type of probability distribution of structural strength is fixed and known, making it possible to predict the tail probabilities from the mean and variance. It is a problem, though, for quasibrittle materials for which the type of strength distribution transitions from Gaussian to Weibullian as the structure size increases. These are heterogeneous materials with brittle constituents, characterized by material inhomogeneities that are not negligible compared to the structure size. Examples include concrete, fiber composites, coarse-grained or toughened ceramics, rocks, sea ice, rigid foams and bone, as well as many materials used in nano- and microscale devices.This study presents a unified theory of strength and lifetime for such materials, based on activation energy controlled random jumps of the nano-crack front, and on the nano-macro multiscale transition of tail probabilities. Part I of this study deals with the case of monotonic and sustained (or creep) loading, and Part II with fatigue (or cyclic) loading. On the scale of the representative volume element of material, the probability distribution of strength has a Gaussian core onto which a remote Weibull tail is grafted at failure probability of the order of 10⁻³. With increasing structure size, the Weibull tail penetrates into the Gaussian core. The probability distribution of static (creep) lifetime is related to the strength distribution by the power law for the static crack growth rate, for which a physical justification is given. The present theory yields a simple relation between the exponent of this law and the Weibull moduli for strength and lifetime. The benefit is that the lifetime distribution can be predicted from short-time tests of the mean size effect on strength and tests of the power law for the crack growth rate. The theory is shown to match closely numerous test data on strength and static lifetime of ceramics and concrete, and explains why their histograms deviate systematically from the straight line in Weibull scale.Although the present unified theory is built on several previous advances, new contributions are here made to address: (i) a crack in a disordered nano-structure (such as that of hydrated Portland cement), (ii) tail probability of a fiber bundle (or parallel coupling) model with softening elements, (iii) convergence of this model to the Gaussian distribution, (iv) the stress-life curve under constant load, and (v) a detailed random walk analysis of crack front jumps in an atomic lattice. The nonlocal behavior is captured in the present theory through the finiteness of the number of links in the weakest-link model, which explains why the mean size effect coincides with that of the previously formulated nonlocal Weibull theory. Brittle structures correspond to the large-size limit of the present theory. An important practical conclusion is that the safety factors for strength and tolerable minimum lifetime for large quasibrittle structures (e.g., concrete structures and composite airframes or ship hulls, as well as various micro-devices) should be calculated as a function of structure size and geometry.