14,386 research outputs found
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.Comment: 25 pages, 17 figures, 4 table
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 , where is the
screening length and the electrode separation. At leading order, the system
initially behaves like an RC circuit with a response time of
(not ), where 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, . 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.Comment: 10 figs, 26 pages (double-column), 141 reference
The relativistic kinetic dispersion relation: Comparison of the relativistic Bhatnagar-Gross-Krook model and Grad's 14-moment expansion
In this paper, we study the Cauchy problem of the linearized kinetic
equations for the models of Marle and Anderson-Witting, and compare these
dispersion relations with the 14-moment theory. First, we propose a
modification of the Marle model to improve the resultant transport coefficients
in accord with those obtained by the full Boltzmann equation. Using the
modified Marle model and Anderson-Witting model, we calculate dispersion
relations that are kinetically correct within the validity of the BGK
approximation. The 14-moment theory that includes the time derivative of
dissipation currents has causal structure, in contrast to the acausal
first-order Chapman-Enskog approximation. However, the dispersion relation of
the 14-moment theory does not accurately describe the result of the kinetic
equation. Thus, our calculation indicates that keeping these second-order terms
does not simply correspond to improving the physical description of the
relativistic hydrodynamics.Comment: 20 pages, 22 figures, accepted for publication in Physica
Incorporating Inductances in Tissue-Scale Models of Cardiac Electrophysiology
In standard models of cardiac electrophysiology, including the bidomain and
monodomain models, local perturbations can propagate at infinite speed. We
address this unrealistic property by developing a hyperbolic bidomain model
that is based on a generalization of Ohm's law with a Cattaneo-type model for
the fluxes. Further, we obtain a hyperbolic monodomain model in the case that
the intracellular and extracellular conductivity tensors have the same
anisotropy ratio. In one spatial dimension, the hyperbolic monodomain model is
equivalent to a cable model that includes axial inductances, and the relaxation
times of the Cattaneo fluxes are strictly related to these inductances. A
purely linear analysis shows that the inductances are negligible, but models of
cardiac electrophysiology are highly nonlinear, and linear predictions may not
capture the fully nonlinear dynamics. In fact, contrary to the linear analysis,
we show that for simple nonlinear ionic models, an increase in conduction
velocity is obtained for small and moderate values of the relaxation time. A
similar behavior is also demonstrated with biophysically detailed ionic models.
Using the Fenton-Karma model along with a low-order finite element spatial
discretization, we numerically analyze differences between the standard
monodomain model and the hyperbolic monodomain model. In a simple benchmark
test, we show that the propagation of the action potential is strongly
influenced by the alignment of the fibers with respect to the mesh in both the
parabolic and hyperbolic models when using relatively coarse spatial
discretizations. Accurate predictions of the conduction velocity require
computational mesh spacings on the order of a single cardiac cell. We also
compare the two formulations in the case of spiral break up and atrial
fibrillation in an anatomically detailed model of the left atrium, and [...].Comment: 20 pages, 12 figure
Linear approach to the orbiting spacecraft thermal problem
We develop a linear method for solving the nonlinear differential equations
of a lumped-parameter thermal model of a spacecraft moving in a closed orbit.
Our method, based on perturbation theory, is compared with heuristic
linearizations of the same equations. The essential feature of the linear
approach is that it provides a decomposition in thermal modes, like the
decomposition of mechanical vibrations in normal modes. The stationary periodic
solution of the linear equations can be alternately expressed as an explicit
integral or as a Fourier series. We apply our method to a minimal thermal model
of a satellite with ten isothermal parts (nodes) and we compare the method with
direct numerical integration of the nonlinear equations. We briefly study the
computational complexity of our method for general thermal models of orbiting
spacecraft and conclude that it is certainly useful for reduced models and
conceptual design but it can also be more efficient than the direct integration
of the equations for large models. The results of the Fourier series
computations for the ten-node satellite model show that the periodic solution
at the second perturbative order is sufficiently accurate.Comment: 20 pages, 11 figures, accepted in Journal of Thermophysics and Heat
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