2,930 research outputs found
Phase field modeling of electrochemistry I: Equilibrium
A diffuse interface (phase field) model for an electrochemical system is
developed. We describe the minimal set of components needed to model an
electrochemical interface and present a variational derivation of the governing
equations. With a simple set of assumptions: mass and volume constraints,
Poisson's equation, ideal solution thermodynamics in the bulk, and a simple
description of the competing energies in the interface, the model captures the
charge separation associated with the equilibrium double layer at the
electrochemical interface. The decay of the electrostatic potential in the
electrolyte agrees with the classical Gouy-Chapman and Debye-H\"uckel theories.
We calculate the surface energy, surface charge, and differential capacitance
as functions of potential and find qualitative agreement between the model and
existing theories and experiments. In particular, the differential capacitance
curves exhibit complex shapes with multiple extrema, as exhibited in many
electrochemical systems.Comment: v3: To be published in Phys. Rev. E v2: Added link to
cond-mat/0308179 in References 13 pages, 6 figures in 15 files, REVTeX 4,
SIUnits.sty. Precedes cond-mat/030817
Interface Morphology During Crystal Growth: Effects of Anisotropy and Fluid Flow
The effect of a parallel shear flow and anisotropic interface kinetics on the onset of instability during growth from a supersaturated solution is analyzed. The model used for anisotropy is based on the microscopic picture of step motion. A shear flow (linear Couette flow or asymptotic suction profile) parallel to the crystal solution interface in the same direction as the step motion decreases interface stability. A shear flow counter to the step motion enhances stability and for sufficiently large shear rates the interface is absolutely morphologically stable. For large wave numbers, the perturbed flow field can be neglected and a simple analytic approximation for the stability-instability demarcation is found
Step Bunching: Influence of Impurities and Solution Flow
Step bunching results in striations even at relatively early stages of its development and in inclusions of mother liquor at the later stages. Therefore, eliminating step bunching is crucial for high crystal perfection. At least 5 major effects causing and influencing step bunching are known: (1) Basic morphological instability of stepped interfaces. It is caused by concentration gradient in the solution normal to the face and by the redistribution of solute tangentially to the interface which redistribution enhances occasional perturbations in step density due to various types of noise; (2) Aggravation of the above basic instability by solution flowing tangentially to the face in the same directions as the steps or stabilization of equidistant step train if these flows are antiparallel; (3) Enhanced bunching at supersaturation where step velocity v increases with relative supersaturation s much faster than linear. This v(s) dependence is believed to be associated with impurities. The impurities of which adsorption time is comparable with the time needed to deposit one lattice layer may also be responsible for bunching; (4) Very intensive solution flow stabilizes growing interface even at parallel solution and step flows; (5) Macrosteps were observed to nucleate at crystal corners and edges. Numerical simulation, assuming step-step interactions via surface diffusion also show that step bunching may be induced by random step nucleation at the facet edge and by discontinuity in the step density (a ridge) somewhere in the middle of a face. The corresponding bunching patterns produce the ones observed in experiment. The nature of step bunching generated at the corners and edges and by dislocation step sources, as well as the also relative importance and interrelations between mechanisms 1-5 is not clear, both from experimental and theoretical standpoints. Furthermore, several laws controlling the evolution of existing step bunches have been suggested, though unambiguous conclusions are still missing. Addressing these issues is the major goal of the present project. The theory addressing the above problem, experimental methods, several figures which include: (1) the spatial wave numbers at which the system is neutrally stable as a function of growth velocity for linear kinetics and supersaturation for nonlinear kinetics; (2) a schematic of the experiment of lysozyme crystal growing under conditions of natural convection; (3) fluctuations in time, t, of the normal growth rate, R(t), vicinal slope, p(t) and Fourier Spectra of R(t), discussions and conclusions are presented
Phase field modeling of electrochemistry II: Kinetics
The kinetic behavior of a phase field model of electrochemistry is explored
for advancing (electrodeposition) and receding (electrodissolution) conditions
in one dimension. We described the equilibrium behavior of this model in [J. E.
Guyer, W. J. Boettinger, J.A. Warren, and G. B. McFadden, ``Phase field
modeling of electrochemistry I: Equilibrium'', cond-mat/0308173]. We examine
the relationship between the parameters of the phase field method and the more
typical parameters of electrochemistry. We demonstrate ohmic conduction in the
electrode and ionic conduction in the electrolyte. We find that, despite making
simple, linear dynamic postulates, we obtain the nonlinear relationship between
current and overpotential predicted by the classical ``Butler-Volmer'' equation
and observed in electrochemical experiments. The charge distribution in the
interfacial double layer changes with the passage of current and, at
sufficiently high currents, we find that the diffusion limited deposition of a
more noble cation leads to alloy deposition with less noble species.Comment: v3: To be published in Phys. Rev. E v2: Attempt to work around
turnpage bug. Replaced color Fig. 4a with grayscale 13 pages, 7 figures in 10
files, REVTeX 4, SIunits.sty, follows cond-mat/030817
Many-worlds interpretation of quantum theory and mesoscopic anthropic principle
We suggest to combine the Anthropic Principle with Many-Worlds Interpretation
of Quantum Theory. Realizing the multiplicity of worlds it provides an
opportunity of explanation of some important events which are assumed to be
extremely improbable. The Mesoscopic Anthropic Principle suggested here is
aimed to explain appearance of such events which are necessary for emergence of
Life and Mind. It is complementary to Cosmological Anthropic Principle
explaining the fine tuning of fundamental constants. We briefly discuss various
possible applications of Mesoscopic Anthropic Principle including the Solar
Eclipses and assembling of complex molecules. Besides, we address the problem
of Time's Arrow in the framework of Many-World Interpretation. We suggest the
recipe for disentangling of quantities defined by fundamental physical laws and
by an anthropic selection.Comment: 11 page
Nontrivial Exponent for Simple Diffusion
The diffusion equation \partial_t\phi = \nabla^2\phi is considered, with
initial condition \phi( _x_ ,0) a gaussian random variable with zero mean.
Using a simple approximate theory we show that the probability p_n(t_1,t_2)
that \phi( _x_ ,t) [for a given space point _x_ ] changes sign n times between
t_1 and t_2 has the asymptotic form p_n(t_1,t_2) \sim
[\ln(t_2/t_1)]^n(t_1/t_2)^{-\theta}. The exponent \theta has predicted values
0.1203, 0.1862, 0.2358 in dimensions d=1,2,3, in remarkably good agreement with
simulation results.Comment: Minor typos corrected, affecting table of exponents. 4 pages, REVTEX,
1 eps figure. Uses epsf.sty and multicol.st
Phase-Field Formulation for Quantitative Modeling of Alloy Solidification
A phase-field formulation is introduced to simulate quantitatively
microstructural pattern formation in alloys. The thin-interface limit of this
formulation yields a much less stringent restriction on the choice of interface
thickness than previous formulations and permits to eliminate non-equilibrium
effects at the interface. Dendrite growth simulations with vanishing solid
diffusivity show that both the interface evolution and the solute profile in
the solid are well resolved
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