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Asymptotic analysis for Korteweg models

2010, Dreyer, Wolfgang, Giesselmann, Jan, Kraus, Christiane, Rohde, Christiane

This paper deals with a sharp interface limit of the isothermal Navier-Stokes-Korteweg system. The sharp interface limit is performed by matched asymptotic expansions of the fields in powers of the interface width. These expansions are considered in the interfacial region (inner expansions) and in the bulk (outer expansion) and are matched order by order. Particularly we consider the first orders of the corresponding inner equations obtained by a change of coordinates in an interfacial layer. For a specific scaling we establish solvability criteria for these inner equations and recover the results within the general setting of jump conditions for sharp interface models.

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Overcoming the shortcomings of the Nernst-Planck model

2012, Dreyer, Wolfgang, Guhlke, Clemens, Müller, Rüdiger

This is a study on electrolytes that takes a thermodynamically consistent coupling between mechanics and diffusion into account. It removes some inherent deficiencies of the popular Nernst-Planck model. A boundary problem for equilibrium processes is used to illustrate the new features of our model.

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Modelling compressible electrolytes with phase transition

2014, Dreyer, Wolfgang, Giesselmann, Jan, Kraus, Christiane

A novel thermodynamically consistent diffuse interface model is derived for compressible electrolytes with phase transitions. The fluid mixtures may consist of N constituents with the phases liquid and vapor, where both phases may coexist. In addition, all constituents may consist of polarizable and magnetizable matter. Our introduced thermodynamically consistent diffuse interface model may be regarded as a generalized model of Allen-Cahn/Navier-Stokes/Poisson type for multi-component flows with phase transitions and electrochemical reactions. For the introduced diffuse interface model, we investigate physically admissible sharp interface limits by matched asymptotic techniques. We consider two scaling regimes, i.e. a non-coupled and a coupled regime, where the coupling takes place between the smallness parameter in the Poisson equation and the width of the interface. We recover in the sharp interface limit a generalized Allen-Cahn/Euler/Poisson system for mixtures with electrochemical reactions in the bulk phases equipped with admissible interfacial conditions. The interfacial conditions satisfy, for instance, a generalized Gibbs-Thomson law and a dynamic Young-Laplace law.

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Rational modeling of electrochemical double layers in thermodynamic non-equilibrium

2014, Dreyer, Wolfgang, Guhlke, Clemens, Müller, Rüdiger

We consider the contact between an electrolyte and a solid electrode. At first we formulate a thermodynamic consistent model that resolves boundary layers at interfaces. The model includes charge transport, diffusion, chemical reactions, viscosity, elasticity and polarization under isothermal conditions. There is a coupling between these phenomena that particularly involves the local pressure in the electrolyte. Therefore the momentum balance is of major importance for the correct description of the layers. The width of the boundary layers is typically very small compared to the macroscopic dimensions of the system. In a second step we thus apply the method of asymptotic analysis to derive a simpler reduced model that does not resolve the boundary layers but instead incorporates the electrochemical properties of the layers into a set of new boundary conditions. For a metal-electrolyte interface, we derive a qualitative description of the double layer capacitance without the need to resolve space charge layers.

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Rational modeling of electrochemical double-layers and derivation of Butler-Volmer equations

2013, Dreyer, Wolfgang, Guhlke, Clemens, Müller, Rüdiger

We derive the boundary conditions for the contact between an electrolyte and a solid electrode. At first we revisit the thermodynamic consistent complete model that resolves the actual electrodeelectrolyte interface and its adjacent boundary layers. The width of these layers is controlled by the Debye length that is typically very small, leading to strongly different length scales in the system. We apply the method of asymptotic analysis to derive a simpler reduced model that does not resolve the boundary layers but instead incorporates the electrochemical properties of the layers into a set of new boundary conditions. This approach fully determines the relation of bulk quantities to the boundary conditions of the reduced model. In particular, the Butler-Volmer equations for electrochemical reactions, which are still under discussion in the literature, are rational consequences of our approach. For illustration and to compare with the literature, we consider a simple generic reaction.

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A compressible mixture model with phase transition

2013, Dreyer, Wolfgang, Giesselmann, Jan, Kraus, Christiane

We introduce a new thermodynamically consistent diffuse interface model of AllenCahn/NavierStokes type for multi-component flows with phase transitions and chemical reactions. For the introduced diffuse interface model, we investigate physically admissible sharp interface limits by matched asymptotic techniques. We consider two scaling regimes, i.e. a non-dissipative and a dissipative regime, where we recover in the sharp interface limit a generalized Allen-Cahn/Euler system for mixtures with chemical reactions in the bulk phases equipped with admissible interfacial conditions. The interfacial conditions satify, for instance, a YoungLaplace and a Stefan type law.

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A quasi-incompressible diffuse interface model with phase transition

2012, Aki, Gonca, Dreyer, Wolfgang, Giesselmann, Jan, Kraus, Christine

This work introduces a new thermodynamically consistent diffuse model for two-component flows of incompressible fluids. For the introduced diffuse interface model, we investigate physically admissible sharp interface limits by matched asymptotic techniques. To this end, we consider two scaling regimes where in one case we recover the Euler equations and in the other case the Navier-Stokes equations in the bulk phases equipped with admissible interfacial conditions. For the Navier-Stokes regime, we further assume the densities of the fluids are close to each other in the sense of a small parameter which is related to the interfacial thickness of the diffuse model.

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New insights on the interfacial tension of electrochemical interfaces and the Lippmann equation

2015, Dreyer, Wolfgang, Guhlke, Clemens, Landstorfer, Manuel, Neumann, Johannes, Müller, Rüdiger

The Lippmann equation is considered as universal relationship between interfacial tension, double layer charge, and cell potential. Based on the framework of continuum thermo-electrodynamics we provide some crucial new insights to this relation. In a previous work we have derived a general thermodynamic consistent model for electrochemical interfaces, which showed a remarkable agreement to single crystal experimental data. Here we apply the model to a curved liquid metal electrode. If the electrode radius is large compared to the Debye length, we apply asymptotic analysis methods and obtain the Lippmann equation. We give precise definitions of the involved quantities and show that the interfacial tension of the Lippmann equation is composed of the surface tension of our general model, and contributions arising from the adjacent space charge layers. This finding is confirmed by a comparison of our model to experimental data of several mercury-electrolyte interfaces. We obtain qualitative and quantitative agreement in the 2V potential range for various salt concentrations. We also discuss the validity of our asymptotic model when the electrode radius is comparable to the Debye length.

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A diffuse interface model for quasi-incrompressible flows : sharp interface limits and numerics

2012, Aki, Gonca, Daube, Johannes, Dreyer, Wolfgang, Giesselmann, Jan, Kränkel, Mirko, Kraus, Christiane

In this contribution, we investigate a diffuse interface model for quasi–incompressible flows. We determine corresponding sharp interface limits of two different scalings. The sharp interface limit is deduced by matched asymptotic expansions of the fields in powers of the interface. In particular, we study solutions of the derived system of inner equations and discuss the results within the general setting of jump conditions for sharp interface models. Furthermore, we treat, as a subproblem, the convective Cahn–Hilliard equation numerically by a Local Discontinuous Galerkin scheme.