Materials Theory最新文献

An electrochemical cell contains three open thermodynamic systems that, in dynamic equilibrium, equalize their electrochemical potentials with that of their surrounding by forming an electric-double-layer-capacitor at the interface of the electrolyte with each of the two electrodes. Since the electrode/electrolyte interfaces are heterojunctions, the electrochemical potentials or Fermi levels of the two materials that contact the electrolyte at the two electrodes determine the voltage of a cell. The voltage is the sum of the voltages of the two interfacial electric-double-layer capacitors at the two electrode/electrolyte interfaces. A theoretical analysis of the thermodynamics that gives a quantitative prediction of the observed voltages in an asymmetric cell with an S₈ relay at the positive electrode is provided. In addition, new discharge data and an X-ray photoelectron spectroscopy analysis of the lithium plated on the positive electrode of a discharged cell is presented. Ab initio, DFT methods were used to calculate the band structure and surface-state energies of the crystalline S₈ solid sulfur relay. The theoretical exposition of the thermodynamics of the operative driving force of the chemical reactions in an electrochemical cell demonstrate that our initial experimental data and conclusions are valid. Other reported observations of lithium plating on the positive electrode, observations that were neither exploited nor their origins specified, are also cited.

We explore new ways of regulating defect behavior in systems of conservation laws. Contrary to usual regularization schemes (such as a vanishing viscosity limit), which attempt to control defects by making them smoother, our schemes result in defects which are more singular, and we thus refer to such schemes as “irregularizations”. In particular, we seek to produce delta shock defects which satisfy a condition of stationarity. We are motivated to pursue such exotic defects by a physical example arising from dislocation dynamics in materials physics, which we describe.

An exact analytical solution of the Fick’s second law was developed and applied to the mixed-mode growth of a multicomponent ellipsoidal precipitate growing with constant eccentricities in the quasi-stationary regime. The solution is exact if the nominal composition, equilibrium concentrations and material properties are assumed constant, and can be applied to compounds having no limitations in the number of components. The solution was compared to the solution calculated by a diffusion-controlled application software and it was found that the solute concentrations at the interface can be determined knowing only the nominal composition, the full equilibrium concentrations and the coefficients of diffusion. The thermodynamic calculations owing to find alternative tie-lines are proven to be useless in the mixed-mode model. From this, it appears that the search of alternative tie-lines is computationally counterproductive, even when the interface has a very high mobility. A more efficient computational scheme is possible by considering that a moving interface is not at equilibrium.

Continuum dislocation dynamics (CDD) aims at representing the evolution of systems of curved and connected dislocation lines in terms of density-like field variables. Here we discuss how the processes of dislocation multiplication and annihilation can be described within such a framework. We show that both processes are associated with changes in the volume density of dislocation loops: dislocation annihilation needs to be envisaged in terms of the merging of dislocation loops, while conversely dislocation multiplication is associated with the generation of new loops. Both findings point towards the importance of including the volume density of loops (or ’curvature density’) as an additional field variable into continuum models of dislocation density evolution. We explicitly show how this density is affected by loop mergers and loop generation. The equations which result for the lowest order CDD theory allow us, after spatial averaging and under the assumption of unidirectional deformation, to recover the classical theory of Kocks and Mecking for the early stages of work hardening.

A formal asymptotic analysis of two classes of phase field models for void growth and coarsening in irradiated solids has been performed to assess their sharp-interface kinetics. It was found that the sharp interface limit of type B models, which include only point defect concentrations as order parameters governed by Cahn-Hilliard equations, captures diffusion-controlled kinetics. It was also found that a type B model reduces to a generalized one-sided classical Stefan problem in the case of a high driving thermodynamic force associated with the void growth stage, while it reduces to a generalized one-sided Mullins-Sekerka problem when the driving force is low in the case of void coarsening. The latter case corresponds to the famous rate theory description of void growth. Type C models, which include point defect concentrations and a non-conserved order parameter to distinguish between the void and solid phases and employ coupled Cahn-Hilliard and Allen-Cahn equations, are shown to represent mixed diffusion and interfacial kinetics. In particular, the Allen-Cahn equation of model C reduces to an interfacial constitutive law representing the attachment and emission kinetics of point defects at the void surface. In the limit of a high driving force associated with the void growth stage, a type C model reduces to a generalized one-sided Stefan problem with kinetic drag. In the limit of low driving forces characterizing the void coarsening stage, however, the model reduces to a generalized one-sided Mullins-Sekerka problem with kinetic drag. The analysis presented here paves the way for constructing quantitative phase field models for the irradiation-driven nucleation and growth of voids in crystalline solids by matching these models to a recently developed sharp interface theory.

We present results of a two-scale model of disordered cellular materials where we describe the microstructure in an idealized manner using a beam network model and then make a transition to a Cosserat-type continuum model describing the same material on the macroscopic scale. In such scale transitions, normally either bottom-up homogenization approaches or top-down reverse modeling strategies are used in order to match the macro-scale Cosserat continuum to the micro-scale beam network. Here we use a different approach that is based on an energetically consistent continuization scheme that uses data from the beam network model in order to determine continuous stress and strain variables in a set of control volumes defined on the scale of the individual microstructure elements (cells) in such a manner that they form a continuous tessellation of the material domain. Stresses and strains are determined independently in all control volumes, and constitutive parameters are obtained from the ensemble of control volume data using a least-square error criterion. We show that this approach yields material parameters that are for regular honeycomb structures in close agreement with analytical results. For strongly disordered cellular structures, the thus parametrized Cosserat continuum produces results that reproduce the behavior of the micro-scale beam models both in view of the observed strain patterns and in view of the macroscopic response, including its size dependence.

The standard way of modeling plasticity in polycrystals is by using the crystal plasticity model for single crystals in each grain, and imposing suitable traction and slip boundary conditions across grain boundaries. In this fashion, the system is modeled as a collection of boundary-value problems with matching boundary conditions. In this paper, we develop a diffuse-interface crystal plasticity model for polycrystalline materials that results in a single boundary-value problem with a single crystal as the reference configuration. Using a multiplicative decomposition of the deformation gradient into lattice and plastic parts, i.e. F(X,t)=F ^L(X,t)F ^P(X,t), an initial stress-free polycrystal is constructed by imposing F ^L to be a piecewise constant rotation field R ⁰(X), and F ^P=R ⁰(X)^T, thereby having F(X,0)=I, and zero elastic strain. This model serves as a precursor to higher order crystal plasticity models with grain boundary energy and evolution.

We present a continuum model of ion-induced surface patterning. The model incorporates the atomic processes of sputtering, re-deposition and surface diffusion, and is shown to display the generic features of the damped Kuramoto-Sivashinsky (KS) equation of non-linear dynamics. Linear and non-linear stability analyses of the evolution equation give estimates of the emerging pattern wavelength and spatial symmetry. The analytical theory is confirmed by numerical simulations of the evolution equation with the Fast Fourier Transform method, where we show the influence of the incident ion angle, flux, and substrate surface temperature. It is shown that large local geometry variations resulting in quadratic non-linearities in the evolution equation dominate pattern selection and stability at long time scales.

Cracks are created by massive breakage of molecular or atomic bonds. The latter, in its turn, leads to the highly localized loss of material, which is the reason why even closed cracks are visible by a naked eye. Thus, fracture can be interpreted as the local material sink. Mass conservation is violated locally in the area of material failure. We consider a theoretical formulation of the coupled mass and momenta balance equations for a description of fracture. Our focus is on brittle fracture and we propose a finite strain hyperelastic thermodynamic framework for the coupled mass-flow-elastic boundary value problem. The attractiveness of the proposed framework as compared to the traditional continuum damage theories is that no internal parameters (like damage variables, phase fields, etc.) are used while the regularization of the failure localization is provided by the physically sound law of mass balance.