Theory for atomic diffusion on fixed and deformable crystal lattices

TL;DR

This paper develops a comprehensive theoretical framework for atomic diffusion on crystal lattices, incorporating nonlinearities, external forces, and lattice deformation, extending classical diffusion theories with new constitutive relations and a generalized Cahn-Hilliard equation.

Contribution

It introduces a novel microbalance-based approach to derive generalized diffusion equations accounting for lattice deformation and phase separation.

Findings

Derivation of a generalized Cahn-Hilliard equation.

Identification of microbalance restrictions on constitutive relations.

Extension of classical diffusion theory to deformable lattices.

Abstract

We develop a theoretical framework for the diffusion of a single unconstrained species of atoms on a crystal lattice that provides a generalization of the classical theories of atomic diffusion and diffusion-induced phase separation to account for constitutive nonlinearities, external forces, and the deformation of the lattice. In this framework, we regard atomic diffusion as a microscopic process described by two independent kinematic variables: (i) the atomic flux, which reckons the local motion of atoms relative to the motion of the underlying lattice, and (ii) the time-rate of the atomic density, which encompasses nonlocal interactions between migrating atoms and characterizes the kinematics of phase separation. We introduce generalized forces power-conjugate to each of these rates and require that these forces satisfy ancillary microbalances distinct from the conventional balance involving the forces that expend power over the rate at which the lattice deforms. A mechanical version of the second law, which takes the form of an energy imbalance accounting for all power expenditures (including those due to the atomic diffusion and phase separation), is used to derive restrictions on the constitutive equations. With these restrictions, the microbalance involving the forces conjugate to the atomic flux provides a generalization of the usual constitutive relation between the atomic flux and the gradient of the diffusion potential, a relation that in conjunction with the atomic balance yields a generalized Cahn-Hilliard equation.