Mesoscopic nonequilibrium thermodynamics of solid surfaces and interfaces with triple junction singularities under the capillary and electromigration forces in anisotropic three-dimensional space

Ogurtani T.

JOURNAL OF CHEMICAL PHYSICS, vol.124, no.14, 2006 (Peer-Reviewed Journal) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 124 Issue: 14
  • Publication Date: 2006
  • Doi Number: 10.1063/1.2185625
  • Journal Indexes: Science Citation Index Expanded, Scopus


A theory of irreversible thermodynamics of curved surfaces and interfaces with triple junction singularities is elaborated to give a full consideration of the effects of the specific surface Gibbs free energy anisotropy in addition to the diffusional anisotropy, on the morphological evolution of surfaces and interfaces in crystalline solids. To entangle this intricate problem, the internal entropy production associated with arbitrary virtual displacements of triple junction and ordinary points on the interfacial layers, embedded in a multicomponent, multiphase, anisotropic composite continuum system, is formulated by adapting a mesoscopic description of the orientation dependence of the chemical potentials in terms of the rotational degree of freedom of individual microelements. The rate of local internal entropy production resulted generalized forces and conjugated fluxes not only for the grain boundary triple junction transversal and longitudinal movements, but also for the ordinary points. The natural combination of the mesoscopic approach coupled with the rigorous theory of irreversible thermodynamics developed previously by the global entropy production hypothesis yields a well-posed, nonlinear, moving free-boundary value problem in two-dimensional (2D) space, as a unified theory. The results obtained for 2D space are generalized into the three-dimensional continuum by utilizing the invariant properties of the vector operators in connection with the descriptions of curved surfaces in differential geometry. This mathematical model after normalization and scaling procedures may be easily adapted for computer simulation studies without introducing any additional phenomenological system parameters (the generalized mobilities), other than the enlarged concept of the surface stiffness.