2 March 2012
What is a phase transition? The first thing that comes to mind is boiling and freezing of water. The material clearly changes its behaviour without any chemical reaction. One way to arrive at a mathematical model is to associate different material behavior, ie., constitutive laws, to different phases. This is a continuum physics viewpoint, and when a law for the switching between phases is specified, we arrive at pde problems. The oldest paper on such a problem by Clapeyron and Lame is nearly 200 years old; it is basically on what has later been called the Stefan problem for the heat equation. The law for switching is given e.g. by the melting temperature. This can be taken to be a phenomenological law or thermodynamically justified as an equilibrium condition. The theory does not explain delayed switching (undercooling) and it does not give insight in structural differences between the phases. To some extent the first can be explained with the help of a free energy associated with the interface between different phases. This was proposed by Gibbs, is relevant on small space scales, and leads to mean curvature equations for the interface – the so-called Gibbs Thompson condition. The equations do not by themselves lead to a unique evolution. Indeed to close the resulting pde’s with a reasonable switching or nucleation law is an open problem. Based on atomistic concepts, making use of surface energy in a purely phenomenological way, Becker and Döring developed a model for nucleation as a kinetic theory for size distributions of nuclei. The internal structure of each phase is still not considered in this ansatz. An easier problem concerns solid-solid phase transitions. The theory is furthest developped in the context of equilibrium statistical mechanics on lattices, starting with the Ising model for ferromagnets. In this context phases correspond to (extremal) equilibrium Gibbs measures in infinite volume. Interfacial free energy appears as a finite volume correction to free energy. The drawback is that the theory is still basically equilibrium and isothermal. There is no satisfactory theory of metastable states and of local kinetic energy in this framework.