Entropy criteria applied to pattern selection in systems with free boundaries

Abstract

The steady state differential or integral equations which describe patterned dissipative structures, typically to be identified with first order phase transformation morphologies like isothermal pearlites, are invariably degenerate in one or more order parameters (the lamellar spacing in the pearlite case). It is often observed that a different pattern is attained at the steady state for each initial condition (the hysteresis or metastable case). Alternatively, boundary perturbations and internal fluctuations during transition up to, or at the steady state, destroy the path coherence. In this case a statistical ensemble of imperfect patterns often emerges which represents a fluctuating but recognizably patterned and unique average steady state. It is cases like cellular, lamellar pearlite, involving an assembly of individual cell patterns which are regularly perturbed by local fluctuation and growth processes, which concern us here. Such weakly fluctuating nonlinear steady state ensembles can be arranged in a thought experiment so as to evolve as subsystems linking two very large mass-energy reservoirs in isolation. Operating on this discontinuous thermodynamic ideal, Onsager’s principle of maximum path probability for isolated systems, which we interpret as a minimal time correlation function connecting subsystem and baths, identifies the stable steady state at a parametric minimum or maximum (or both) in the dissipation rate. This nonlinear principle is independent of the Principle of Minimum Dissipation which is applicable in the linear regime of irreversible thermodynamics. The statistical argument is equivalent to the weak requirement that the isolated system entropy as a function of time be differentiable to the second order despite the macroscopic pattern fluctuations which occur in the subsystem. This differentiability condition is taken for granted in classical stability theory based on the 2nd Law. The optimal principle as applied to isothermal and forced velocity pearlites (in this case maximal) possesses a Le Chatelier (perturbation) Principle which can be formulated exactlyvia Langer’s conjecture that “each lamella must grow in a direction which is perpendicular to the solidification front”. This is the first example of such an equivalence to be experimentally and theoretically recognized in nonlinear irreversible thermodynamics. A further application to binary solidification cells is reviewed. In this case the optimum in the dissipation is a minimum and the closure between theory and experiment is excellent. Other applications in thermal-hydraulics, biology, and solid state physics are briefy described.