Phase-Field Model of Freeze Casting

TL;DR

This paper develops a detailed phase-field model to simulate the anisotropic pattern formation during directional ice solidification, revealing how kinetic anisotropy influences lamellae drift and interface dynamics.

Contribution

It introduces a quantitative phase-field model incorporating anisotropic kinetics and faceted interfaces for water-based solutions, advancing understanding of pattern formation mechanisms.

Findings

Spontaneous parity breaking leads to drifting ice lamellae.

Drifting velocity is controlled by basal plane kinetics.

Model remains quantitative with computationally feasible parameters.

Abstract

Directional solidification of water-based solutions has emerged as a versatile technique for templating hierarchical porous materials. However, the underlying mechanisms of pattern formation remain incompletely understood. In this work, we present a detailed derivation and analysis of a quantitative phase-field model for simulating this nonequilibrium process. The phase-field model extends the thin-interface formulation of dilute binary alloy solidification with anti-trapping to incorporate the highly anisotropic energetic and kinetic properties of the partially faceted ice-water interface. This interface is faceted in the basal plane normal to the <0001> directions and atomically rough in other directions within the basal plane. On the basal plane, the model reproduces a linear or nonlinear kinetic relationship that can be linked to experimental measurements. In both cases, spontaneous parity breaking of the solidification front is observed, leading to the formation of partially faceted ice lamellae that drift laterally in one of the <0001> directions. We demonstrate that the drifting velocity is controlled by the kinetics on the basal plane and converges as the thickness of the diffuse solid-liquid interface decreases. Furthermore, we examine the effect of the form of the kinetic anisotropy, which is chosen here such that the inverse of the kinetic coefficient varies linearly from a finite value in the <0001> directions to zero in all other directions within the basal plane. Our results indicate that the drifting velocity of ice lamellae is not affected by the slope of this linear relation, and the radius and undercooling at the tip of an ice lamella converge at relatively small slope values. Consequently, the phase-field simulations remain quantitative with computationally tractable choices of both the interface thickness and the slope assumed in the form of the kinetic anisotropy.