Mechanistic investigation of nucleation kinetics in heterogeneous ice crystallization: the role of cooling rate, surface energy, surface nanostructure, and wetting state

The mechanism of nucleation in heterogeneous ice crystallization is important but remains unclear in spite of decades-long research. This study aims at investigating the nucleation kinetics in heterogeneous ice crystallization through molecular dynamics simulations, and comprehensively elucidating the effect of cooling rate, surface energy, surface nanostructure, and wetting state on the nucleation behaviours. More than 300 cases were simulated using monatomic water (mW) model based on a modified Stillinger-Weber (SW) potential. The dynamic nucleation and crystallization behaviours, along with the evolution of the largest ice nucleus, total ice clusters, kinetic energy, and interaction energy between nanodroplet and substrate, were investigated. Increasing the cooling rate and higher surface energy could promote the ice nucleation, but may lead to a tendency to transform into metastable interfacial ice and 4-coordinated molecule types, and create ice-free layer near the substrate due to the strong interaction strength. What's more, the effect of size match between the accessible width and ice lattice constant depends on the wetting states. In Cassie-Baxter state, the size match effect could promote the ice nucleation, while in Wenzel state it is not pronounced and decreasing the contact area by increasing the nanogroove width would inhibit the nucleation process. This work will be valuable in understanding the mechanism of nucleation kinetics in heterogeneous ice crystallization and provide guidance in promoting or inhibiting ice formation.