Universal Scaling of Freezing Morphodynamics in Polymer Solution Droplets

TL;DR

This study reveals that the morphology and freezing dynamics of polymer solution droplets are governed by a single dimensionless parameter, the Capillary--Lewis number, which unifies behavior across diverse conditions and highlights the transition from transport to elastic-dominated regimes.

Contribution

It introduces a minimal transport-mechanics framework that links solute redistribution to interfacial deformation during freezing, unifying diverse behaviors through the Capillary--Lewis number.

Findings

Droplet morphology and freezing time collapse onto a master curve over nine orders of magnitude.

A transition occurs near a Capillary--Lewis number of one, indicating the limit of solute diffusion.

Deviations from the master curve occur when elastic effects dominate over viscous effects.

Abstract

Freezing of complex fluids is central to a wide range of natural and technological processes, where the interplay between heat transport, solute redistribution, and interfacial deformation gives rise to complex morphologies. Unlike simple liquids, polymer solutions exhibit strongly coupled transport and rheological properties that evolve dynamically during solidification, making their freezing behavior difficult to predict. Here, we examine the freezing of polymer solution droplets spanning dilute to entangled regimes. We find that droplet morphology and freezing dynamics in viscous solutions are governed by a single dimensionless parameter, the Capillary--Lewis number, which captures the competition between viscous stresses, capillarity, and solute transport. Circularity, radial deformation, and freezing time collapse onto a master curve spanning nine orders of magnitude, revealing a transition near unity corresponding to the point at which solute diffusion can no longer relax concentration gradients ahead of the freezing interface. This collapse holds across distinct polymer chemistries within the viscous fluid regime, while deviations emerge when the material exhibits elastic-dominated response ($G' > G''$), indicating the breakdown of purely transport--capillary control. These results establish a minimal transport--mechanics framework linking solute redistribution to interfacial deformation during freezing polymer solutions.