Polymer-Regulated Freezing of Water Droplets Revealed by Synchrotron X-ray Imaging and Raman Spectroscopy

Abstract: Adding a polymer to a sessile water droplet not only lowers its freezing point but also suppresses the tip singularity that forms during its freezing on cold substrates. Here, we employ synchrotron X-ray and Raman imaging to elucidate the spatiotemporal mechanism underlying tip suppression in an aqueous polyvinyl alcohol (PVA) solution, a model polymer solution. As the polymer concentration increases, we observe slower propagation of the freezing front, reduced bubble entrapment, and a progressively more rounded apex across the volumes and molecular weights examined. X-ray tomography reveals that frozen PVA droplets retain low X-ray transmittance domains in their interiors and at the surface, and Raman spectral mapping confirms that these domains correspond to PVA-enriched regions, providing direct evidence of freeze-induced polymer segregation. These findings indicate that PVA is redistributed heterogeneously during water solidification rather than shifting bulk properties homogeneously, providing a spatially resolved framework for interpreting the observed tip blunting and the suppression of discrete bubble entrapment. Our work identifies freeze-induced polymer segregation as a pathway by which a dissolved polymer regulates both the external shape and the internal structure of a freezing droplet, and these findings shed light on potential applications in freezing-based processes such as freeze-casting and cryopreservation.