Homogeneous freezing of water droplets for different volumes and cooling rates

Abstract

To understand the crystallization of aqueous solutions in the atmosphere, biological specimens, or pharmaceutical formulations, the rate at which ice nucleates from pure liquid water must be quantified. There is still an orders-of-magnitude spread in the homogeneous nucleation rate of water measured using different instruments, with the most important source of uncertainty being that of the measured temperature. Microfluidic platforms can generate hundreds to thousands of monodisperse water-in-oil droplets, unachievable by most other techniques. However, most microfluidic devices previously used to quantify homogeneous ice nucleation rates have reported high temperature uncertainties, between ±0.3 and ±0.7 K. We use the recently developed Microfluidic Ice Nuclei Counter Zurich (MINCZ) to observe the freezing of spherical water droplets with two diameters (75 and 100 μm) at two cooling rates (1 and 0.1 K min⁻¹). By varying both droplet volume and cooling rate, we were able to probe a temperature range of 236.5–239.3 K with an accuracy of ±0.2 K, providing reliable data where previously determined nucleation rates suffered from large uncertainties and inconsistencies, especially at temperatures above 238 K. From these data and from Monte Carlo simulations, we demonstrate the importance of obtaining a sufficiently large dataset so that underlying nucleation rates are not overestimated at higher temperatures. Finally, we obtain new parameters for a previous parameterisation by fitting to our newly measured nucleation rates, enabling its use in applications where ice formation needs to be predicted.