Bulk water freezing dynamics on superhydrophobic surfaces

In this study, we elucidate the mechanisms governing the heat-transfer mediated, non-thermodynamic limited, freezing delay on non-wetting surfaces for a variety of characteristic length scales, Lc (volume/surface area, 3 mm < Lc < 6 mm) using carefully designed freezing experiments in a temperature-controlled, zero-humidity environment on thin water slabs. To probe the effect of surface wettability, we investigated the total time for room temperature water to completely freeze into ice on superhydrophilic (θaapp→ 0°), hydrophilic (0° < θa < 90°), hydrophobic (90° < θa < 125°), and superhydrophobic (θaapp→ 180°) surfaces. Our results show that at macroscopic length scales, heat conduction through the bulk water/ice layer dominates the freezing process when compared to heat conduction through the functional coatings or nanoscale gaps at the superhydrophobic substrate-water/ice interface. In order to verify our findings, and to determine when the surface structure thermal resistance approaches the water/ice resistance, we fabricated and tested the additional substrates coated with commercial superhydrophobic spray coatings, showing a monotonic increase in freezing time with coating thickness. The added thermal resistance of thicker coatings was much larger than that of the nanoscale superhydrophobic features, which reduced the droplet heat transfer and increased the total freezing time. Transient finite element method heat transfer simulations of the water slab freezing process were performed to calculate the overall heat transfer coefficient at the substrate-water/ice interface during freezing, and shown to be in the range of 1-2.5 kW/m²K for these experiments. The results shown here suggest that in order to exploit the heat-transfer mediated freezing delay, thicker superhydrophobic coatings must be deposited on the surface, where the coating resistance is comparable to the bulk water/ice conduction resistance.