Freezing or solidification of impacting droplets is omnipresent in nature and technology, be it a rain droplet falling on a supercooled surface, be it in inkjet printing where often molten wax is used, be it in added manufacturing or in metal production processes or in extreme ultraviolet lithography (EUV) for the chip production where molten tin is used to generate the EUV radiation. For many of these industrial applications, a detailed understanding of the solidification process is essential. Here, by adopting a totally new optical technique in the context of freezing, namely TIR (Total-Internal-Reflection), we elucidate the freezing kinetics during the solidification of a droplet while it impacts on an undercooled surface. We show for the first time that at sufficiently high undercooling a peculiar freezing morphology exists that involves sequential advection of frozen fronts from the centre of the droplet to its boundaries. This phenomenon is examined by combining elements of classical nucleation theory to the large scale hydrodynamics on the droplet scale, bringing together two subfields which traditionally have been quite separated. Furthermore, we report a peculiar self-peeling phenomenon of a frozen splat that is driven by the existence of a transient crystalline state during solidification.
Surface icing affects the safety and performance of numerous processes in technology. Previous studies mostly investigated freezing of individual droplets. The interaction among multiple droplets during freezing is investigated less, especially on nanotextured icephobic surfaces, despite its practical importance as water droplets never appear in isolation, but in groups. Here we show that freezing of a supercooled droplet leads to spontaneous self-heating and induces strong vaporization. The resulting, rapidly propagating vapor front causes immediate cascading freezing of neighboring supercool…
Water droplet freezing is a common phenomenon in our daily life. In both natural scenarios and industrial production, different surface inclinations bring distinctive deformation and freezing dynamics to frozen droplets. We explore the freezing of pendent and sessile droplets at different Bond number regimes. The effect of gravity on the droplet freezing process is analyzed by considering droplet morphology, freezing front dynamics, and freezing time. It is found that gravity can significantly influence droplet freezing processes via shaping the initial droplet, resulting in the flattening or …
Understanding the dynamics during freezing of nanofluid droplets is of importance from a fundamental and practical viewpoint. While the freezing of a water droplet has been extensively studied, little information is available about the characteristics of freezing a nanofluid droplet. Here, we report unique shape changes observed during the freezing process of a nanofluid droplet. Instead of forming a pointy tip on the frozen deionized water droplet, we found that the top of a frozen nanofluid droplet exhibits a flat plateau shape and such plateau becomes larger with increasing nanoparticle con…
Understanding the dynamics in the deposition of water droplets onto solid surfaces is of importance from both fundamental and practical viewpoints. While the deposition of a water droplet onto a heated surface is extensively studied, the characteristics of depositing a droplet onto a cold surface and the phenomena leading to such behavior remain elusive. Here we report the formation of a triple condensate halo observed during the deposition of a water droplet onto a cold surface, due to the interplay between droplet impact dynamics and vapor diffusion. Two subsequent condensation stages occur …
Liquid droplets impacting a superhydrophobic surface decorated with micro-scale posts often bounce off the surface. However, by decreasing the impact velocity droplets may land on the surface in a fakir state, and by increasing it posts may impale droplets that are then stuck on the surface. We use a two-phase lattice-Boltzmann model to simulate droplet impact on superhydrophobic surfaces, and show that it may result in a fakir state also for reasonable high impact velocities. This happens more easily if the surface is made more hydrophobic or the post height is increased, thereby making the i…
The structural evolution of suspensions upon freezing is studied with optical microscopy in a suspended droplet configuration. Droplets have millimeter size and consist in an aqueous mixture of silica particles while the surroundings phase is hexane. Freeze-thaw cycles are applied to this system and a two-step freezing mechanism evidenced. A fast adiabatic growth of dendrites that invade the full droplets is first observed, and occurs within a few milliseconds. Then a slow process lasts for several seconds and corresponds to the release of solidification latent heat into the hexane phase. The …
Polymer-Regulated Freezing of Water Droplets Revealed by Synchrotron X-ray Imaging and Raman Spectroscopy
Ulsan National Institute of Science and Technology (UNIST)（蔚山科学技术院）；Korea Polar Research Institute (KOPRI)（韩国极地研究所）；Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH)（浦项科技大学波项加速器实验室）；UNIST Research Center for Soft and Living Matter, Ulsan National Institute of Science and Technology (UNIST)（蔚山科学技术院软体与生命物质研究中心）
Would a raindrop impacting on a coarse beach behave differently from that impacting on a desert of fine sand? We study this question by a series of model experiments, where the packing density of the granular target, the wettability of individual grains, the grain size, the impacting liquid, and the impact speed are varied. We find that by increasing the grain size and/or the wettability of individual grains the maximum droplet spreading undergoes a transition from a capillary regime towards a viscous regime, and splashing is suppressed. The liquid-grain mixing is discovered to be the underlyi…
A liquid droplet impacting on a solvophobic surface normally rebounds. The rebound is suppressed by a small amount of dissolved polymer. In this work, using multi-body dissipative particle dynamics simulations, two anti-rebound mechanisms, the slow-retraction and the slow-hopping mechanisms, are identified. Which of them dominates depends on the polymer-surface attraction strength. However, these two mechanisms are not excluding each other but may coexist. During the droplet rebound, the surface-adsorbed polymer acts in two ways: the adsorbed beads mediate solvent-surface interactions, and hig…
Models without an explicit time dependence, called singular models, are widely used for fitting the distribution of temperatures at which water droplets freeze. In 1950 Levine developed the original singular model. His key assumption was that each droplet contained many nucleation sites, and that freezing occurred due to the nucleation site with the highest freezing temperature. The fact that freezing occurs due to the maximum value out of large number of nucleation temperatures, means that we can apply the results of what is called extreme-value statistics. This is the statistics of the extre…
Freezing of water droplets placed on the bare and superhydrophobic surfaces of polymer wedges are studied both experimentally and computationally. Two-dimensional numerical calculations of the transient temperature field in a chilled polymer wedge show that the direction of heat flux from the droplet through the thermal contact region with the wedge differs significantly from the normal to the wedge surface. This is the physical cause of the recently observed asymmetric cooling of the droplet. A novel approximate computational model is proposed that takes into account the variable area of the …
In this work we measured Surface Energy and Freezing Temperature of supercooled water droplets in air. We find that freezing of water droplets is triggered at the water-air interface and that freezing progresses faster on the surface than in the bulk. The Freezing Point of water droplets is strongly depressed by dryness in air and how humidity triggers freezing. Additionally it is shown to be a Surface phenomenon related to a transfer of Entropy from water vapour to the surface of ice.
Macro-textured superhydrophobic surfaces can reduce droplet-substrate contact times of impacting water droplets, however, surface designs with similar performance for significantly more viscous liquids are missing, despite their importance in nature and technology such as for chemical shielding, food staining repellency, and supercooled (viscous) water droplet removal in anti-icing applications. Here, we introduce a deterministic, controllable and up-scalable method to fabricate superhydrophobic surfaces with a 3D-printed architecture, combining arrays of alternating surface protrusions and in…
Close to the triple point, the surface of ice is covered by a thin liquid layer (so-called quasi-liquid layer) which crucially impacts growth and melting rates. Experimental probes cannot observe the growth processes below this layer, and classical models of growth by vapor deposition do not account for the formation of premelting films. Here, we develop a mesoscopic model of liquid-film mediated ice growth, and identify the various resulting growth regimes. At low saturation, freezing proceeds by terrace spreading, but the motion of the buried solid is conveyed through the liquid to the outer…
Ice accumulation hinders the performance of, and poses safety threats for infrastructure both on the ground and in the air. Previously, rationally designed superhydrophobic surfaces have demonstrated some potential as a passive means to mitigate ice accretion; however, further studies on material solutions that reduce impalement and contact time for impacting supercooled droplets and can also repel droplets that freeze during surface contact are urgently needed. Here we demonstrate the collaborative effect of substrate flexibility and surface nanotexture on enhancing both icephobicity and the …
When a liquid droplet impacts a hot solid surface, enough vapor may be generated under it as to prevent its contact with the solid. The minimum solid temperature for this so-called Leidenfrost effect to occur is termed the Leidenfrost temperature, or the dynamic Leidenfrost temperature when the droplet velocity is non-negligible. We observe the wetting/drying and the levitation dynamics of the droplet impacting on an (isothermal) smooth sapphire surface using high speed total internal reflection imaging, which enables us to observe the droplet base up to about 100 nm above the substrate surfac…
We experimentally investigated the splashing of dense suspension droplets impacting a solid surface, extending prior work to the regime where the viscosity of the suspending liquid becomes a significant parameter. The overall behavior can be described by a combination of two trends. The first one is that the splashing becomes favored when the kinetic energy of individual particles at the surface of a droplet overcomes the confinement produced by surface tension. This is expressed by a particle-based Weber number $We_p$. The second is that splashing is suppressed by increasing the viscosity of …
A small amount of polymer dissolved in a droplet suppresses droplet rebound when it impinges on a supersolvophobic surface. This work investigates impacting dynamics of a droplet of dilute polymer solution depending on the molecular weight and the concentration of the polymer by using multi-body dissipative particle dynamics simulations. Either the longer polymer or the high polymer concentration suppresses rebound of a droplet although its shear viscosity and the liquid-vapor surface tension are not different from those of a pure solvent droplet. We found a new mechanism of the anti-rebound i…
The transport of small quantities of liquid on a solid surface is inhibited by the resistance to motion caused by the contact between the liquid and the solid. To overcome such resistance, motion can be externally driven through gradients in electric fields, but these all inconveniently involve the input of external energy. Alternatively, gradients in physical shape and wettability - the conical shape of cactus spines to create self-propelled motion. However, such self-propelled motion to date has limited success in overcoming the inherent resistance to motion of the liquid contact with the so…
The interaction of objects with a moving solidification front is a common feature of many industrial and natural processes such as metal processing, the growth of single-crystals, the cryopreservation of cells, or the formation of sea ice. Solidification fronts interact with objects with different outcomes, from the total rejection to their complete engulfment. We image the freezing of emulsions in 5D (space, time, and solute concentration) with confocal microscopy. We show the solute induces long-range interactions that determine the solidification microstructure. The local increase of solute…
I employ the van der Waals theory of Baus and coworkers to analyze the fast, adiabatic decay of a supercooled liquid in a closed vessel with which the solidification process usually starts. By imposing a further constraint on either the system volume or pressure, I use the maximum-entropy method to quantify the fraction of liquid that is transformed into solid as a function of undercooling and of the amount of a foreign gas that could possibly be also present in the test tube. Upon looking at the implications of thermal and mechanical insulation for the energy cost of forming a solid droplet w…
The effect of freezing on contact line motion is a scientific challenge in the understanding of the solidification of capillary flows. In this letter, we experimentally investigate the spreading and freezing of a water droplet on a cold substrate. We demonstrate that solidification stops the spreading because the ice crystals catch up with the advancing contact line. Indeed, we observe the formation and growth of ice crystals along the substrate during the drop spreading, and show that their velocity equals the contact line velocity when the drop stops. Modelling the growth of the crystals, we…
The complicated dynamics of the contact line of a moving droplet on a solid substrate often hamper the efficient modeling of microfluidic systems. In particular, the selection of the effective boundary conditions, specifying the contact line motion, is a controversial issue since the microscopic physics that gives rise to this displacement is still unknown. Here, a sharp interface, continuum-level, novel modeling approach, accounting for liquid/solid micro-scale interactions assembled in a disjoining pressure term, is presented. By following a unified conception (the model applies both to the …
Recent experiments with droplets impacting a macro-textured superhydrophobic surfaces revealed new regimes of bouncing with a remarkable reduction of the contact time. We present here a comprehensive numerical study that reveals the physics behind these new bouncing regimes and quantify the role played by various external and internal forces that effect the dynamics of a drop impacting a complex surface. For the first time, three-dimensional simulations involving macro-textured surfaces are performed. Aside from demonstrating that simulations reproduce experiments in a quantitative manner, the…
