Faster Nucleation of Ice at the Three-Phase Contact Line: Influence of Interfacial Chemistry.

Controlling the nucleation of ice is important in many areas including atmospheric sciences, cryopreservation, food science, and infrastructure protection. Presently, we conduct controlled experiments and analysis to uncover the influence of surface chemistry at the three-phase line on ice nucleation. We show that ice nucleation is faster upon replacing the air at the water-air interface with oils like silicone oil and almond oil. We show via statistically meaningful and carefully designed experiments that ice nucleation occurs at a higher temperature at an aluminum-water-silicone oil (or almond oil) interface as compared to an aluminum-water-air interface. We show that the location of ice nucleation can be controlled (in situations with multiple locations for ice nucleation) by controlling the interfacial chemistry at the three-phase line. We develop a model (which utilizes classical nucleation theory) to study the combined influence of two interfaces on a seed crystal of ice originating at the three-phase contact line. This model can evaluate the thermodynamic competition between nucleation at the three -phase line and heterogeneous nucleation at an interface. The model shows that three-phase contact lines usually result in a higher driving force than heterogeneous nucleation, which speeds up nucleation kinetics. Overall, our experiments and modeling uncover several useful insights into the influence of three-phase lines on nucleation during contact freezing.

Pool Boiling of Nanofluids on Biphilic Surfaces: An Experimental and Numerical Study.

This study addresses the combination of customized surface modification with the use of nanofluids, to infer on its potential to enhance pool-boiling heat transfer. Hydrophilic surfaces patterned with superhydrophobic regions were developed and used as surface interfaces with different nanofluids (water with gold, silver, aluminum and alumina nanoparticles), in order to evaluate the effect of the nature and concentration of the nanoparticles in bubble dynamics and consequently in heat transfer processes. The main qualitative and quantitative analysis was based on extensive post-processing of synchronized high-speed and thermographic images. To study the nucleation of a single bubble in pool boiling condition, a numerical model was also implemented. The results show an evident benefit of using biphilic patterns with well-established distances between the superhydrophobic regions. This can be observed in the resulting plot of the dissipated heat flux for a biphilic pattern with seven superhydrophobic spots, δ = 1/d and an imposed heat flux of 2132 w/m2. In this case, the dissipated heat flux is almost constant (except in the instant t* ≈ 0.9 when it reaches a peak of 2400 W/m2), whilst when using only a single superhydrophobic spot, where the heat flux dissipation reaches the maximum shortly after the detachment of the bubble, dropping continuously until a new necking phase starts. The biphilic patterns also allow a controlled bubble coalescence, which promotes fluid convection at the hydrophilic spacing between the superhydrophobic regions, which clearly contributes to cool down the surface. This effect is noticeable in the case of employing the Ag 1 wt% nanofluid, with an imposed heat flux of 2132 W/m2, where the coalescence of the drops promotes a surface cooling, identified by a temperature drop of 0.7 °C in the hydrophilic areas. Those areas have an average temperature of 101.8 °C, whilst the average temperature of the superhydrophobic spots at coalescence time is of 102.9 °C. For low concentrations as the ones used in this work, the effect of the nanofluids was observed to play a minor role. This can be observed on the slight discrepancy of the heat dissipation decay that occurred in the necking stage of the bubbles for nanofluids with the same kind of nanoparticles and different concentration. For the Au 0.1 wt% nanofluid, a heat dissipation decay of 350 W/m2 was reported, whilst for the Au 0.5 wt% nanofluid, the same decay was only of 280 W/m2. The results of the numerical model concerning velocity fields indicated a sudden acceleration at the bubble detachment, as can be qualitatively analyzed in the thermographic images obtained in this work. Additionally, the temperature fields of the analyzed region present the same tendency as the experimental results.

Aluminum-Based Promotion of Nucleation of Carbon Dioxide Hydrates.

Gas hydrate formation has several applications in CO2 sequestration, flow assurance, and desalination. Nucleation of hydrates is constrained by very high induction (wait) times, which necessitates the use of complex nucleation promotion techniques to form hydrates. Presently, we report the discovery of a simple, passive nucleation promotion technique, wherein an aluminum surface significantly accelerates nucleation of CO2hydrates. Statistically meaningful measurements of induction times for CO2 hydrate nucleation were undertaken using water droplets as individual microsystems for hydrate formation. The influence of various metal surfaces, droplet size, CO2 dissolution time, and the presence of salts in water on nucleation kinetics was characterized. Interestingly, we observe nucleation initiation only on aluminum surfaces, the influence of which cannot be replicated by salts of aluminum. We discover that the aluminum-water interface is responsible for nucleation promotion. We hypothesize that hydrogen bubbles generated at the aluminum-water interface are responsible for nucleation promotion.

Acoustic detection of electrostatic suppression of the Leidenfrost state.

At high temperatures, a droplet can rest on a cushion of its vapor (the Leidenfrost effect). Application of an electric field across the vapor gap fundamentally eliminates the Leidenfrost state by attracting liquid towards the surface. This study uses acoustic signature tracking to study electrostatic suppression of the Leidenfrost state on solid and liquid surfaces. It is seen that the liquid-vapor instabilities that characterize suppression on solid surfaces can be detected acoustically. This can be the basis for objective measurements of the threshold voltage and frequency required for suppression. Acoustic analysis provides additional physical insights that would be challenging to obtain with other measurements. On liquid surfaces, the absence of an acoustic signal indicates a different suppression mechanism (instead of instabilities). Acoustic signature tracking can also detect various boiling patterns associated with electrostatically assisted quenching. Overall, this work highlights the benefits of acoustics as a tool to better understand electrostatic suppression of the Leidenfrost state, and the resulting heat transfer enhancement.

Fundamental interfacial mechanisms underlying electrofreezing.

This article reviews the fundamental interfacial mechanisms underlying electrofreezing (promotion of ice nucleation via the application of an electric field). Electrofreezing has been an active research topic for many decades, with applications in food preservation, cryopreservation, cryogenics and ice formation. There is substantial literature detailing experimental and simulations-based studies, which aim to understand the complex mechanisms underlying accelerated ice nucleation in the presence of electric fields and electrical charge. This work provides a critical review of all such studies. It is noted that application-focused studies of electrofreezing are excluded from this review; such studies have been previously reviewed in literature. This review focuses only on fundamental studies, which analyze the physical mechanisms underlying electrofreezing. Topics reviewed include experimental studies on electrofreezing (DC and AC electric fields), pyroelectricity-based control of freezing, molecular dynamics simulations of electrofreezing, and thermodynamics-based explanations of electrofreezing. Overall, it is seen that electrofreezing can enable disruptive advancements in the control of liquid-to-solid phase change, and that our current understanding of the underlying mechanisms can be significantly improved through further studies of various interfacial effects coming into play.

Electrostatic Suppression of the Leidenfrost State on Liquid Substrates.

An applied electric field can fundamentally eliminate the Leidenfrost effect (formation of a vapor layer at the solid-liquid interface at high temperatures). This study analyzes electrostatic suppression of the Leidenfrost state on liquid substrates. Electrostatic suppression on silicone oil and Wood's metal (liquid alloy) is studied via experimentation, high-speed imaging, and analyses. It is seen that the nature of electrostatic suppression can be drastically different from that on a solid substrate. First, the Leidenfrost droplet completely penetrates into the silicone oil substrate and converts to a thin film under an electric field. This is due to the existence of an electric field inside the substrate and the deformability of the silicone oil interface. A completely different type of suppression is observed for Wood's metal and solid substrates, which have low deformability and lack an electric field in the substrate. Second, the minimum voltage to trigger suppression is significantly lower on silicone oil when compared to Wood's metal and solid substrates. Fundamental differences between these transitions are analyzed, and a multiphysics analytical model is developed to predict the vapor layer thickness on deformable liquids. Overall, this study lays the foundation for further studies on electrostatic manipulation of the Leidenfrost state on liquids.

Metal-Foam-Based Ultrafast Electronucleation of Hydrates at Low Voltages.

The induction time for the nucleation of hydrates can be significantly reduced by electronucleation, which consists of applying an electrical potential across the hydrate precursor solution. This study reveals that open-cell aluminum foam electrodes can reduce the electronucleation induction time by 150× when compared to nonfoam electrodes. Experiments with tetrahydrofuran hydrates show that aluminum foam electrodes trigger near-instantaneous nucleation (in only tens of seconds) at low voltages. Furthermore, this study suggests that two distinct interfacial mechanisms influence electronucleation, namely, electrolytic bubble generation and the formation of metal ion complex-based coordination compounds. These mechanisms (which depend on the electrode material and polarity) affect the induction time to vastly different extents. Coordination compound formation (verified via detection of metal ions in solution) exerts a much greater influence on electronucleation than the mechanistic effects associated with bubble generation. This work uncovers the benefits of using foams to promote electronucleation and shows that foams lead to more deterministic (as opposed to stochastic) nucleation when compared with nonfoam electrodes.

Electronucleation for Rapid and Controlled Formation of Hydrates.

Nucleation of hydrates involves very long induction times (hours to days), which is a challenge for applications requiring rapid hydrate formation. This study introduces and analyzes the use of electric fields to accelerate and control hydrate nucleation. Experiments with tetrahydrofuran (THF) hydrates reveal that the induction time can be reduced by 100×, by applying an electrical potential across the precursor solution. The induction time rapidly decreases with increasing voltages and is on the order of a few minutes at 100 V. It is seen that voltage-induced current flow in the solution is responsible for electronucleation. Very low currents (microamperes) are sufficient for electronucleation. Nucleation promotion can be attributed to phenomena associated with bubble formation due to chemical reactions at the electrodes. Overall, this study lays the foundation for the control and promotion of nucleation by electric fields, and enables possibilities for instantaneous nucleation.

Saltwater icephobicity: Influence of surface chemistry on saltwater icing.

Most studies on icephobicity focus on ice formation with pure water. This manuscript presents studies to understand the influence of surfaces on saltwater ice nucleation and propagation. Experiments are conducted to quantify the influence of surface chemistry on saltwater ice nucleation and to understand the utility of superhydrophobic surfaces for saltwater icephobicity. These experiments are conducted with pure water and two sodium chloride solutions, which represent the salinity of seawater and briny produced water. It is seen that the presence of salt slows down the ice front propagation velocity significantly. Saltwater droplet impact dynamics on superhydrophobic surfaces are also different from pure water. Saltwater droplets retract more and a greater fraction of impacting liquid is repelled from the superhydrophobic surface. It is seen that the greater bounciness of saltwater droplets is a result of slower ice nucleation propagation kinetics. These experiments indicate that superhydrophobic surfaces will have better resistance to impact icing with saltwater than pure water and can remain useful at temperatures as low as -40 °C. Overall, this work is a starting point for further studies on heterogeneous nucleation in saltwater and serves as a bridge between the widely studied freshwater icephobic surfaces and saltwater-related applications.

Electrofreezing of water droplets under electrowetting fields.

Electrofreezing is the electrically induced nucleation of ice from supercooled water. This work studies ice nucleation in electrowetted water droplets, wherein there is no electric field inside the droplet resting on a dielectric layer. Instead, there is an interfacial electric field and charge buildup at the solid-liquid interface. This situation is in contrast to most previous electrofreezing studies, which have used bare electrodes, involve current flow, and have a volumetric electric field inside the liquid. Infrared and high-speed visualizations of static water droplets are used to analyze surface electrofreezing. Ultrahigh electric fields of up to 80 V/µm are applied, which is one order of magnitude higher than in previous studies. The results facilitate an in-depth understanding of various mechanisms underlying electrofreezing. First, it is seen that interfacial electric fields alone can significantly elevate freezing temperatures by more than 15 °C, in the absence of current flow. Second, the magnitude of electrofreezing induced temperature elevation saturates at high electric field strengths. Third, the polarity of the interfacial charge does not significantly influence electrofreezing. Overall, it is seen that electrofreezing nucleation kinetics is primarily influenced by the three-phase boundary and not the solid-liquid interface. Through careful electrofreezing measurements on dielectric layers with pinholes to allow current flow, the individual role of electric fields and electric currents on electrofreezing is isolated. It is seen that both the electric field and the electric current influence electrofreezing; however, the physical mechanisms are very different.

Heat transfer enhancement accompanying Leidenfrost state suppression at ultrahigh temperatures.

The well-known Leidenfrost effect is the formation of a vapor layer between a liquid and an underlying hot surface. This insulating vapor layer severely degrades heat transfer and results in surface dryout. We measure the heat transfer enhancement and dryout prevention benefits accompanying electrostatic suppression of the Leidenfrost state. Interfacial electric fields in the vapor layer can attract liquid toward the surface and promote wetting. This principle can suppress dryout even at ultrahigh temperatures exceeding 500 °C, which is more than 8 times the Leidenfrost superheat for organic solvents. Robust Leidenfrost state suppression is observed for a variety of liquids, ranging from low electrical conductivity organic solvents to electrically conducting salt solutions. Elimination of the vapor layer increases heat dissipation capacity by more than 1 order of magnitude. Heat removal capacities exceeding 500 W/cm(2) are measured, which is 5 times the critical heat flux (CHF) of water on common engineering surfaces. Furthermore, the heat transfer rate can be electrically controlled by the applied voltage. The underlying science is explained via a multiphysics analytical model which captures the coupled electrostatic-fluid-thermal transport phenomena underlying electrostatic Leidenfrost state suppression. Overall, this work uncovers the physics underlying dryout prevention and demonstrates electrically tunable boiling heat transfer with ultralow power consumption.

Influence of substrate elasticity on droplet impact dynamics.

Droplet impact dynamics is vital to the understanding of several phase-change and heat-transfer phenomena. This work examines the role of substrate elasticity on the spreading and retraction behavior of water droplets impacting flat and textured superhydrophobic substrates. Experiments reveal that droplet retraction on flat surfaces decreases with decreasing substrate elasticity. This trend is confirmed through a careful measurement of droplet impact dynamics on multiple PDMS surfaces with varying elastic moduli and comparison with impact dynamics on hard silicon surfaces. These findings reveal that surfaces tend to become more wettable upon droplet impact as the elastic modulus is decreased. First-order analyses are developed to explain this reduced retraction in terms of increased viscoelastic dissipation on soft substrates. Interestingly, superhydrophobic surfaces display substrate-elasticity-invariant impact dynamics. These findings are critical when designing polymeric surfaces for fluid-surface interaction applications.

Dynamics of ice nucleation on water repellent surfaces.

Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water-surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of heterogeneous nucleation at the water-substrate interface. This work also includes an analysis (based on classical nucleation theory) to estimate various homogeneous and heterogeneous nucleation rates in icing situations. The key finding is that ice nucleation delay on superhydrophobic surfaces is more prominent at moderate degrees of supercooling, while closer to the homogeneous nucleation temperature, bulk and air-water interface nucleation effects become equally important. The study presented here offers a comprehensive perspective on the efficacy of textured surfaces for nonicing applications.

Predictive model for ice formation on superhydrophobic surfaces.

The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies.

Design of ice-free nanostructured surfaces based on repulsion of impacting water droplets.

Materials that control ice accumulation are important to aircraft efficiency, highway and powerline maintenance, and building construction. Most current deicing systems include either physical or chemical removal of ice, both energy and resource-intensive. A more desirable approach would be to prevent ice formation rather than to fight its build-up. Much attention has been given recently to freezing of static water droplets resting on supercooled surfaces. Ice accretion, however, begins with the droplet/substrate collision followed by freezing. Here we focus on the behavior of dynamic droplets impacting supercooled nano- and microstructured surfaces. Detailed experimental analysis of the temperature-dependent droplet/surface interaction shows that highly ordered superhydrophobic materials can be designed to remain entirely ice-free down to ca. -25 to -30 °C, due to their ability to repel impacting water before ice nucleation occurs. Ice accumulated below these temperatures can be easily removed. Factors contributing to droplet retraction, pinning and freezing are addressed by combining classical nucleation theory with heat transfer and wetting dynamics, forming the foundation for the development of rationally designed ice-preventive materials. In particular, we emphasize the potential of hydrophobic polymeric coatings bearing closed-cell surface microstructures for their improved mechanical and pressure stability, amenability to facile replication and large-scale fabrication, and opportunities for greater tuning of their material and chemical properties.

Preventing the Cassie-Wenzel transition using surfaces with noncommunicating roughness elements.

Control and switching of liquid droplet states on artificially structured surfaces have significant applications in the field of microfluidics. The present work introduces the concept of using structured surfaces consisting of noncommunicating roughness elements to prevent the transition of a droplet from the Cassie to the Wenzel state. The use of noncommunicating roughness elements leads to a confinement of the medium under the droplet in its Cassie state. Transition to the Wenzel state on such surfaces requires expulsion of this confined medium, which offers significantly increased resistance to the Wenzel transition unlike surfaces consisting of communicating roughness elements. This enhances the robustness of the Cassie state and significantly minimizes the possibility of the Cassie-Wenzel transition. In the present work, the resistance of a surface to the Wenzel transition is measured in terms of the electrowetting (EW) voltage required to trigger this transition. It is seen that surfaces with noncommunicating roughness elements (cratered surfaces) require significantly higher voltages to trigger the Wenzel transition than corresponding surfaces with communicating roughness elements. The findings from the present work also indicate that EW-induced droplet morphology control characteristics show a strong dependence on the nature of the roughness elements (communicating versus noncommunicating). Different aspects of droplet morphology and EW-induced state transition control on surfaces with noncommunicating roughness elements are analyzed; it is seen that such surfaces offer significant possibilities for the development of robust superhydrophobic surfaces.

Electrowetting-based control of droplet transition and morphology on artificially microstructured surfaces.

Electrowetting (EW) has recently been demonstrated as a powerful tool for controlling droplet morphology on smooth and artificially structured surfaces. The present work involves a systematic experimental investigation of the influence of electrowetting in determining and altering the state of a static droplet resting on an artificially microstructured surface. Extensive experimentation is carried out to benchmark a previously developed energy-minimization-based model that analyzed the influence of interfacial energies, surface roughness parameters, and electric fields in determining the apparent contact angle of a droplet in the Cassie and Wenzel states under the influence of an EW voltage. The EW voltage required to trigger a transition from the Cassie state to the Wenzel state is experimentally determined for surfaces having a wide range of surface parameters (surface roughness and fraction of surface area covered with pillars). The reversibility of the Cassie-Wenzel transition upon the removal of the EW voltage is also quantified and analyzed. The experimental results from the present work form the basis for the design of surfaces that enable dynamic control of droplet morphology. A significant finding from the present work is that nonconservative dissipative forces have a significant influence in opposing fluid flow inside the microstructured surface that inhibits reversibility of the Cassie-Wenzel transition. The artificially structured surfaces considered in this work have microscale roughness feature sizes that permits direct visual observation of EW-induced Cassie-Wenzel droplet transition; this is the first reported visual confirmation of EW-induced droplet state transition.

Electrowetting-based control of static droplet states on rough surfaces.

Electrowetting (EW) is a powerful tool to control fluid motion at the microscale and has promising applications in the field of microfluidics. The present work analyzes the influence of an electrowetting voltage in determining and altering the state of a static droplet resting on a rough surface. An energy-minimization-based modeling approach is used to analyze the influence of interfacial energies, surface roughness parameters, and electric fields in determining the apparent contact angle of a droplet in the Cassie and Wenzel states under the influence of an EW voltage. The energy-minimization-based approach is also used to analyze the Cassie-Wenzel transition under the influence of an EW voltage and estimate the energy barrier to transition. The results obtained show that EW is a powerful tool to alter the relative stabilities of the Cassie and Wenzel states and enable dynamic control of droplet morphology on rough surfaces. The versatility and generalized nature of the present modeling approach is highlighted by application to the prediction of the contact angle of a droplet on an electrowetted rough surface consisting of a dielectric layer of nonuniform thickness.