Threshold current density for diffusion-controlled stability of electrolytic surface nanobubbles.

Understanding the stability mechanism of surface micro/nanobubbles adhered to gas-evolving electrodes is essential for improving the efficiency of water electrolysis, which is known to be hindered by the bubble coverage on electrodes. Using molecular simulations, the diffusion-controlled evolution of single electrolytic nanobubbles on wettability-patterned nanoelectrodes is investigated. These nanoelectrodes feature hydrophobic islands as preferential nucleation sites and allow the growth of nanobubbles in the pinning mode. In these simulations, a threshold current density distinguishing stable nanobubbles from unstable nanobubbles is found. When the current density remains below the threshold value, nucleated nanobubbles grow to their equilibrium states, maintaining their nanoscopic size. However, for the current density above the threshold value, nanobubbles undergo unlimited growth and can eventually detach due to buoyancy. Increasing the pinning length of nanobubbles increases the degree of nanobubble instability. By connecting the current density with the local gas oversaturation, an extension of the stability theory for surface nanobubbles [Lohse and Zhang, Phys. Rev. E 91, 031003(R) (2015)] accurately predicts the nanobubble behavior found in molecular simulations, including equilibrium contact angles and the threshold current density. For larger systems that are not accessible to molecular simulations, continuum numerical simulations with the finite difference method combined with the immersed boundary method are performed, again demonstrating good agreement between numerics and theories.

Performance Enhancement of Electrocatalytic Hydrogen Evolution through Coalescence-Induced Bubble Dynamics.

The evolution of electrogenerated gas bubbles during water electrolysis can significantly hamper the overall process efficiency. Promoting the departure of electrochemically generated bubbles during (water) electrolysis is therefore beneficial. For a single bubble, a departure from the electrode surface occurs when buoyancy wins over the downward-acting forces (e.g., contact, Marangoni, and electric forces). In this work, the dynamics of a pair of H2 bubbles produced during the hydrogen evolution reaction in 0.5 M H2SO4 using a dual platinum microelectrode system is systematically studied by varying the electrode distance and the cathodic potential. By combining high-speed imaging and electrochemical analysis, we demonstrate the importance of bubble-bubble interactions in the departure process. We show that bubble coalescence may lead to substantially earlier bubble departure as compared to buoyancy effects alone, resulting in considerably higher reaction rates at a constant potential. However, due to continued mass input and conservation of momentum, repeated coalescence events with bubbles close to the electrode may drive departed bubbles back to the surface beyond a critical current, which increases with the electrode spacing. The latter leads to the resumption of bubble growth near the electrode surface, followed by buoyancy-driven departure. While less favorable at small electrode spacing, this configuration proves to be very beneficial at larger separations, increasing the mean current up to 2.4 times compared to a single electrode under the conditions explored in this study.

Freezing-induced topological transition of double-emulsion.

Solidification of complex liquids is pertinent to numerous natural and industrial processes. Here, we examine the freezing of a W/O/W double-emulsion, i.e., water-in-oil compound droplets dispersed in water. We show that the solidification of such hierarchical emulsions can trigger a topological transition; for example, in our case, we observe the transition from the stable W/O/W state to a (frozen) O/W single-emulsion configuration. Strikingly, this transition is characterised by sudden expulsion of the inner water drop from the encapsulating oil droplet. We propose that this topological transition is triggered by the freezing of the encapsulating oil droplet from the outside in, putting tension on the inner water drop thus, destabilizing the W/O/W configuration. Using high-speed imaging we characterize the destabilization process. Interestingly, we find that below a critical size of the inner drop, Rin,crit ≈ 19 µm, the topological transition does not occur any more and the double-emulsion remains stable, in line with our interpretation.

Buoyancy-driven attraction of active droplets.

For dissolving active oil droplets in an ambient liquid, it is generally assumed that the Marangoni effect results in repulsive interactions, while the buoyancy effects caused by the density difference between the droplets, diffusing product and the ambient fluid are usually neglected. However, it has been observed in recent experiments that active droplets can form clusters due to buoyancy-driven convection (Krüger et al. Eur. Phys. J. E, vol. 39, 2016, pp. 1-9). In this study, we numerically analyze the buoyancy effect, in addition to the propulsion caused by Marangoni flow (with its strength characterized by Péclet number Pe). The buoyancy effects have their origin in (i) the density difference between the droplet and the ambient liquid, which is characterized by Galileo number Ga, and (ii) the density difference between the diffusing product (i.e. filled micelles) and the ambient liquid, which can be quantified by a solutal Rayleigh number Ra. We analyze how the attracting and repulsing behaviour of neighbouring droplets depends on the control parameters Pe, Ga, and Ra. We find that while the Marangoni effect leads to the well-known repulsion between the interacting droplets, the buoyancy effect of the reaction product leads to buoyancy-driven attraction. At sufficiently large Ra, even collisions between the droplets can take place. Our study on the effect of Ga further shows that with increasing Ga, the collision becomes delayed. Moreover, we derive that the attracting velocity of the droplets, which is characterized by a Reynolds number Red, is proportional to Ra1/4/(ℓ/R), where ℓ/R is the distance between the neighbouring droplets normalized by the droplet radius. Finally, we numerically obtain the repulsive velocity of the droplets, characterized by a Reynolds number Rerep, which is proportional to PeRa-0.38. The balance of attractive and repulsive effect leads to Pe ~ Ra0.63, which agrees well with the transition curve between the regimes with and without collision.

Launching a Drop via Interplay of Buoyancy and Stick-Jump Dissolution.

According to Archimedes' principle, a submerged object with a density lower than that of aqueous acid solution is more buoyant than a smaller one. In this work, a remarkable phenomenon is reported wherein a dissolving drop on a substrate rises in the water only after it has diminished to a much smaller size, though the buoyancy is smaller. The drop consisting of a polymer solution reacts with the acid in the surrounding, yielding a water-soluble product. During drop dissolution, water-rich microdroplets form within the drop, merging with the external aqueous phase along the drop-substrate boundary. Two key elements determine the drop rise dynamics. The first is the stick-jump behavior during drop dissolution. The second is that buoyancy exerts a strong enough force on the drop at an Archimedean number greater than 1, while the stick-jump behavior is ongoing. The time of the drop rise is controlled by the initial size and the reaction rate of the drop. This novel mechanism for programmable drop rise may be beneficial for many future applications, such as microfluidics, microrobotics, and device engineering where the spontaneous drop detachment may be utilized to trigger a cascade of events in a dense medium.

Bistability in Radiatively Heated Melt Ponds.

Melting and solidification processes, intertwined with convective flows, play a fundamental role in geophysical contexts. One of these processes is the formation of melt ponds on glaciers, ice shelves, and sea ice. It is driven by solar radiation and is of great significance for Earth's heat balance, as it significantly lowers the albedo. Through direct numerical simulations and theoretical analysis, we unveil a bistability phenomenon in the melt pond dynamics. As solar radiation intensity and the melt pond's initial depth vary, an abrupt transition occurs: this tipping point transforms the system from a stable fully frozen state to another stable equilibrium state, characterized by a distinct melt pond depth. The physics of this transition can be understood within a heat flux balance model, which exhibits excellent agreement with our numerical results. Together with the Grossmann-Lohse theory for internally heated convection, the model correctly predicts the bulk temperature and the flow strength within the melt ponds, offering insight into the coupling of phase transitions with adjacent turbulent flows and the interplay between convective melting and radiation-driven processes.

Solutal Marangoni effect determines bubble dynamics during electrocatalytic hydrogen evolution.

Understanding and manipulating gas bubble evolution during electrochemical water splitting is a crucial strategy for optimizing the electrode/electrolyte/gas bubble interface. Here gas bubble dynamics are investigated during the hydrogen evolution reaction on a well-defined platinum microelectrode by varying the electrolyte composition. We find that the microbubble coalescence efficiency follows the Hofmeister series of anions in the electrolyte. This dependency yields very different types of H2 gas bubble evolution in different electrolytes, ranging from periodic detachment of a single H2 gas bubble in sulfuric acid to aperiodic detachment of small H2 gas bubbles in perchloric acid. Our results indicate that the solutal Marangoni convection, induced by the anion concentration gradient developing during the reaction, plays a critical role at practical current density conditions. The resulting Marangoni force on the H2 gas bubble and the bubble departure diameter therefore depend on how surface tension varies with concentration for different electrolytes. This insight provides new avenues for controlling bubble dynamics during electrochemical gas bubble formation.

Thin-Film-Mediated Deformation of Droplet during Cryopreservation.

Freezing of dispersions is omnipresent in science and technology. While the passing of a freezing front over a solid particle is reasonably understood, this is not so for soft particles. Here, using an oil-in-water emulsion as a model system, we show that when engulfed into a growing ice front, a soft particle severely deforms. This deformation strongly depends on the engulfment velocity V, even forming pointy-tip shapes for low values of V. We find such singular deformations are mediated by interfacial flows in nanometric thin liquid films separating the nonsolidifying dispersed droplets and the solidifying bulk. We model the fluid flow in these intervening thin films using a lubrication approximation and then relate it to the deformation sustained by the dispersed droplet.

Sodium chloride inhibits effective bubbly drag reduction in turbulent bubbly Taylor-Couette flows.

Using the Taylor-Couette geometry we experimentally investigate the effect of salt on drag reduction caused by bubbles present in the flow. We combine torque measurements with optical high-speed imaging to relate the bubble size to the drag experienced by the flow. Previous studies have shown that a small percentage of air (4%) can lead to dramatic drag reduction (40%). In contrast to previous laboratory experiments, which mainly used fresh water, we will vary the salinity from that of fresh water to the average salinity of ocean water. We find that the drag reduction is increasingly more inhibited for increasing salt concentrations, going from 40% for fresh water to just 15% for sea water. Salts present in the working fluid inhibit coalescence events, resulting in smaller bubbles in the flow and, with that, a decrease in the drag reduction. Above a critical salinity, increasing the salinity has no further effect on the size of bubbles in the flow and thus the drag experienced by the flow. Our new findings demonstrate the importance of sodium chloride on the bubbly drag reduction mechanism, and will further challenge naval architects to implement promising air lubrication systems on marine vessels. This article is part of the theme issue 'Taylor-Couette and related flows on the centennial of Taylor's seminal Philosophical Transactions paper (part 1)'.

Impact Forces of Water Drops Falling on Superhydrophobic Surfaces.

A falling liquid drop, after impact on a rigid substrate, deforms and spreads, owing to the normal reaction force. Subsequently, if the substrate is nonwetting, the drop retracts and then jumps off. As we show here, not only is the impact itself associated with a distinct peak in the temporal evolution of the normal force, but also the jump-off, which was hitherto unknown. We characterize both peaks and elucidate how they relate to the different stages of the drop impact process. The time at which the second peak appears coincides with the formation of a Worthington jet, emerging through flow focusing. Even low-velocity impacts can lead to a surprisingly high second peak in the normal force, even larger than the first one, namely when the Worthington jet becomes singular due to the collapse of an air cavity in the drop.

Evaporation of a Sessile Colloidal Water-Glycerol Droplet: Marangoni Ring Formation.

The transport and aggregation of particles in suspensions is an important process in many physicochemical and industrial processes. In this work, we study the transport of particles in an evaporating binary droplet. Surprisingly, the accumulation of particles occurs not only at the contact line (due to the coffee-stain effect) or at the solid substrate (due to sedimentation) but also at a particular radial position near the liquid-air interface, forming a "ring", which we term as the Marangoni ring. The formation of this ring is primarily attributed to the solutal Marangoni flow triggered by the evaporation dynamics of the water-glycerol droplet. Experiments and simulations show fair agreement in the volume evolution and the general structure of the solutal Marangoni flow, that is, the Marangoni vortex. Experiments show that the location of the Marangoni ring is strongly correlated with the Marangoni vortex. However, finite element numerical simulations fail to describe the particle distribution seen in the experiments. Interestingly, the particles not only accumulate to form the Marangoni ring but also assemble as colloidal crystals close to the liquid-air interface, yielding iridescence. The formation of the colloidal crystals in the experiments is strong evidence that non-hydrodynamic interactions, which are not represented in the simulations, also play a significant role in our system.

Surface Nanodroplet-Based Extraction Combined with Offline Analytic Techniques for Chemical Detection and Quantification.

Liquid-liquid extraction based on surface nanodroplets can be a green and sustainable technique to extract and concentrate analytes from a sample flow. However, because of the extremely small volume of each droplet (<10 fL, tens of micrometers in base radius and a few or less than 1 µm in height), only a few in situ analytical techniques, such as surface-enhanced Raman spectroscopy, were applicable for the online detection and analysis based on nanodroplet extraction. To demonstrate the versatility of surface nanodroplet-based extraction, in this work, the formation of octanol surface nanodroplets and extraction were performed inside a 3 m Teflon capillary tube. After extraction, surface nanodroplets were collected by injecting air into the tube, by which the contact line of surface droplets was collected by the capillary force. As the capillary allows for the formation of ∼1012 surface nanodroplets on the capillary wall, ≥2 mL of octanol can be collected after extraction. The volume of the collected octanol was enough for the analysis of offline analytical techniques such as UV-vis, GC-MS, and others. Coupled with UV-vis, reliable extraction and detection of two common water pollutants, triclosan and chlorpyrifos, was shown by a linear relationship between the analyte concentration in the sample solution and UV-vis absorbance. Moreover, the limit of detection (LOD) as low as 2 × 10-9 M for triclosan (∼0.58 µg/L) and 3 × 10-9 M for chlorpyrifos (∼1.05 µg/L) could be achieved. The collected surface droplets were also analyzed via gas chromatography (GC) and fluorescence microscopy. Our work shows that surface nanodroplet extraction may potentially streamline the process in sample pretreatment for sensitive chemical detection and quantification by using common analytic tools.

Transition in the growth mode of plasmonic bubbles in binary liquids.

Multi-component fluids with phase transitions show a plethora of fascinating phenomena with rich physics. Here we report on a transition in the growth mode of plasmonic bubbles in binary liquids. By employing high-speed imaging we reveal that the transition is from slow evaporative to fast convective growth and accompanied by a sudden increase in radius. The transition occurs as the three-phase contact line reaches the spinodal temperature of the more volatile component leading to massive, selective evaporation. This creates a strong solutal Marangoni flow along the bubble which marks the beginning of convective growth. We support this interpretation by simulations. After the transition the bubble starts to oscillate in position and in shape. Though different in magnitude the frequencies of both oscillations follow the same power law , which is characteristic of bubble shape oscillations, with the surface tension σ as the restoring force and the bubble's added mass as inertia. The transitions and the oscillations both induce a strong motion in the surrounding liquid, opening doors for various applications where local mixing is beneficial.

Resonance behavior of a compliant piezo-driven inkjet channel with an entrained microbubble.

Microbubbles entrained in a piezo-driven drop-on-demand printhead disturb the acoustics of the microfluidic ink channel and, thereby, the jetting behavior. Here, the resonance behavior of an ink channel as a function of the microbubble size and number of bubbles is studied through theoretical modeling and experiments. The system is modeled as a set of two coupled harmonic oscillators: one corresponds to the compliant ink channel and the other corresponds to the microbubble. The predicted and measured eigenfrequencies are in excellent agreement. It was found that the resonance frequency is independent of the bubble size as long as the compliance of the bubble dominates over that of the piezo actuator. An accurate description of the eigenfrequency of the coupled system requires the inclusion of the increased inertance of the entrained microbubble due to confinement. It is shown that the inertance of a confined bubble can be accurately obtained by using a simple potential flow approach. The model is further validated by the excellent agreement between the modeled and measured microbubble resonance curves. The present work, therefore, provides physical insight into the coupled dynamics of a compliant ink channel with an entrained microbubble.

Aspect Ratio Dependence of Heat Transfer in a Cylindrical Rayleigh-Bénard Cell.

While the heat transfer and the flow dynamics in a cylindrical Rayleigh-Bénard (RB) cell are rather independent of the aspect ratio Γ (diameter/height) for large Γ, a small-Γ cell considerably stabilizes the flow and thus affects the heat transfer. Here, we first theoretically and numerically show that the critical Rayleigh number for the onset of convection at given Γ follows Ra_{c,Γ}∼Ra_{c,∞}(1+CΓ^{-2})^{2}, with C≲1.49 for Oberbeck-Boussinesq (OB) conditions. We then show that, in a broad aspect ratio range (1/32)≤Γ≤32, the rescaling Ra→Ra_{ℓ}≡Ra[Γ^{2}/(C+Γ^{2})]^{3/2} collapses various OB numerical and almost-OB experimental heat transport data Nu(Ra,Γ). Our findings predict the Γ dependence of the onset of the ultimate regime Ra_{u,Γ}∼[Γ^{2}/(C+Γ^{2})]^{-3/2} in the OB case. This prediction is consistent with almost-OB experimental results (which only exist for Γ=1, 1/2, and 1/3) for the transition in OB RB convection and explains why, in small-Γ cells, much larger Ra (namely, by a factor Γ^{-3}) must be achieved to observe the ultimate regime.

Surface Properties of Colloidal Particles Affect Colloidal Self-Assembly in Evaporating Self-Lubricating Ternary Droplets.

In this work, we unravel the role of surface properties of colloidal particles on the formation of supraparticles (clusters of colloidal particles) in a colloidal Ouzo droplet. Self-lubricating colloidal Ouzo droplets are an efficient and simple approach to form supraparticles, overcoming the challenge of the coffee stain effect in situ. Supraparticles are an efficient route to high-performance materials in various fields, from catalysis to carriers for therapeutics. Yet, the role of the surface of colloidal particles in the formation of supraparticles using Ouzo droplets remains unknown. Therefore, we used silica particles as a model system and compared sterically stabilized versus electrostatically stabilized silica particles─positively and negatively charged. Additionally, we studied the effect of hydration. Hydrated negatively charged silica particles and sterically stabilized silica particles form supraparticles. Conversely, dehydrated negatively charged silica particles and positively charged amine-coated particles form flat film-like deposits. Notably, the assembly process is different for all the four types of particles. The surface modifications alter (a) the contact line motion of the Ouzo droplet and (b) the particle-oil and particle-substrate interactions. These alterations modify the particle accumulation at the various interfaces, which ultimately determines the shape of the final deposit. Thus, by modulating the surface properties of the colloidal particles, we can tune the shape of the final deposit, from a spheroidal supraparticle to a flat deposit. In the future, this approach can be used to tailor the supraparticles for applications such as optics and catalysis, where the shape affects the functionality.

Self-Propelled Detachment upon Coalescence of Surface Bubbles.

The removal of microbubbles from substrates is crucial for the efficiency of many catalytic and electrochemical gas evolution reactions in liquids. The current work investigates the coalescence and detachment of bubbles generated from catalytic decomposition of hydrogen peroxide. Self-propelled detachment, induced by the coalescence of two bubbles, is observed at sizes much smaller than those determined by buoyancy. Upon coalescence, the released surface energy is partly dissipated by the bubble oscillations, working against viscous drag. The remaining energy is converted to the kinetic energy of the out-of-plane jumping motion of the merged bubble. The critical ratio of the parent bubble sizes for the jumping to occur is theoretically derived from an energy balance argument and found to be in agreement with the experimental results. The present results provide both physical insight for the bubble interactions and practical strategies for applications in chemical engineering and renewable energy technologies like electrolysis.

Leidenfrost Effect as a Directed Percolation Phase Transition.

Volatile drops deposited on a hot solid can levitate on a cushion of their own vapor, without contacting the surface. We propose to understand the onset of this so-called Leidenfrost effect through an analogy to nonequilibrium systems exhibiting a directed percolation phase transition. When performing impacts on superheated solids, we observe a regime of spatiotemporal intermittency in which localized wet patches coexist with dry regions on the substrate. We report a critical surface temperature, which marks the upper bound of a large range of temperatures in which levitation and contact coexist. In this range, with decreasing temperature, the equilibrium wet fraction increases continuously from zero to one. Also, the statistical properties of the spatiotemporally intermittent regime are in agreement with that of the directed percolation universality class. This analogy allows us to redefine the Leidenfrost temperature and shed light on the physical mechanisms governing the transition to the Leidenfrost state.

Droplet plume emission during plasmonic bubble growth in ternary liquids.

Plasmonic bubbles are of great relevance in numerous applications, including catalytic reactions, micro/nanomanipulation of molecules or particles dispersed in liquids, and cancer therapeutics. So far, studies have been focused on bubble nucleation in pure liquids. Here we investigate plasmonic bubble nucleation in ternary liquids consisting of ethanol, water, and trans-anethole oil, which can show the so-called ouzo effect. We find that oil (trans-anethole) droplet plumes are produced around the growing plasmonic bubbles. The nucleation of the microdroplets and their organization in droplet plumes is due to the symmetry breaking of the ethanol concentration field during the selective evaporation of ethanol from the surrounding ternary liquids into the growing plasmonic bubbles. Numerical simulations show the existence of a critical Marangoni number Ma (the ratio between solutal advection rate and the diffusion rate), above which the symmetry breaking of the ethanol concentration field occurs, leading to the emission of the droplet plumes. The numerical results agree with the experimental observation that more plumes are emitted with increasing ethanol-water relative weight ratios and hence Ma. Our findings on the droplet plume formation reveal the rich phenomena of plasmonic bubble nucleation in multicomponent liquids and help to pave the way to achieve enhanced mixing in multicomponent liquids in chemical, pharmaceutical, and cosmetic industries.

Fabrication of freestanding Pt nanowires for use as thermal anemometry probes in turbulence measurements.

We report a robust fabrication method for patterning freestanding Pt nanowires for use as thermal anemometry probes for small-scale turbulence measurements. Using e-beam lithography, high aspect ratio Pt nanowires (~300 nm width, ~70 µm length, ~100 nm thickness) were patterned on the surface of oxidized silicon (Si) wafers. Combining wet etching processes with dry etching processes, these Pt nanowires were successfully released, rendering them freestanding between two silicon dioxide (SiO2) beams supported on Si cantilevers. Moreover, the unique design of the bridge holding the device allowed gentle release of the device without damaging the Pt nanowires. The total fabrication time was minimized by restricting the use of e-beam lithography to the patterning of the Pt nanowires, while standard photolithography was employed for other parts of the devices. We demonstrate that the fabricated sensors are suitable for turbulence measurements when operated in constant-current mode. A robust calibration between the output voltage and the fluid velocity was established over the velocity range from 0.5 to 5 m s-1 in a SF6 atmosphere at a pressure of 2 bar and a temperature of 21 °C. The sensing signal from the nanowires showed negligible drift over a period of several hours. Moreover, we confirmed that the nanowires can withstand high dynamic pressures by testing them in air at room temperature for velocities up to 55 m s-1.