Nanoparticle-nanobubble interactions: Charge inversion and re-entrant condensation of amidine latex nanoparticles driven by bulk nanobubbles.

HYPOTHESIS: The stability of colloidal suspensions can be influenced by supersaturation of the supporting electrolyte with gas. It has been proposed that this effect can be attributed to the formation of nanobubbles on the surface of the colloidal particles, in turn influencing DLVO forces. While previous interpretations have focused primarily on van der Waals interactions, probing positively charged particles can provide complementary insight into electrostatic interactions. EXPERIMENTS: High-power water electrolysis creates an aqueous solution supersaturated with oxygen and hydrogen. We study the ability of this solution to influence the electrophoretic properties of positive nanoparticles as a function of the particle-gas ratio. Both the ζ-potential and the effective hydrodynamic diameter of the resulting nanoentities were studied using dynamic light scattering for a range of nanoparticle sizes. FINDINGS: Gas-saturated solution interacts strongly with positive nanoparticles by decreasing and ultimately reversing the sign of their ζ-potential, which we attribute to the nucleation of negatively charged bubbles at the solid-liquid interface. This leads to re-entrant condensation of the particles near their point of zero charge, as directly observed via an increase in hydrodynamic diameter and macroscopic aggregation. These results indicate that modulation of electrostatic interactions can be the dominant mechanism for gas-particle interactions in these systems.

Direct Measurement of the Differential Capacitance of Solvent-Free and Dilute Ionic Liquids.

Differential capacitance is a key quantity in the understanding of electrical double-layer charging of electrolytes. However, experimental observations of ionic liquid systems are controversial, inconsistent, and often unable of confirming or refuting existing theories as well as highlighting discrepancies between the measurement techniques. We study the differential capacitance in both pure and dilute ionic liquids at room temperature. Using chronoamperometry to measure the differential capacitance of the liquids at a polycrystalline platinum electrode, we find good agreement between the measured capacitance curves and the extended mean-field model of Goodwin-Kornyshev [Goodwin, Z. A.; et al. Electrochim. Acta. 2017, 225, 190-197]. A crossover is found from the pure to the dilute regime, as shown by a transition from a camel-shape capacitance curve to a U-like one, together with a nonmonotonic dependence of capacitance with electrolyte concentration.

Near-Wall Molecular Ordering of Dilute Ionic Liquids.

The interfacial behavior of ionic liquids promises tunable lubrication as well as playing an integral role in ion diffusion for electron transfer. Diluting the ionic liquids optimizes bulk parameters, such as electric conductivity, and one would expect dilution to disrupt the near-wall molecular ordering. We study this ordering in the ionic liquids [Emim]+[NTf2]-, [Emim]+[DCA]-, and [C4mpyr]+[NTf2]-, diluted in the solvent dimethyl sulfoxide. We found a structural crossover from well-ordered ionic liquids to a well-ordered solvent with increasing dilution, but this occurs nonlinearly, with solvent molecules initially space-filling and solvating and later disrupting the ionic layers. This is of key importance for ionic liquids as optimized tunable nanolubricants.

Nanobubble-Nanoparticle Interactions in Bulk Solutions.

Nanobubbles form stable colloids in supersaturated solutions. Here we demonstrate the ability of these solutions to interact with Au nanoparticle suspensions. The principle goal was to demonstrate particle modification, similar to froth flotation, and we do indeed see bubble-particle interactions. However, unlike in froth flotation, where bubble-particle interactions are driven mainly through collisions, for bulk nanobubble solutions we find that the principle interaction is through nucleation of new nanobubbles on the particles.

Deformability Assessment of Waterborne Protozoa Using a Microfluidic-Enabled Force Microscopy Probe.

Many modern filtration technologies are incapable of the complete removal of Cryptosporidium oocysts from drinking-water. Consequently, Cryptosporidium-contaminated drinking-water supplies can severely implicate both water utilities and consumers. Existing methods for the detection of Cryptosporidium in drinking-water do not discern between non-pathogenic and pathogenic species, nor between viable and non-viable oocysts. Using FluidFM, a novel force spectroscopy method employing microchannelled cantilevers for single-cell level manipulation, we assessed the size and deformability properties of two species of Cryptosporidium that pose varying levels of risk to human health. A comparison of such characteristics demonstrated the ability of FluidFM to discern between Cryptosporidium muris and Cryptosporidium parvum with 86% efficiency, whilst using a measurement throughput which exceeded 50 discrete oocysts per hour. In addition, we measured the deformability properties for untreated and temperature-inactivated oocysts of the highly infective, human pathogenic C. parvum to assess whether deformability may be a marker of viability. Our results indicate that untreated and temperature-inactivated C. parvum oocysts had overlapping but significantly different deformability distributions.

Particle tracking around surface nanobubbles.

The exceptionally long lifetime of surface nanobubbles remains one of the biggest questions in the field. One of the proposed mechanisms for producing the stability is the dynamic equilibrium model, which describes a constant flux of gas in and out of the bubble. Here, we describe results from particle tracking experiments carried out to measure this flow. The results are analysed by measuring the Voronoï cell size distribution, the diffusion, and the speed of the tracer particles. We show that there is no detectable difference in the movement of particles above nanobubble-laden surfaces as compared to ones above nanobubble-free surfaces.

Nonintrusive optical visualization of surface nanobubbles.

Individual surface nanobubbles are visualized with nonintrusive optical interference-enhanced reflection microscopy, demonstrating that their formation is not a consequence of the hitherto used intrusive atomic force microscopy technique. We then use this new and fast technique to demonstrate that surface nanobubbles form in less than a few seconds after ethanol-water exchange, which is the standard procedure for their preparation, and examine how they react to temperature variations.

Directional liquid spreading over chemically defined radial wettability gradients.

We investigate the motion of liquid droplets on chemically defined radial wettability gradients. The patterns consist of hydrophobic fluorinated self-assembled monolayers (SAMs) on oxidized silicon substrates. The design comprises a central hydrophobic circle of unpatterned SAMs surrounded by annular regions of radially oriented stripes of alternating wettability, i.e., hydrophilic and hydrophobic. Variation in the relative width of the stripes allows control over the macroscopic wettability. When a droplet is deposited in the middle, it will start to move over to the radially defined wettability gradient, away from the center because of the increasing relative surface area of hydrophilic matter for larger radii in the pattern. The focus of this article is on a qualitative description of the characteristic motion on such types of anisotropic patterns. The influence of design parameters such as pattern dimensions, steepness of the gradient, and connection between different areas on the behavior of the liquid are analyzed and discussed in terms of advancing and receding contact lines, contact angles, spatial extent, and overall velocity of the motion.

A deliberation on nanobubbles at surfaces and in bulk.

Surface and bulk nanobubbles are two types of nanoscopic gaseous domain that have recently been discovered in interfacial physics. Both are expected to be unstable to dissolution because of the high internal pressure driving diffusion and the surface tension which squeezes the gas out, but there is a rapidly growing body of experimental evidence that demonstrates both bubble types to be stable. However, the two types of bubbles also differ in many respects: surface nanobubble stability is most probably assisted by the nearby wall, which can repel the water (in the case of hydrophobicity), accept physisorbed gas molecules, and reduce the surface area through which outfluxing can occur; bulk nanobubbles, on the other hand, must stabilise themselves. This is perhaps through ionic shielding, perhaps through diffusive shielding, or perhaps through both. Herein, the features of both bubble types are described individually, their common and disparate features are discussed, and emerging applications are examined.

Temperature dependence of surface nanobubbles.

The temperature dependence of nanobubbles was investigated experimentally using atomic force microscopy. By scanning the same area of the surface at temperatures from 51 °C to 25 °C it was possible to track geometrical changes of individual nanobubbles as the temperature was decreased. Interestingly, nanobubbles of the same size react differently to this temperature change; some grow whilst others shrink. This effect cannot be attributed to Ostwald ripening, since the growth and shrinkage of nanobubbles appears to occur in distinct patches on the substrate. The total nanobubble volume per unit area shows a maximum around 33 °C, which is comparable with literature where experiments were carried out with increasing temperature. This underlines the stability of surface nanobubbles.

Diffusive shielding stabilizes bulk nanobubble clusters.

Using molecular dynamics, we study the nucleation and stability of bulk nanobubble clusters. We study the formation, growth, and final size of bulk nanobubbles. We find that, as long as the bubble-bubble interspacing is small enough, bulk nanobubbles are stable against dissolution. Simple diffusion calculations provide an excellent match with the simulation results, giving insight into the reason for the stability: nanobubbles in a cluster of bulk nanobubbles protect each other from diffusion by a shielding effect.

Localized removal of layers of metal, polymer, or biomaterial by ultrasound cavitation bubbles.

We present an ultrasonic device with the ability to locally remove deposited layers from a glass slide in a controlled and rapid manner. The cleaning takes place as the result of cavitating bubbles near the deposited layers and not due to acoustic streaming. The bubbles are ejected from air-filled cavities micromachined in a silicon surface, which, when vibrated ultrasonically at a frequency of 200 kHz, generate a stream of bubbles that travel to the layer deposited on an opposing glass slide. Depending on the pressure amplitude, the bubble clouds ejected from the micropits attain different shapes as a result of complex bubble interaction forces, leading to distinct shapes of the cleaned areas. We have determined the removal rates for several inorganic and organic materials and obtained an improved efficiency in cleaning when compared to conventional cleaning equipment. We also provide values of the force the bubbles are able to exert on an atomic force microscope tip.

Knudsen gas provides nanobubble stability.

We provide a model for the remarkable stability of surface nanobubbles to bulk dissolution. The key to the solution is that the gas in a nanobubble is of Knudsen type. This leads to the generation of a bulk liquid flow which effectively forces the diffusive gas to remain local. Our model predicts the presence of a vertical water jet immediately above a nanobubble, with an estimated speed of ∼3.3 m/s, in good agreement with our experimental atomic force microscopy measurement of ∼2.7 m/s. In addition, our model also predicts an upper bound for the size of nanobubbles, which is consistent with the available experimental data.

Surface nanobubbles as a function of gas type.

We experimentally investigate the nucleation of surface nanobubbles on PFDTS-coated silicon as a function of the specific gas dissolved in water. In each case, we restrict ourselves to equilibrium conditions (c = 100%, T(liquid) = T(substrate)). Not only is nanobubble nucleation a strong function of gas type, but there also exists an optimal system temperature of ∼35 -40 °C where nucleation is maximized, which is weakly dependent on gas type. We also find that the contact angle is a function of the nanobubble radius of curvature for all gas types investigated. Fitting this data allows us to describe a line tension that is dependent on the type of gas, indicating that the nanobubbles sit on top of adsorbed gas molecules. The average line tension was τ ≈ -0.8 nN.

Nanobubbles and micropancakes: gaseous domains on immersed substrates.

Surface nanobubbles and micropancakes are two recent discoveries in interfacial physics. They are nanoscopic gaseous domains that form at the solid/liquid interface. The fundamental interest focuses on the fact that they are surprisingly stable to dissolution, lasting for at least 10-11 orders of magnitude longer than the classical expectation. So far, many articles have been published that describe various different nucleation methods and 'ideal' systems and experimental techniques for nanobubble research, and we are now at the stage where we can begin to investigate the fundamental questions in detail. In this topical review, we summarize the current state of research in the field and give an overview of the partial answers that have been proposed or that can be inferred to date. We relate nanobubbles and micropancakes, and we try to build a framework within which nucleation may be understood. We also discuss evidence for and against different aspects of nanobubble stability, as well as suggesting what still needs to be done to obtain a full understanding.

Surface bubble nucleation stability.

Recent research has revealed several different techniques for nanoscopic gas nucleation on submerged surfaces, with findings seemingly in contradiction with each other. In response to this, we have systematically investigated the occurrence of surface nanobubbles on a hydrophobized silicon substrate for various different liquid temperatures and gas concentrations, which we controlled independently. We found that nanobubbles occupy a distinct region of this parameter space, occurring for gas concentrations of approximately 100%-110%. Below the nanobubble region we did not detect any gaseous formations on the substrate, whereas micropancakes (micron wide, nanometer high gaseous domains) were found at higher temperatures and gas concentrations. We moreover find that supersaturation of dissolved gases is not a requirement for nucleation of bubbles.

Dynamic dewetting through micropancake growth.

We experimentally investigate the dynamics of nanometer-high, micrometer-wide gassy layers at the interface between a hydrophobic solid and bulk water. These micropancakes grow laterally in time, on the timescale of an hour, leading to partial dewetting of the solid. The growth is directional, mediated by chemical roughness on the substrate, and transient, occurring within the first hour after liquid deposition. We use circularity to measure the roundness of a micropancake (circularity C = 2(piA)(1/2)/L, where A is the surface area and L is the perimeter). The growth is anisotropic, as demonstrated by a decrease in circularity with time. However, once a micropancake reaches size saturation, its bulk rearranges its shape in order to minimize the length of its three-phase line. We interpret this combination of growth followed by bulk rearrangement as dynamic dewetting.

Convective roll dynamics in liquid 4He near the onset of convection.

We present results of experiments on Rayleigh-Bénard convection in liquid 4He at several temperatures. We show visually that with carefully defined boundary conditions the basic convection state consists of parallel rolls which are aligned in one of two directions, the angle thus defined as being temperature dependent and we attempt to explain this behavior. We also show directly the skew-varicose instability acting on the basic state and correlate it with fluctuations in the temperature difference across the fluid layer.