Session D4: DFD Minisymposium: Nanobubbles

Experimental Studies of Nanobubbles at Solid-Water Interfaces

When a hydrophobic substrate is in contact with water, gas bubbles thinner than 100 nm can form at the interface and stay for long time under ambient conditions. These nanobubbles have significant influence on a range of interfacial processes. For example, they give rise to hydrodynamic slip on the boundary, initiate the rupture of thin liquid films, facilitate the long-ranged interactions between hydrophobic surfaces, and enhance the attachment of a macroscopic bubble to the substrate. Experimentally, it is nontrivial to characterize such small fragile bubbles and unravel their fundamental physical properties. Based on our established procedure for the nanobubble formation, we have systematically studied the formation, stability and response of nanobubbles to external fields (e.g. sonication, pressure drop and temperature rise). By following the bubble morphology by atomic force microscopy, we show that the loss or gain of the nanobubble volume is achieved mainly by the change in the bubble height. The pinning on the three-phase boundary has significant implication on the properties of nanobubbles under various conditions. This talk will cover the effects of the substrate structures on the nanobubble formation, and the response of nanobubbles to the gas dissolution, the temperature increase, the extended gentle ultrasound or the substantial pressure drop in the environment.   

Dynamic equilibrium explanation for nanobubbles unusual temperature and saturation dependence

Recent experimental evidence demonstrates that nanobubbles exhibit unusual behavior in response to changes in temperature and gas saturation in the liquid, an observation that may shed light on the mysterious origin of their stability. In this talk, we discuss an alternate formulation of the dynamic equilibrium mechanism for nanobubbles that predicts rich behavior in agreement with these measurements. Namely, we show that stable nanobubbles exist in narrow temperature and dissolved gas concentration ranges, that there is a maximum and minimum possible bubble size, and that nanobubble radii decrease with temperature. We also discuss these predictions in the context of other current hypotheses for nanobubble stability such as the recently-proposed diffusive ``traffic jam'' model.   

A new theory of bubble stability: Implications for nanobubbles at surfaces and in bulk solution

Nanobubbles on hydrophobic surfaces can be imaged using Atomic Force Microscopy and are implicated in the very long-range attraction measured between hydrophobic surfaces. However, the widely accepted theory of bubble dissolution predicts that small bubbles under the influence of Laplace pressure should rapidly dissolve resulting in bubble lifetimes of less than a second.\footnote{Epstein, P. S.; Plesset, M. S., \textit{Journal of Chemical Physics }\textbf{1950,} \textit{18} (11), 1505-1509.} Such short lifetimes should preclude nanobubbles from having an effect on surface force measurements or being observed by AFM,\footnote{Ljunggren, S.; Eriksson, J. C., \textit{Colloids and Surfaces a-Physicochemical and Engineering Aspects }\textbf{1997,} \textit{130}, 151-155.} yet nanobubbles are readily observed by AFM and widely implicated in force measurements between hydrophobic surfaces. This has led to a number of attempts at describing their unexpected stability, though no explanation is currently widely accepted. Additionally, nanobubbles have contact angles substantially greater (measured through the more dense liquid phase) than the equivalent macroscopic contact angle. It is clear that nanobubbles at surfaces pose a number of problems that are yet to be resolved. Additionally, recent reports of long-lived nanobubbles in bulk solution add to the mystery. Here we present a new theory describing the stability of nanobubbles. We calculate their lifetimes as a function of gas supersaturation and explain the long lifetimes observed. The same theory predicts that bulk nanobubbles should be stable under certain circumstances. Further, in an extension of this work we explain the difference in contact angle between the nanoscopic and macroscopic measurements and describe in detail the process by which nanobubbles are formed during solvent exchange. Experimental evidence is presented supporting this new approach and showing that this theoretical framework has parallels in other nucleated systems.   

Surface nanobubbles: Theory, numerics and experiments

When a solid is brought into contact with water, surface nanobubbles can be formed at the solid-liquid interface. These nanobubbles are small; their height is of order 10nm and their lateral sizes vary from 10-100 nm. Initially, the only proof of the existence of surface nanobubbles was delivered by atomic force microscopy. Later, additional techniques such as infrared attenuated total reflectance have confirmed the existence of gaseous domains on the solid-liquid interface. Before this overwhelming evidence, the existence of surface nanobubbles was controversial because they possess some unusual properties. For example, nanobubbles are surprisingly robust against dissolution by diffusion and Laplace pressure: Instead of the expected lifetime of about a microsecond, nanobubbles are found to survive for several hours and in some cases even several days. Additionally, surface nanobubbles are flatter than predicted by Young's law and are able to resist strong tensile stresses ($\sim$-6~MPa), rather than serving as a nucleation site for a macroscopic bubble. A deep understanding of surface nanobubbles is crucial for practical applications ({\em e.g.} drag reduction in microfluidic devices) but nanobubbles also pose fundamental questions on the validity of continuum models at the nanoscale. In this talk, we will discuss these open questions in detail by considering theoretical efforts and molecular dynamics simulations. Theoretically, we study the consequences of a pinned contact line. We find that the pinned contact line can explain the long lifetimes and many other nanobubble properties. From molecular dynamics results, we clarify the influence of the gas species on the contact angle. Finally, we will discuss some very recent experimental and theoretical work on the effects of an acoustic field on nanobubbles. We provide experimental data combined with a theoretical analysis and find that the acoustic driving can cause the nanobubbles to grow by rectified diffusion.   

A theory for metastabilities in bubble nucleation: can it help explaining nanobubbles?

The stability and the very existence of nanobubbles on a solid-liquid interface is a conundrum that has been puzzling the community of researchers working in the field since their discovery through AFM measurements in the late nineties. Nanobubbles are typically flat, with height on the order of 5-10 nm and lateral size order 100 nm or less. Pinning of the contact line presumably plays a crucial role and, based on classical estimates, they should dissolve almost immediately while they are instead reported to persist for days. Recently we developed a novel theoretical approach that is able to predict the heterogeneous nucleation path, and to explain the catalytic effect of geometrical defects in lowering the associated free-energy barrier (Giacomello et al., PRL 2012). The theory bridges the scales from nanometer to micron, and is then suitable for dealing with nanobubbles, as shown by comparison with advanced rare-event techniques used to evaluate the metastability in the atomistic context (Giacomello et al., Langmuir 2012). The interest of the approach is that it can provide an estimate for the transition frequency, i.e. the average lifetime of a metastable configuration. As will be discussed, the model can in principle be enriched to account for the interaction of the gas phase with the solid, indicated as responsible for the almost universal contact angle observed in the nanobubbles (Weijs et al., PRL 2012). If nanobubbles can be explained in the context of equilibrium statistical ensembles, as long-lived metastable states associated with a complex free-energy landscape, the work under way could shed new light on the elusive subject of their persistence. At present we cannot however exclude substantial non-equilibrium effects, outside the concept of metastability in the strict statistical-mechanics sense and associated, e.g., with thermal gradients.