Vincent S. J. Craig

Boundary slip in Newtonian liquids: a review of experimental studies

For several centuries fluid dynamics studies have relied upon the assumption that when a liquid flows over a solid surface, the liquid molecules adjacent to the solid are stationary relative to the solid. This no-slip boundary condition (BC) has been applied successfully to model many macroscopic experiments, but has no microscopic justification. In recent years there has been an increased interest in determining the appropriate BCs for the flow of Newtonian liquids in confined geometries, partly due to exciting developments in the fields of microfluidic and microelectromechanical devices and partly because new and more sophisticated measurement techniques are now available. An increasing number of research groups now dedicate great attention to the study of the flow of liquids at solid interfaces, and as a result a large number of experimental, computational and theoretical studies have appeared in the literature. We provide here a review of experimental studies regarding the phenomenon of slip of Newtonian liquids at solid interfaces. We dedicate particular attention to the effects that factors such as surface roughness, wettability and the presence of gaseous layers might have on the measured interfacial slip. We also discuss how future studies might improve our understanding of hydrodynamic BCs and enable us to actively control liquid slip.

Mechanism of cationic surfactant adsorption at the solid-aqueous interface

Until recently, the rapid time scales associated with the formation of an adsorbed surfactant layer at the solid-aqueous interface has prevented accurate investigation of adsorption kinetics. This has led to the mechanism of surfactant adsorption being inferred from thermodynamic data. These explanations have been further hampered by a poor knowledge of the equilibrium adsorbed surfactant morphology, with the structure often misinterpreted as simple monolayers or bilayers, rather than the discrete surface aggregates that are present in many surfactant-substrate systems. This review aims to link accepted equilibrium data with more recent kinetic and structural information in order to describe the adsorption process for ionic surfactants. Traditional equilibrium data, such as adsorption isotherms obtained from depletion approaches, and the most popular methods by which these data are interpreted are examined. This is followed by a description of the evidence for discrete aggregation on the substrate, and the morphology of these aggregates. Information gained using techniques such as atomic force microscopy, fluorescence quenching and neutron reflectivity is then reviewed. With this knowledge, the kinetic data obtained from relatively new techniques with high temporal resolution, such as ellipsometry and optical reflectometry, are examined. On this basis the likely mechanisms of adsorption are proposed.

Very Small Bubbles at Surfaces: the Nanobubble Puzzle

Atomic Force Microscope images and other experiments show us that very small stable bubbles, known as nanobubbles, can be present on surfaces despite well founded theoretical considerations that predict otherwise. Nanobubbles are thought to play a role in the rupture of thin films during froth flotation, hydrodynamic slip over surfaces, interaction forces between hydrophobic surfaces and influence the electroplating and electrolysis processes. Here we describe what is known of nanobubbles and discuss the challenges in understanding nanobubble morphology and stability.

The Influence of Chain Length and Electrolyte on the Adsorption Kinetics of Cationic Surfactants at the Silica-aqueous Solution Interface

The equilibrium and kinetic aspects of the adsorption of alkyltrimethylammonium surfactants at the silica-aqueous solution interface have been investigated using optical reflectometry. The effect of added electrolyte, the length of the hydrocarbon chain, and of the counter- and co-ions has been elucidated. Increasing the length of the surfactant hydrocarbon chain results in the adsorption isotherm being displaced to lower concentrations. The adsorption kinetics indicate that above the cmc micelles are adsorbing directly to the surface and that as the chain length increases the hydrophobicity of the surfactant has a greater influence on the adsoption kinetics. While the addition of 10 mM KBr increases the CTAB maximal surface excess, there is no corresponding increase for the addition of 10 mM KCl to the CTAC system. This is attributed to the decreased binding efficiency of the chloride ion relative to the bromide ion. Variations in the co-ion species (Li, Na, K) have little effect on the adsorption rate and surface excess of CTAC up to a bulk electrolyte concentration of 10 mM. However, the rate of adsorption is increased in the presence of electrolyte. Slow secondary adsorption is seen over a range of concentrations for CTAC in the absence of electrolyte and importantly in the presence of LiCl; the origin of this slow adsorption is attributed to a structural barrier to adsorption.

Cleaning using nanobubbles: Defouling by electrochemical generation of bubbles

Here we demonstrate that nanobubbles can be used as cleaning agents both for the prevention of surface fouling and for defouling surfaces. In particular nanobubbles can be used to remove proteins that are already adsorbed to a surface, as well as for the prevention of nonspecific adsorption of proteins. Nanobubbles were produced on highly oriented pyrolytic graphite (HOPG) surfaces electrochemically and observed by atomic force microscopy (AFM). Nanobubbles produced by electrochemical treatment for 20 s before exposure to bovine serum albumin (BSA) were found to decrease protein coverage by 26-34%. Further, pre-adsorbed protein on a HOPG surface was also removed by formation of electrochemically produced nanobubbles. In AFM images, the coverage of BSA was found to decrease from 100% to 82% after 50 s of electrochemical treatment. The defouling effect of nanobubbles was also investigated using radioactively labeled BSA. The amount of BSA remaining on a stainless steel surface decreased by approximately 20% following 3 min of electrochemical treatment and further cycles of treatment effectively removed more BSA from the surface. In situ observations indicate that the air-water interface of the nanobubble is responsible for the defouling action of nanobubbles.

Water droplet motion control on superhydrophobic surfaces: Exploiting the Wenzel-to-Cassie transition

Water droplets on rough hydrophobic surfaces are known to exist in two states; one in which the droplet is impaled on the surface asperities (Wenzel state) and the other, a superhydrophobic state in which air remains trapped beneath the droplet (Cassie state). Here, we demonstrate that water droplets can transit from the Wenzel-to-Cassie state even though the former is energetically favored. We find that two distinct superhydrophobic states are produced. One is a true Cassie state, whereas the other exhibits superhydrophobicity in the absence of a vapor phase being trapped in the surface roughness. Furthermore, we can selectively drive the motion of water droplets on tilted structured hydrophobic surfaces by exploiting Wenzel-to-Cassie transitions. This can be achieved by heating the substrate or by directly heating the droplet using a laser.

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.

Ion-Beam-Induced Porosity of GaN

Wurtzite GaN films bombarded with heavy ions (197Au+) show anomalous swelling of the implanted region with corresponding volume expansion up to ∼50%. Results show that this phenomenon is due to the formation of a porous layer of amorphous GaN. An important implication of this study for the fabrication of GaN-based devices is that amorphization of GaN should be avoided during ion implantation.

The link between ion specific bubble coalescence and Hofmeister effects is the partitioning of ions within the interface.

Specific ion effects are ubiquitous in soft matter systems and are most readily observed at high salt concentrations where long-range electrostatic forces are screened. In biological systems, ion-specificity is universal and is necessary to introduce the complexity required to carry out the processes of life. Many specific ion effects fall within the Hofmeister paradigm, whereby the strengths of action of the anions and cations follow a well-defined order, independent of the counterion. In contrast, specific ion effects evident in bubble coalescence inhibition depend on the combination of ions, and this phenomenon can be codified using simple ion-combining rules not evident in the Hofmeister systems. Here we show that these disparate specific ion effects have the same origin: They result from the variation in ion affinity for the solution interface. Equilibrium affinities explain Hofmeister effects, whereas we argue that the cation/anion combination controls bubble coalescence inhibition because of dynamic interfacial processes occurring at the more deformable gas-water interface.

Interfacial nanobubbles are leaky: Permeability of the gas/water interface

Currently there is no widespread agreement on an explanation for the stability of surface nanobubbles. One means by which several explanations can be differentiated is through the predictions they make about the degree of permeability of the gas-solution interface. Here we test the hypothesis that the gas-solution interface of surface nanobubbles is permeable by experimental measurements of the exchange of carbon dioxide. We present measurements by attenuated total reflection Fourier transform infrared (ATR-FTIR) and atomic force microscopy (AFM), demonstrating that the gas inside surface nanobubbles is not sealed inside the bubbles, but rather exchanges with the dissolved gas in the liquid phase. Such gas transfer is measurable by using the infrared active gas CO2. We find that bubbles formed in air-saturated water that is then perfused with CO2-saturated water give rise to distinctive gaseous CO2 signals in ATR-FTIR measurements. Also the CO2 gas inside nanobubbles quickly dissolves into the surrounding air-saturated water. AFM images before and after fluid exchange show that CO2 bubbles shrink upon exposure to air-equilibrated liquid but remain stable for hours. Also air bubbles in contact with CO2-saturated water increase in size and Ostwald ripening occurs more rapidly due to the relatively high gas solubility of CO2 in water.