Experimental and theoretical study of adsorption of synthesized amino acid core derived surfactants at an air/water interface.

The adsorption characteristics of amino acid surfactants, synthesized as substances with different volumes and hydrophilic head properties, have been previously described experimentally, without robust theoretical explanation. A theoretical model enabling the characterization of the adsorption behavior and physicochemical properties of this type of biodegradable surfactants, based on molecular structure, would be beneficial for assessment of their usefulness in colloids and interface science in comparison with typical surface-active substances. In this paper, the adsorption behaviour of synthesized amino acid surfactants at the liquid/gas interface was analyzed experimentally (by surface tension measurements using two independent techniques) and theoretically by means of an elaborate model, considering the volume of the surfactant hydrophilic "head" and its ionization degree. It was shown that the adsorption behavior of the synthesized compounds can be successfully described by the proposed model, including the Helfand-Frisch-Lebowitz isotherm based on the equation of state of 2D hard disk-like particles, with molecular properties of surfactant particles obtained using molecular dynamics simulations (MDS). Model parameters allow for direct comparison of physicochemical properties of synthesized amino acid surfactants with other ionic and non-ionic surface-active substances. Furthermore, it was revealed that intermolecular hydrogen bonds allow the formation of surfactant dimers with high surface activity.

"Bubble-on-demand" generator with precise adsorption time control.

The paper presents the principles of our new single bubble generator, which allows a precise control of bubble formation in pure liquids and surfactant solutions, i.e., their detachment frequency and the adsorption time at their motionless surface. We show that the bubbles with equilibrium size can be produced at the capillaries of various orifice diameters (0.022-0.128 mm) on demand and with outstanding reproducibility. Moreover, it is shown that a fully automatized and programmable bubble trap, synchronized with bubble detachment frequency, can be used to (i) control the radius of the released bubble and (ii) precisely adjust the initial adsorption coverage over the surface of detaching bubble, and hence to study the influence of adsorption coverage degree on kinetics of dynamic adsorption layer formation at the rising bubble surface.

Formation and influence of the dynamic adsorption layer on kinetics of the rising bubble collisions with solution/gas and solution/solid interfaces.

BACKGROUND: The DAL (dynamic adsorption layer) formation, that is, the establishment of uneven distribution of adsorption coverage over the rising bubble surface, with significantly diminished coverage at the upstream pole, is the factor of crucial importance for the bubble motion parameters and kinetic of the bubble collisions with various interfaces. The DAL presence can influence the stability of the thin liquid films formed by the colliding bubble at solution/gas and solution solid interfaces. AIM: The purpose of this paper is to critically review the existing state of art regarding the influence of the DAL formation and existence on the bubble motion parameters as well as kinetics of coalescence at free solution surface and three phase contact (TPC) formation at solid/liquid interfaces of different hydrophilic/hydrophobic properties. CONCLUSIONS: Despite the fact that up to now there is no direct experimental evidence showing DAL existence, it is documented by experimental data showing clear correlation between bubble local velocity variations and shape pulsations as well as lifetimes of the liquid film formed by the colliding bubble at gas/liquid and gas/solid interfaces.

Gas dissolution in antibubble dynamics.

Antibubbles are ephemeral objects. Their lifetime is driven by the slow drainage of the air shell from the bottom to the top of the antibubble under the action of hydrostatic pressure. We show in this paper that this argument is only valid if the water used to make the surfactant mixture is saturated in air. Otherwise, two paths are used by the air, which conduct to the thinning and the eventual collapse of the air shell: the drainage from the bottom to the top of the antibubble and the dissolution of the air into the liquid. Using degassed water dramatically shortens the lifetime of the antibubbles, as observed experimentally and rationalised by time-dependent simulations. Consequently, the antibubble lifetime is not only correlated with physical and chemical properties of the air-liquid interface but also with the gas content of the liquid. We also show that pure gas dissolution does not depend on the antibubble radius, a behaviour that allows to rationalise unexplained experimental data found in literature.

Air at hydrophobic surfaces and kinetics of three phase contact formation.

This review focuses on the importance of air presence at hydrophobic solid surfaces for wetting film rupture and kinetics of three phase contact formation. Affinity to air is a typical feature of hydrophobic surfaces, but it has been often either overlooked or not taken into consideration. When the hydrophobic surface, contacted earlier with air, is immersed into water then air can stay attached to the surface. The origin of long range hydrophobic forces and data showing that these interactions were due to the bridging of nanobubbles attached to the hydrophobic surfaces are discussed. A major part of the review is devoted to the description and analysis of data showing that air (nano-, micro-bubbles and/or air film) present at a hydrophobic surface facilitated rupture of the liquid film and three phase contact formation during bubble collisions with flat Teflon plates of different surface roughness. Although all Teflon plates were highly hydrophobic (contact angles ca. 100 degrees -130 degrees ) the time of the three phase contact (TPC) formation and attachment of the colliding bubble was strongly affected by the plate surface roughness. The time of the TPC formation was shortened from over 80 down to 2-3 ms when the roughness was increased from below 1 microm to over 50 microm. Higher surface roughness means that larger amounts of air was entrapped during the Teflon plates' immersion in water. Additional experimental evidence is given, showing that facilitation of the TPC formation and the bubble attachment was due to air presence and re-distribution over the Teflon surfaces: i) prolonging the plate immersion time resulted in quicker attachment; ii) irregular and disappearing air pockets were recorded at a Teflon surface; iii) a satellite bubble left at a Teflon surface during the first collision facilitated the attachment; iv) attachment always occurred during the first collision in the case of a very rough "Teflon V" surface, but in highly concentrated n-octanol and n-heptanol solutions there was bouncing and attachment occurred during the second collision, moreover; v) the degree of bubble kinetic energy transferred into surface energy was significantly smaller during collisions with hydrophobic (Teflon) surfaces than with the hydrophilic ones. The mechanism of air entrapment and redistribution over Teflon plates immersed in water is presented.