Plamen Tchoukov

Role of Asphaltenes in Stabilizing Thin Liquid Emulsion Films

Drainage kinetics, thickness, and stability of water-in-oil thin liquid emulsion films obtained from asphaltenes, heavy oil (bitumen), and deasphalted heavy oil (maltenes) diluted in toluene are studied. The results show that asphaltenes stabilize thin organic liquid films at much lower concentrations than maltenes and bitumen. The drainage of thin organic liquid films containing asphaltenes is significantly slower than the drainage of the films containing maltenes and bitumen. The films stabilized by asphaltenes are much thicker (40-90 nm) than those stabilized by maltenes (∼10 nm). Such significant variation in the film properties points to different stabilization mechanisms of thin organic liquid films. Apparent aging effects, including gradual increase of film thickness, rigidity of oil/water interface, and formation of submicrometer size aggregates, were observed for thin organic liquid films containing asphaltenes. No aging effects were observed for films containing maltenes and bitumen in toluene. The increasing stability and lower drainage dynamics of asphaltene-containing thin liquid films are attributed to specific ability of asphaltenes to self-assemble and form 3D network in the film. The characteristic length of stable films is well beyond the size of single asphaltene molecules, nanoaggregates, or even clusters of nanoaggregates reported in the literature. Buildup of such 3D structure modifies the rheological properties of the liquid film to be non-Newtonian with yield stress (gel like). Formation of such network structure appears to be responsible for the slower drainage of thin asphaltenes in toluene liquid films. The yield stress of liquid film as small as ∼10(-2) Pa is sufficient to stop the drainage before the film reaches the critical thickness at which film rupture occurs.

Interaction between Air Bubbles and Superhydrophobic Surfaces in Aqueous Solutions

Superhydrophobic surfaces are usually characterized by a high apparent contact angle of water drops in air. Here we analyze the inverse situation: Rather than focusing on water repellency in air, we measure the attractive interaction of air bubbles and superhydrophobic surfaces in water. Forces were measured between microbubbles with radii R of 40-90 μm attached to an atomic force microscope cantilever and submerged superhydrophobic surfaces. In addition, forces between macroscopic bubbles (R = 1.2 mm) at the end of capillaries and superhydrophobic surfaces were measured. As superhydrophobic surfaces we applied soot-templated surfaces, nanofilament surfaces, micropillar arrays with flat top faces, and decorated micropillars. Depending on the specific structure of the superhydrophobic surfaces and the presence and amount of entrapped air, different interactions were observed. Soot-templated surfaces in the Cassie state showed superaerophilic behavior: Once the electrostatic double-layer force and a hydrodynamic repulsion were overcome, bubbles jumped onto the surface and fully merged with the entrapped air. On nanofilaments and micropillar arrays we observed in addition the formation of sessile bubbles with finite contact angles below 90° or the attachment of bubbles, which retained their spherical shape.

Black dots as a detector of self-assembly in thin liquid films

Abstract Experiments with different types of amphiphilic substances exhibit two stable tendencies. (1) The surface tension/concentration curves (Δσ/Cs) display well-defined kink and plateau sectors. (2) Free thin liquid films (foam films) from solutions with concentrations in the plateau regions drain until ‘black dots’ appear and then rupture almost immediately. A general theoretical scheme is developed that suggests a mechanism connecting the formation of black dots with the onset and the reorganization of smaller self-assembled aggregates (premicelles) in the bulk of the solution and on the interfaces. The results show that the black dots in free thin liquid films may serve as an indicator of the presence and reorganization of self-assembled structures in amphiphilic solutions.

Simultaneous measurement of dynamic force and spatial thin film thickness between deformable and solid surfaces by integrated thin liquid film force apparatus

Interactions involving deformable surfaces reveal a number of distinguishing physicochemical characteristics that do not exist in interactions between rigid solid surfaces. A unique fully custom-designed instrument, referred to as integrated thin liquid film force apparatus (ITLFFA), was developed to study the interactions between one deformable and one solid surface in liquid. Incorporating a bimorph force sensor with interferometry, this device allows for the simultaneous measurement of the time-dependent interaction force and the corresponding spatiotemporal film thickness of the intervening liquid film. The ITLFFA possesses the specific feature of conducting measurement under a wide range of hydrodynamic conditions, with a displacement velocity of deformable surfaces ranging from 2 μm s-1 to 50 mm s-1. Equipped with a high speed camera, the results of a bubble interacting with hydrophilic and partially hydrophobic surfaces in aqueous solutions indicated that ITLFFA can provide information on interaction forces and thin liquid film drainage dynamics not only in a stable film but also in films of the quick rupture process. The weak interaction force was extracted from a measured film profile. Because of its well-characterized experimental conditions, ITLFFA permits the accurate and quantitative comparison/validation between measured and calculated interaction forces and temporal film profiles.

Probing Boundary Conditions at Hydrophobic Solid–Water Interfaces by Dynamic Film Drainage Measurement

A newly developed dynamic force apparatus was used to determine hydrodynamic boundary conditions of a liquid on a hydrophobic silica surface. For a given approach velocity of bubble to solid surfaces in an electrolyte solution, a reduced dimple formation and faster film drainage were observed by increasing the hydrophobicity of silica surfaces, indicating a significant change in hydrodynamic boundary conditions of water molecules from an immobile to a mobile water-hydrophobic silica interface. By comparing the measured film profiles with the predictions from the Stokes-Reynolds-Young-Laplace model, the slippage boundary condition of water on the hydrophobic silica surface of surface nanoroughness was quantified. Increasing the surface hydrophobicity was found to increase the mobility of water in the thin liquid film, promoting faster drainage of the liquid. For a given hydrophobicity of solids, the mobility of water occurred only above a critical bubble approach velocity and increased with increasing bubble approach velocity. In contrast, similar experiments with hydrophobized mica surfaces showed no-slip boundary condition of water at the molecularly smooth hydrophobic surface. The results collectively suggest that the observed mobility of water with more than 100 nm in thickness on the studied hydrophobic silica surfaces was due to the nanoroughness of hydrophobic surfaces. Such finding sheds light on one possible way of reducing the friction of water on hydrophobic solid surfaces by creating nanostructured surface of nanoroughness.