Coupling between protein-laden films and a shearing bulk flow

Two-dimensional protein crystallization on lipid monolayers at a quiescent air/water interface is now a well-established process, but it only operates under a very restricted set of conditions and on a very slow time scale. We have recently been able to significantly extend the conditions under which the proteins will crystallize as well as speed up the process by subjecting the interface to a shearing flow. Here, we investigate the two-way coupling between a protein-laden film and the bulk flow that provides the interfacial shear. This flow in a stationary open cylinder is driven by the constant rotation of the floor. Using the Boussinesq-Scriven surface model for a Newtonian interface coupled to the Navier-Stokes equations for the bulk flow, we find that the surface shear viscosity of protein-laden films under most conditions is small or negligible. This is the case for films subjected to constant shearing flow, regardless of the duration of the flow. However, when the film is intermittently sheared, significant surface shear viscosity is evident. In these cases, the surface shear viscosity is not uniform across the film.     

Viscous coalescence of expanding low-viscosity drops; the dueling drops experiment

A new experimental device was designed and developed for the systematic study of the interaction of two, very small low viscosity expanding drops that were pushed out of the ends of two aligned opposing capillaries into a polymeric liquid. The idea of this experiment is to mimic the interactions of two expanding bubbles during the formation of polymeric foams; for convenience, we call this device the dueling drops experiment. In the current setup, we are able to grow drops (50-200 microm maximum diameter) at a controlled flow rate (down to 0.1 microl/day). Optical observation of the pair of growing drops was achieved by the use of an optical zoom lens system for a side view, and a "long-range" microscope for a top view, thus ensuring complete alignment of the capillaries and partial observation of the thin-film. Measurements are reported for the drainage time between the apparent initial contact of the drops and film rupture. A simple scaling theory was developed based on the drainage of two approaching flat disk-like interfaces, the radius of which expands throughout the interaction as the volume of the drop increases.     

Patterns from drying drops

The objective of this review is to investigate different deposition patterns from dried droplets of a range of fluids: paints, polymers and biological fluids. This includes looking at mechanisms controlling the patterns and how they can be manipulated for use in certain applications such as medical diagnostics and nanotechnology.     

Bubble entrainment with drops

The study reported here was undertaken because recent research on nucleate boiling has implicated vapor entrainment by drops as a mechanism for vapor bubble nucleation. The mechanism has been called secondary nucleation. The purpose of this research was to determine the behavior of entrained air bubbles when a drop of liquid strikes a liquid surface. A liquid drop striking the surface of a pool of the same liquid was found usually to entrain large numbers of small air bubbles. Some of these bubbles are frequently carried rapidly deep into the pool by a vortex ring but many can be deposited in a trail or left floating on the surface. Air bubble entrainment was observed with water and several organic liquids and some differences were noted. Drops with diameters from 200 μm to 4 mm were studied. Sometimes hundreds of bubbles were entrained some with diameters up to 100 μm. These results lend support to the secondary nucleation hypothesis and indicate further research on vapor bubble entrainment under conditions more typical of boiling would be appropriate.     

Oxygen tensioactivity on liquid-metal drops

The influence of oxygen on the surface tension of liquid metals is a topic of undoubted interest as the formation of oxide films, or even oxygen contamination of the metal interface, represents the main source of error in determining the surface tension. The evaluation of gas-atmosphere mass exchanges under stationary conditions allows the evaluation of an effective oxygen pressure at which the oxidation of metal becomes evident. This effective oxygen pressure can be considered as a property of the system and, according to experimental evidence, can be many orders of magnitude greater than the equilibrium pressure. The measurement of the surface tension is a good way of studying interface properties, their temporal change and their connections to transport and reaction rates. This paper represents a review of a work undertaken with the aim of understanding oxygen mass transport at the liquid metal surface in relation to the study of capillary phenomena at high temperature.     

Photoinduced pH drops in water

A 2-hydroxyazobenzene platform has been evaluated to photorelease protons in aqueous solutions. Three different systems relying on molecular, supramolecular and polymeric strategies have been investigated in order to tune the water solubility and the thermodynamic and kinetic properties. This paper first reports on the syntheses and the physico chemical analyses for each system. Subsequently, we show that the three strategies are appropriate to reversibly photo-generate tunable pH drops in water up to one pH unit amplitude and at the 10-100 s timescale, upon transient illumination at 365 nm.     

Electrophoresis of concentrated mercury drops

The electrophoretic behavior of concentrated monodispersed, positively charged mercury drops is investigated theoretically. The present study extends previous analyses by considering arbitrary surface potentials, double-layer polarization, and the interaction between adjacent double layers. The coupled equations describing the spatial variations in the flow field, the electric field, and the concentration field are solved by a pseudo-spectral method. For a low surface potential phi(r), the mobility increases monotonically with kappaalpha; kappa and alpha are respectively the reciprocal Debye length and the radius of a mercury drop. For medium and high phi(r), the mobility curve has a reflection point, which arises from the interaction of adjacent double layers, for kappaalpha. Also, if phi(r) is high, the mobility curve may exhibit a local minimum as kappaalpha varies. This phenomenon is pronounced if the concentration of the dispersed phase is high. If the double layer is thick, the mobility increases with phi(r), and the reverse is true if it is thin. We show that the higher the concentration of the dispersed phase the smaller the mobility, and as kappaalpha becomes large the mobility approaches a constant value, which is independent of the concentration of the dispersed phase. The mobility of mercury drops is larger than that of the corresponding rigid particles.     

Gunshot residues on paraffin drops

In an attempt to facilitate the removal of gunpowder residues from the skin, a simplified method has been tested as compared to the commonly used one of brushing with liquid paraffin. The removing material is still paraffin, but it is dropped from a lighted paraffin candle onto the first interdigital space of the hand. Maps were constructed for gunpowder residues on hands after pistol firing and the first interdigital space was found to be the most significant. Analysis of paraffin “blanks” from candles showed them to be free from antimony, barium and copper. Many samples were examined from the left and the right hands of individuals who had or had not fired a pistol. The results clearly show that from the content of Sb, primarily, and also of Ba, it is possible to identify the person who fired the pistol. Due to the random distribution of copper coming from the skin, this element appears not to be meaningful for the identification of pistol firers. Some practical cases of suicides and shootings are reported.     

Dendrimer pattern formation in evaporating drops

The redistribution of organic solutes during drop evaporation is a nanoscale self-assembly process with relevance to technologies ranging from inkjet printing of organic displays to synthesis of biosmart interfaces for sensing and screening. We have used solutions of dendrimer molecules with incrementally varying terminal site chemistry to explore whether the condensed dendrimer patterns resulting from microdroplet evaporation sensitively depend on, and are characteristic of, the surface chemistry of the solute molecules. This hypothesis has been experimentally confirmed by comparing the behavior of microdroplets of G4, G4-25%C12, and G4-50%C12 dendrimers dissolved in pentanol and deposited on mica substrates. For the dilute concentration studied here, the presence of periodically 'scalloped' dendrimer rings is ubiquitous. The instability wavelength of the scalloped rings is found to be proportional to the width of the ring, similar to observations of the rim instability in dewetting holes. The effect of dendrimer surface chemistry is obvious in the detailed structure of the self-assembled rings. G4 rings are diffuse and disordered with no evidence for layered growth. G4-25%C12 exhibits highly ordered ring structures and the onset of monomolecular terracing. G4-50%C12 exhibits highly periodic scallops and very distinct monomolecular height terraced growth of the rings with flat terraces and sharply defined steps. On the basis of these results, it is likely that the morphology of condensed molecule-based ring patterns formed by evaporation of microdroplets on surfaces can be used as a 'fingerprint' to identify, for example, solute molecule surface chemistry and concentration and function as a sensor for a variety of biochemical events.     

As-placed contact angles for sessile drops

As-placed contact angle is the contact angle a drop adapts as a result of its placement on a surface. As expected, the as-placed contact angle, thetaAP, of a sessile drop on a horizontal surface decreases with the drop size due to the increase in hydrostatic pressure. We present a theoretical prediction for thetaAP which shows that it is a unique function of the advancing contact angle, thetaA, drop size, and material properties (surface tensions and densities). We test our prediction with published and new data. The theory agrees with the experiments. From the relation of the as-placed contact angle to drop size the thermodynamic equilibrium contact angle is also calculated.     

Shear-induced coalescence of emulsified oil drops

Crude oil droplets, when suspended in water, possess negative surface charges which give rise to double-layer repulsive forces between the drops. According to conventional DLVO theory, the magnitude of this repulsion (based on the measured zeta potential) is more than sufficient to prevent coalescence of the droplets. Indeed, when two such droplets were brought together on direct (i.e., "head-on") approach, coalescence was rarely observed. Upon oblique approach, however, the same droplets were seen to coalesce readily. An oblique encounter must necessarily give rise to lateral relative motion-or shearing-between the droplet surfaces. It is speculated that, if the charge distributions at the droplet surfaces were heterogeneous, lateral shearing would facilitate many encounters between surface patches of different zeta potentials across the intervening water film. If the repulsion across any local region were sufficiently weak to allow formation of an oil bridge across the water film, coalescence of the drops would follow inevitably. With the hypothesis of surface heterogeneity, it is not necessary to invoke any additional colloidal interactions (such as "hydrophobic forces") to account for the observed droplet-droplet coalescence. This finding may have important implications for the underlying mechanisms of emulsion stability in general and the commercial extraction of bitumen from oil sands in particular.     

Equilibrium of drops on inclined fibers

Why is it that drops do not slip down inclined thin fibers or spider silks? The possible explanation is based on the existence of fiber size, which causes a sustaining force that pins these drops. Following this explanation, the drop remains in equilibrium until a critical value of the sustaining force is reached. We suggest an alternative analyses, from the point of view of the inclined fiber at which the drop slips down is predicted. This result does not depend explicitly on silk surface roughness, but only on the drop size and surface tensions.     

On the behavior of dew drops

It may be observed that, when dew drops form, although they may be positioned randomly on flat leaves, they tend to accumulate at the pointed ends of thin, slightly conical growths. We discuss here the basic physics leading to this phenomenon.     

Lysozyme pattern formation in evaporating drops

Liquid droplets containing suspended particles deposited on a solid, flat surface generally form ringlike structures due to the redistribution of solute during evaporation (the "coffee ring effect"). The forms of the deposited patterns depend on interactions between solute(s), solvent, and substrate. In this study, deposition patterns from droplets of a simplified model biological fluid (DI water + lysozyme) are examined by scanning probe and optical microscopy. The overall lysozyme residue morphology is complex (with both a perimeter "rim" and undulating interior) but varies little with concentration. However, the final packing of lysozyme molecules is strongly dependent on initial concentration.     

Rescaling the dynamics of evaporating drops

The dynamics of evaporation of wetting droplets is investigated experimentally in an extended range of drop sizes to provide trends relevant for a theoretical analysis. A model is proposed, which generalizes Tanner's law in the presence of evaporation. A qualitative agreement is obtained, which represents a first step toward the solution of a very old, complex problem.     

Spreading of liquid drops over dry surfaces

Spreading of thin, axisymmetric, non-volatile, Newtonian liquid drops over a dry, smooth, flat solid surface is considered both theoretically and experimentally in the case of complete wetting. The drop profile is solved analytically by matching the “outer” solution for large film thicknesses, where only the capillary effects are important, with the “inner” solution for small film thicknesses, where the viscous and disjoining pressure effects are comparable to capillary effects. It is shown that the apparent radius of the wetted spot, the apex height of the drop, and the apparent advancing dynamic contact angle follow different power laws in time and the advancing dynamic contact angle follows a power law in capillary number. Both the prefactor and the exponent of each power law are derived theoretically. Good agreement between the theory predictions and experimental measurements is shown for both the prefactor and exponent of each power law. It is necessary to emphasize that the theory suggested does not include any fitting parameters.     

Salt-induced protein phase transitions in drying drops

Protein phase transitions in drying sessile drops of protein-salt-water colloidal systems were studied by means of optical and atom-force microscopy. The following sequence of events was observed during drop drying: attachment of a drop to a glass support; redistribution of colloidal phase due to hydrodynamic centrifugal stream; protein ring formation around the edge; formation of protein spatial structures inside a protein ring that pass into gel in the middle of the drop; salt crystallization in the shrinking gel. It was assumed that rapid drying of a protein ring over the circle of high colloidal volume fraction and low strength of interparticle attraction leads to formation of colloidal glass, whereas gel forms only in the middle of the drop at very low protein volume fraction and strong attraction between the particles. Before gelation, colloidal particles form fractal clusters. In dried drops of salt-free protein solutions, no visual protein structures were observed. Structural evolution of protein in sessile drying drops of protein-salt aqueous colloidal solutions is discussed on the basis of experimental data.     

Shape and buckling transitions in solid-stabilized drops

We study shape and buckling transitions of particle-laden sessile and pendant droplets that are forced to shrink in size. Monodisperse polystyrene particles were placed at the interface between water and decane at conditions that are known to produce hexagonal, crystalline arrangements on flat interfaces. As the volumes of the drops are reduced, the surface areas are likewise diminished. This effectively compresses the particle monolayer coating and induces a transition from a fluid film to a solid film. Since the particles are firmly attached to the interface by capillary forces, the shape transitions are reversible and shape/volume curves are the same for drainage and inflation. Measurements of the internal pressure of the drops reveal a strong transition in this variable as the buckling transition is approached.     

Characterization of rough surfaces with vibrated drops

Wetting transitions were studied with vertically-vibrated drops on various artificial and natural rough substrates. Alternative pathways of wetting transitions were observed. The model of wetting transition is presented. Multiple minima of the Gibbs free energy of a drop deposited on a rough surface explain alternative pathways of wetting transitions. We demonstrate that a wetting transition occurs when the constant force resulting from vibrations, Laplace and hydrostatic pressure acts on the triple line. It is shown that the final wetting states are mainly the Cassie impregnating wetting state with water penetrating the pores in the outer vicinity of the droplet or the Wenzel state with water inside the pores under the droplet whereas the substrate ahead the drop is dry.     

Wetting and evaporation of binary mixture drops

Experimental results on the wetting behavior of water, methanol, and binary mixture sessile drops on a smooth, polymer-coated substrate are reported. The wetting behavior of evaporating water/methanol drops was also studied in a water-saturated environment. Drop parameters (contact angle, shape, and volume) were monitored in time. The effects of the initial relative concentrations on subsequent evaporation and wetting dynamics were investigated. Physical mechanisms responsible for the various types of wetting behavior during different stages are proposed and discussed. Competition between evaporation and hydrodynamic flow are evoked. Using an environment saturated with water vapor allowed further exploration of the controlling mechanisms and underlying processes. Wetting stages attributed to differential evaporation of methanol were identified. Methanol, the more volatile component, evaporates predominantly in the initial stage. The data, however, suggest that a small proportion of methanol remained in the drop after the first stage of evaporation. This residual methanol within the drop seems to influence subsequent wetting behavior strongly.