Effect of thermal treatment on interfacial properties of beta-lactoglobulin

The changes in the secondary conformation and surface hydrophobicity of beta-lactoglobulin subjected to different thermal treatments were characterized at pH values of 7, 5.5 and 4 using circular dichroism (CD) and hydrophobic dye binding. Heating resulted in a decrease in alpha-helix content with a corresponding increase in random coil at all pH values, this change being more pronounced for small heating times. Heating also resulted in an increase in surface hydrophobicity as a result of partial denaturation, this increase being more pronounced at pH 4. Thermal treatment resulted in a shift of the spread monolayer isotherm at air-water interface to smaller area per molecule due to increased flexibility and more loop formation. Thermal treatment led to an increase in interfacial shear elasticity and viscosity of adsorbed beta-lactoglobulin layer at pH 5.5 and 7. Interfacial shear elasticity, shear viscosity, stability of beta-lactoglobulin stabilized emulsion and average coalescence time of a single droplet at a planar oil-water interface with adsorbed protein layer exhibited a maximum for protein subjected to 15 min heat treatment at pH 7. At pH 5.5, the interfacial shear rheological properties and average single drop coalescence time were maximum for 15 min heat treatment whereas emulsion stability was maximum for 5 min heat treatment. At pH 7, thermal treatment was found to enhance foam stability. Analysis of thin film drainage indicated that interfacial shear rheological properties do not influence thin film drainage.     

Numerical simulation of droplet coalescence behavior in gas phase under the coupling of electric field and flow field

The coalescence behavior of droplets in an electric field belongs to the important research contents of electrohydrodynamics. Based on the phase field method of the Cahn–Hilliard equation, the electric field and the flow field are coupled to establish the numerical model of twin droplet coalescence in a coupled field. The effects of flow rate, electric field strength, droplet diameter, and interfacial tension on the coalescence behavior of droplets during the coalescence process were investigated. The results show that the dynamic behavior of the droplets is divided into coalescence, after coalescence rupture, and no coalescence under the coupling of electric field and flow field. The proper increase of the electric field strength will accelerate the coalescence of the droplets, and the high electric field strength causes the droplets to burst after coalescence. Excessive flow rates make droplets less prone to coalescence. Under the coupling field, the larger the droplet interface tension, the smaller the droplet diameter, the smaller the flow rate, and the shorter the droplet coalescence time. The results provide a theoretical basis for the application of electrostatic coalescence in gas–liquid separation technology.     

Rupture of draining foam films due to random pressure fluctuations

A generalized formalism for the rupture of a draining foam film due to imposed random pressure fluctuations, modeled as a Gaussian white noise, is presented in which the flow inside the film is decomposed into a flow due to film drainage and a flow due to imposed perturbation. The evolution of the amplitude of perturbation is described by a stochastic differential equation. The rupture time distribution is calculated from the sample paths of perturbation amplitude as the time for this amplitude to equal one-half the film thickness and is calculated for different amplitudes of imposed perturbations, film thicknesses, electrostatic interactions, viscosities, and interfacial mobilities. The probability of film rupture is high for thicker films, especially at smaller times, as a result of faster growth of perturbations in a thick film due to a smaller disjoining pressure gradient. Larger viscosity, larger surface viscosity, higher Marangoni number, and smaller imposed pressure fluctuation result in slower growth of perturbation of a draining film, thus leading to larger rupture time. It is shown that a composite rupture time distribution combining short time simulation results with equilibrium distribution is a good approximation.     

Coalescence of droplets in viscoelastic matrix with diffuse interface under simple shear flow

The coalescence process of two droplets in simple shear flow was modeled and simulated by the diffuse interface method. The collision between two droplets was investigated. The systems with small Peclet number, which denotes highly diffuse ability of concentration, were found to coalesce faster and easier due to the overlap of interfacial layers. The effect of matrix elasticity on droplet coalescence was studied thoroughly. The matrix elasticity was found to decrease the hydrodynamic interactions between droplets, and delay the coalescence process. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1856–1869, 2007     

Evolution of droplet size distribution and composition in miniemulsions

A fundamental understanding of the formation, degradation and polymerization of miniemulsions has been hindered by difficulties in quantifying their monomer droplet size distribution (DSD). In this work, particle sizing techniques including capillary hydrodynamic fractionation, acoustic attenuation spectroscopy, surfactant titration, and microscopy were adapted to characterize miniemulsion DSDs. The key ingredient in miniemulsions is the costabilizer, a low water solubility compound that limits monomer diffusion from the smaller to larger droplets (Ostwald ripening). The DSD evolution of styrene miniemulsions employing hexadecane (HD) as costabilizer was characterized. With less costabilizer, droplets were initially smaller, but increased in average size with time, and their DSDs broadened. These changes were slowed with addition of extra surfactant after homogenization. After several days, the average droplet size increased to about 150 nm regardless of the amount of HD or surfactant used. The HD content of separated portions of centrifuged miniemulsions was measured and showed significant Ostwald ripening within minutes after preparation. The further evolution of the DSD is attributed primarily to droplet coalescence. Less composition change occurred with either higher HD content or post‐homogenization surfactant addition, both of which led to minimization of free energy, increasing stability. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1529–1544     

Effect of viscosity ratio on the morphology of PET microfibrils in uncompatibilized and compatibilized drawn PET/PP/TiO2 blends

Uncompatibilized and compatibilized (polypropylene‐grafted maleic anhydride (PP‐g‐MA) as compatibilizer) PET (polyethylene terephthalate)/PP (polypropylene)/TiO₂ drawn strands were prepared by extrusion of the blends and cold drawing of the extrudates. In the uncompatibilized drawn strand, the generated PET microfibrils show large aspect ratio and wide distribution in diameter; whereas in the compatibilized drawn strand numbers of short needle‐like PET formations appear and demonstrate uniform diameter distribution. Derived from PET droplets, the microfibril morphology is greatly influenced by the size of PET droplets in the extrudates: small droplet deforms into needle‐like shape and large one becomes microfibril. In the compatibilized PET/PP/TiO₂ extrudate, the size of PET droplet is much smaller than that in the uncompatibilized one. The reduction of droplet size is attributed to the low viscosity ratio between dispersed phase and matrix, which facilitates the break up of the dispersed PET droplets. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 555–562, 2009     

Zooming in on the role of surfactants in droplet coalescence at the macroscale and microscale

Coalescence of dispersed micrometer-scale droplets is an essential step toward the separation of emulsions. The thin film between droplets must form, drain, and rupture for coalescence to occur. In surfactant-stabilized emulsions, the film drainage and droplet coalescence processes are known to be hindered because of reduced interfacial mobility. However, a clear correlation between this mobility and the underlying surfactant transport and interfacial response to shear and dilatational deformations is undercharacterized. For microscale droplets, the effect of surfactant transport to the interface and along the interface is often difficult to isolate from other bulk effects on emulsion stability. In this work, we review surfactant-mitigated coalescence in both macroscale and microscale experiments, highlighting the importance of interfacial curvature and length scales when establishing a correlation between coalescence theory and film mobility.     

A numerical study on the coalescence of emulsion droplets in a constricted capillary tube

Using a new computational model, we have studied the dynamics and coalescence of a pair of two-dimensional droplets in pressure-driven flow through a constricted capillary tube, which is a prototype problem for the analysis of the interaction of emulsion droplets in porous media. We present simulations that quantify the effects of various system parameters on the droplet stability. These include the capillary number, the interfacial tension, the suspended-to-suspending-phase viscosity ratio, the valence and concentration of added electrolytes, the droplet-to-pore-size ratio, the pore-body-to-throat-size ratio, and the type of pore geometry. Our simulations show that the capillary number Ca plays an important role in determining whether the drops coalesce. At low Ca, drops deform only slightly and coalescence occurs at the entrance of the pore throat, whereas significant deformation enables the drops move through the pore without coalescence at high Ca. Coalescence is favored at intermediate values of the viscosity ratio. The destabilizing effect of added electrolytes is found to be insignificant for 10-mum drops, but significant for micron-size drops. Among the geometric-related parameters, the drop-to-pore-size ratio is the most significant.     

Numerical simulation of deformation behavior of droplet in gas under the electric field and flow field coupling

The water droplets in the process of electrostatic coalescence are important when studying electrohydrodynamics. In the present study, the electric field and flow field are coupled through the phase field method based on the Cahn–Hilliard formulation. A numerical simulation model of single droplet deformation under the coupling field was established. It simulated the deformation behavior of the movement of a droplet in the continuous phase and took the impact of droplet deformation into consideration which is affected by two-phase flow velocity, electric field strength, the droplet diameter, and the interfacial tension. The results indicated that under the single action of the flow field, when the flow velocity was lower, the droplet diameter was greater as was the droplet deformation degree. When the flow velocity was increased, the droplet deformation degree of a small-diameter droplet was at its maximum size, the large-diameter droplet had a smaller deformation degree, and the middle-diameter droplet was at a minimum deformation degree. When the flow velocity was further increased, the droplet diameter was smaller, and the droplet deformation degree was greater. Under the coupled effect of the electric field and flow field, the two-phase flow velocity and the electric field strength were greater, and the degree of droplet deformation was greater. While the droplet diameter and interfacial tension were smaller, the degree of droplet deformation was greater. Droplet deformation degree increased along with the two-phase flow velocity. The research results provided a theoretical basis for gas–liquid separation with electrostatic coalescence technology.     

Some mechanisms of immiscible fluid displacement in small networks

We report experimental observations on immiscible displacement in two small networks using three different pairs of fluids, air-oil, air-water, and oil-water, to vary the wettability. The experiments were run for a wide range of capillary number, from 10⁻⁷ to 10⁻³. Various mechanisms are observed. These are film spreading and drainage, Haines' jump, free slip and stick-slip meniscus motion, contact angle hysteresis, snap-off, coalescence, and blocking of film and bubble. For the air-oil case, oil is perfectly wetting in the network. In imbibition, the displacement occurs first via thin film spreading, followed by snap-off of menisci, and then by piston-like displacement at low flow rates. As the flow rate increases, piston-like displacement dominates because film spreading is comparatively slow. Snap-off of menisci in the throats is a necessary condition for air trapping. In drainage, meniscus snap-off and coalescence are observed in one network. For both imbibition and drainage, during each snap-off or piston-like displacement event, all menisci move freely along the channels to adjust their curvatures, due to the lubrication of the wetting film. For the other two fluid pairs at low flow rates, this curvature readjustment through free slipping of meniscus is not observed, presumably due to the absence of wetting film during the displacement. At high flow rate, oscillation of menisci due to volumetric competition is observed. Neither wetting film spreading nor throat snap-off is observed. Stick and slip motion of meniscus is observed, probably due to the roughness and/or heterogeneous wettability of the solid surface. For the oil-water system the wettability seems to be time dependent. Coalescence between two menisci can occur in the throat, in the pore, or at the pore-throat boundary during displacement. Trapping of the displaced phase is due to its being bypassed or snapped off in the throat.     

The outstanding ability of nanosilica to stabilize dispersions of Nylon 6 droplets in a polypropylene matrix

The effectiveness of hydrophobically modified nanosilica (NS) as interfacial modifying agent for immiscible polymer blends is evaluated. Blends of polypropylene (PP) with 20% of polyamide 6 (PA) and 5% hydrophobic NS were prepared by melt mixing. Compression molded sheets and extruded films were evaluated by scanning electron microscopy, transmission electron microscopy, tensile testing, and rheological measurements. Hydrophobic NS particles strongly reduce the polydispersity and droplet size of the dispersed phase, as a result of their preferential location at the interface. NS promotes outstanding stability of blend dispersion regardless of the processing or post‐processing technique employed. The viscoelastic terminal zone shows a plateau for PP/PA/NS, which corresponds to a suspension‐like behavior. Under large amplitude oscillatory shear, the increment in the non‐linearity parameter Q evidences the interactions between NS and blend components. Therefore, NS is an excellent morphological stabilizer that prevents coalescence, but cannot promote interfacial adhesion between immiscible PP and PA phases. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1567–1579     

Model for drop coalescence in a locally isotropic turbulent flow field

The proposed model views drop coalescence in a turbulent flow field as a two-step process consisting of formation of a doublet due to drop collisions followed by coalescence of the individual droplets in a doublet due to the drainage of the intervening film of continuous phase under the action of colloidal (van der Waals and electrostatic) and random turbulent forces. The turbulent flow field was assumed to be locally isotropic. A first-passage-time analysis was employed for the random process of intervening continuous-phase film thickness between the two drops of a doublet in order to evaluate the first two moments of coalescence-time distribution of the doublet. The average drop coalescence time of the doublet was dependent on the barrier for coalescence due to the net repulsive force (net effect of colloidal repulsive and turbulent attractive forces). The predicted average drop coalescence time was found to be smaller for larger turbulent energy dissipation rates, smaller surface potentials, larger drop sizes, larger ionic strengths, and larger drop size ratios of unequal-sized drop pairs. The predicted average drop coalescence time was found to decrease whenever the ratio of average turbulent force to repulsive force barrier became larger. The calculated coalescence-time distribution was broader, with a higher standard deviation, at lower energy dissipation rates, higher surface potentials, smaller drop sizes, and smaller size ratios of unequal drop pairs. The model predictions of average coalescence-rate constants for tetradecane-in-water emulsions stabilized by sodium dodecyl sulfate (SDS) in a high-pressure homogenizer agreed fairly well with the inferred experimental values as reported by Narsimhan and Goel (J. Colloid Interface Sci. 238 (2001) 420-432) at different homogenizer pressures and SDS concentrations.     

Localized electric field induced transition and miniaturization of two‐phase flow patterns inside microchannels

Strategic application of external electrostatic field on a pressure‐driven two‐phase flow inside a microchannel can transform the stratified or slug flow patterns into droplets. The localized electrohydrodynamic stress at the interface of the immiscible liquids can engender a liquid‐dielectrophoretic deformation, which disrupts the balance of the viscous, capillary, and inertial forces of a pressure‐driven flow to engender such flow morphologies. Interestingly, the size, shape, and frequency of the droplets can be tuned by varying the field intensity, location of the electric field, surface properties of the channel or fluids, viscosity ratio of the fluids, and the flow ratio of the phases. Higher field intensity with lower interfacial tension is found to facilitate the oil droplet formation with a higher throughput inside the hydrophilic microchannels. The method is successful in breaking down the regular pressure‐driven flow patterns even when the fluid inlets are exchanged in the microchannel. The simulations identify the conditions to develop interesting flow morphologies, such as (i) an array of miniaturized spherical or hemispherical or elongated oil drops in continuous water phase, (ii) “oil‐in‐water” microemulsion with varying size and shape of oil droplets. The results reported can be of significance in improving the efficiency of multiphase microreactors where the flow patterns composed of droplets are preferred because of the availability of higher interfacial area for reactions or heat and mass exchange.     

Particle motion near a deformable fluid interface

The present paper reports on one aspect of our recent studies of the hydrodynamic interactions of two deformable particles in a viscous fluid. This general hydrodynamics problem represents an initial step toward a fundamental invertigation of particle/ drop or droplet/droplet interactions in processes such as coalescence and flotation where both hydrodynamic and colloidal effects may be important. Here we consider only the limiting problem of translation of a rigid sphere with constant velocity normal to the plane of an initially flat interface. The Reynolds number is assumed to be vanishingly small; however, no restriction is imposed on the magnitude of the interface deformation.A primary focus of our research has been the qualitative dependence of the mode of interface deformation on the viscosity ratio, and on appropriate non-dimensional measures of interfacial tension and the density difference across the interface. In some instances, the deformation is relatively small and a so called “film drainage” configuration is attained as the particle passes across the plane of the undeformed interface. In other cases. however, the particle passes well into the domain of the second fluid while still surrounded by a layer of the first fluid that is connected to its original domain by a thin column (or “tail”) of fluid behind the sphere. In these latter cases, the rate of thinning of the tail is greate than the rate of thinning of the fluid layer around the particle; thus suggesting a second mode of particle “breakingthrough”, in addition to that associated with the film drainage configuration.     

Kinetics of flow‐induced coalescence and form relaxation in polymer blends as studied by rheo small angle light scattering

The kinetics of flow‐induced coalescence in PS/PMMA (polystyrene/polymethylmethacrylate) blends containing 1 wt% and 5 wt% PMMA was measured by rheo small angle light scattering under conditions of non‐deformed droplets. The results are in agreement with a coalescence model which includes binary hydrodynamic interactions. Under conditions where droplet deformation occurs, coalescence is suppressed and the interfacial tension was determined from the form relaxation time on the basis of the Palierne model.     

Cationic photopolymerization of liquid fullerene derivative under visible light

We describe the synthesis and cationic photopolymerization of a C₆₀ derivative bearing a 2,4,6‐tris(epoxynonyloxy)phenyl moiety (FB9ox). Rheological analysis of monomer indicates that temperature of 130 °C yields sufficiently low viscosity for polymerization. A thin film of the liquid monomer has been cationically photopolymerized with a photoinitiator system of curcumin and p‐(octyloxyphenyl)phenyliodonium hexafluoroantimonate, which harvests 424 nm light instead of commonly used ultraviolet light. The degree of polymerization was determined with ATR‐IR. The reaction is the first recorded photopolymerization of a fullerene derivative thin film. The polymer exhibits good mechanical and chemical stabilities. The polymerization can also be achieved by annealing at 150 °C without illumination, but with a smaller degree of polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5194–5201, 2008     

Investigations into the electrical and coalescence behaviour of water-in-crude oil emulsions in high voltage gradients

The stability of water-in-crude oil emulsions when subjected to high voltage electric fields depends on the nature of the crude oil and the presence of chemical additives. Optical microscopy, conductivity and coalescence measurements have revealed two distinct types of behaviour, designated type I and type II. These are shown to be related to the crude oil/water interfacial rheological properties. For incompressible crude oil/water films, droplet—droplet coalescence is hindered and chains of water droplets are established. These increase the electrical conductivity of the emulsion (type I behaviour). On the other hand, efficient droplet—droplet coalescence accompanied by minimal conduction occurs in electric fields if the interfacial film is compressible (type II).     

Luminescence properties of soluble 2,2′,7,7′‐Tetrakis(2‐(9‐hexyl‐9H‐carbazol‐3‐yl)‐vinyl)‐9,9′‐spirobifluorene‐labeled dendrimers: Photoluminescence and electroluminescence

New light emitting dendrimers were synthesized by reacting 3,5‐bis‐(3,5‐bis‐benzyloxy‐benzyloxy)‐benzoic acid or 3,5‐bis‐[3,5‐bis‐(3,5‐bis‐benzyloxy‐benzyloxy)‐benzyloxy]‐benzoic acid with a carbazolyl vinyl spirobifluorene moiety. A blue‐emitting core dye was encapsulated by multibenzyloxy dendrons, and two dendrimers having different densities of dendrons were prepared. Photoluminescence (PL) studies of the dendrimers demonstrated that at the higher density of benzyloxy dendrons, the featureless vibronic transitions were improved, causing lesser excimer emission. The similarity of the solution and solid emission spectra of the larger dendrimer, 10 , revealed the suppression of molecular aggregation in the solid film, which is attributed to the presence of the bulky benzyloxy dendrons. The electroluminescence spectra of multilayered devices made using 10 predominantly exhibited blue emissions; similar emission was observed in the PL spectra of its thin film. The multilayered devices made using 3 , 9 , and 10 showed luminances of 1021 cd m^?2 at 5 V, 916 cd m^?2 at 6 V, and 851 cd m^?2 at 6.5 V, respectively. The largest dendrimer, 10 , bearing a greater number of benzyloxy dendrons, exhibited a blue‐like emission with CIE 1931 chromaticity coordinates of x = 0.16 and y = 0.13, which is due to the influence of a higher shielding effect. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 501–514, 2008     

Effect of ionic surfactants on drainage and equilibrium thickness of emulsion films

This paper presents new theoretical and experimental results that quantify the role of surfactant adsorption and the related interfacial tension changes and interfacial forces in the emulsion film drainage and equilibrium. The experimental results were obtained with plane-parallel microscopic films from aqueous sodium dodecyl sulphate solutions formed between two toluene droplets using an improved micro-interferometric technique. The comparison between the theory and the experimental data show that the emulsion film drainage and equilibrium are controlled by the DLVO interfacial forces. The effect of interfacial viscosity and interfacial tension gradient (the Marangoni number) on the film drainage is also significant.     

Effect of droplet size on the dielectric properties of PDLC films

Polymer dispersed liquid crystal (PDLC) films (5CB/PMMA, 60/40) of different droplet size were prepared by a solvent-induced phase separation method under different N₂ flow speeds. The effects of droplet size on the thermal transitions of the LC and various dielectric properties such as dielectric constant, conductance, dielectric loss, and the electric field induced in a droplet were examined. The configuration of the LC in the film with smaller droplets can be identified by comparing the dielectric constant of the film with the one predicted by Boettcher's mixture formula. In addition, the effect of droplet size on the electro-optical response of the PDLC film was investigated. Variations of the conductance and the dielectric constant of the film were analyzed under various AC frequencies, with the purpose of elucidating the polarization mechanism of the LC molecules in the droplet. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1373–1381, 1997