Numerical assessment of ultrasound supported coalescence of water droplets in crude oil

In this study, a numerical assessment of the coalescence of binary water droplets in water-in-oil emulsion was conducted. The investigation addressed the effect of various parameters on the acoustic pressure and coalescence time of water droplets in oil phase. These include transducer material, initial droplet diameter (0.05–0.2 in), interfacial tension (0.012–0.082 N/m), dynamic viscosity (10.6–530 mPas), temperature (20–100 °C), US (ultra sound) frequency (26.04–43.53 kHz) and transducer power (2.5–40 W). The materials assessed are lead zirconate titanate (PZT), lithium niobate (LiNbO₃), zinc oxide (ZnO), aluminum nitride (AlN), polyvinylidene fluoride (PVDF), and barium titanate (BaTiO₃). The numerical simulation of the binary droplet coalescence showed good agreement with experimental data in the literature. The US implementation at a fixed frequency produced enhanced coalescence (t = 5.9–8.5 ms) as compared to gravitational settling (t = 9.8 ms). At different ultrasound (US) frequencies and transducer materials, variation in the acoustic pressure distribution was observed. Possible attenuation of the US waves, and the subsequent inhibitive coalescence effect under various US frequencies and viscosities, were discussed. Moreover, the results showed that the coalescence time reduced across the range of interfacial tensions which was considered. This reduction can be attributed to the fact that lower interfacial tension produces emulsions which are relatively more stable. Hence, at lower interface tension between the water and crude oil, there was more resistance to the coalescence of the water droplets due to their improved emulsion stability. The increment of the Weber number at higher droplet sizes leads to a delay in the recovery of the droplet to spherical forms after their starting deformation. These findings provide significant insights that could aid further developments in demulsification of crude oil emulsions under varying US and emulsion properties.     

Continuous director-field transformation of nematic tactoids

We theoretically investigate the director field inside spindle-shaped nematic droplets, known as tactoids. Tactoids typically form in dispersions of rod-like colloidal particles. By optimising the bulk elastic and surface energies, we find that the director field crosses over smoothly from a homogeneous to a bipolar configuration with increasing droplet size, in a process that we postulate to involve two virtual point defects that move in from infinity towards the poles on the surface of the droplet. Our calculations show that these hypothesised virtual defects become true surface point defects or boojums only in the limit of infinite droplet volume, and that the more elongated the droplets are, the larger their volume has to be before a uniform director field distorts so as to become discernibly bipolar. The theory agrees well with available experimental data on the size dependence of the aspect ratio of tactoids.Received: 31 October 2003, Published online: 2 March 2004PACS: 61.30.St Lyotropic phases - 64.70.Md Transitions in liquid crystals - 81.16.Dn Self-assembly - 82.70.Dd Colloids     

Optimization of acoustic parameters for ultrasonic separation of emulsions with different physical properties

Ultrasound is an emerging and promising method for demulsification, which is highly affected by acoustic parameters and emulsion properties. Herein, a series of microscopic and dehydration experiments are carried out to investigate the parameter optimization of ultrasonic separation. The results show that the optimal acoustic parameters highly depend on the emulsion properties. For low frequency ultrasonic standing waves (USWs), mechanical vibrations not only facilitate droplet collision and coalescence, but also disperse the surfactant absorbed on the interface to decrease the interfacial strength. Therefore, low frequency ultrasound is suitable for separating emulsions with high viscosity and high interfacial strength. Increasing the energy density to produce moderate cavitation can increase demulsification efficiency. However, excessive cavitation results in secondary emulsification. In high frequency USWs, the droplets migrate directionally and form bandings, thereby promoting droplet coalescence. Therefore, high frequency ultrasound is favorable for separating emulsions with low dispersed phase content and small droplet size. Increasing the energy density can accelerate the aggregation of droplets, however, excessive energy density causes acoustic streaming that disturbs the aggregated droplets, resulting in reduced demulsification efficiency. This work presents rules for acoustic parameter optimization, further advancing industrial applications of ultrasonic separation.     

Ultrasound assisted preparation of water in oil emulsions and their application in arsenic (V) removal from water in an emulsion liquid membrane process

Water in oil emulsions are prepared by using an ultra-sonication device and used in an emulsion liquid membrane process in order to recover arsenic (V) ions from an aqueous medium. The aim of this work is the investigation of the effect of emulsifier concentration and composition, and also sonication time on the emulsion droplet size and the extraction efficiency in order to obtain stable emulsions with small droplets that favor the extraction. Results show that ultrasonic waves reduce internal droplet size which enhances the extraction of arsenic. In addition, internal droplet size is decreased initially and then increased by increasing Span 80 concentration. On the other hand, by increasing Span 80 concentration, extraction amount is increased and then decreased. Furthermore, emulsifier blends provide more stability for the emulsion. Increasing concentration of Tween 20 as a hydrophilic emulsifier up to an optimum concentration decreases internal droplet size and increases extraction amount. By increasing sonication time up to 4 min, the internal droplet size is decreased and the extraction amount is increased. If sonication time is increased further, the internal droplet size is increased and the extraction amount is decreased.     

Enhanced creaming of milk fat globules in milk emulsions by the application of ultrasound and detection by means of optical methods

The effects of application of ultrasonic waves to recombined milk emulsions (3.5% fat, 7% total solids) and raw milk on fat destabilization and creaming were examined. Coarse and fine recombined emulsions (D[4,3]=9.3 μm and 2.7 μm, respectively) and raw milk (D[4,3]=4.9 μm) were subjected to ultrasound for 5 min at 35°C and 400 kHz or 1.6 MHz (using a single transducer) or 400 kHz (where the emulsion was sandwiched between two transducers). Creaming, as calculated from Turbiscan measurements, was more evident in the coarse recombined emulsion and raw milk compared to that of the recombined fine emulsion. Micrographs confirmed that there was flocculation and coalescence in creamed layer of emulsion. Coalescence was confirmed by particle size measurement. These results imply that ultrasound has potential to pre-dispose fat particles in milk emulsions to creaming in standing wave systems and in systems with inhomogeneous sound distributions.     

Features of the motion of particles suspended in liquid under an applied field

It is experimentally shown that a tenfold-hundredfold increase in the effective diffusion coefficient along the direction perpendicular to an applied electric field takes place in various emulsions and suspensions. It is caused by electrophoretic motion of particles. In inverse emulsions and many suspensions, only a certain fraction of dispersed material is contained in particles whose average radius is determined by the dynamic light scattering method. It is shown that the average coherence time of light scattered by silicon particle suspensions at a constant laser power depends on the beamdiameter. This means that semiconductor particles are characterized by strong nonlinearity.     

Pickering emulsion polymerization of polyaniline/LiCoO2 nanoparticles used as cathode materials for lithium batteries

The oil in water (o/w) emulsions were prepared using aniline dissolved in toluene and LiCoO₂ particles as stabilizers (Pickering emulsions). Pickering emulsions are stabilized by adsorbed solid particles instead of emulsifier molecules. The mean droplet diameter of emulsions was controlled by the mass ratio M (oil)/M (solid particles). The emulsions showed great stability during 3 days. The composite materials containing LiCoO₂ and the conductive polymer polyaniline (PANI) have been prepared by means of polymerization of aniline emulsion stabilized by LiCoO₂ particles. The composite materials were characterized by nanosphere and nanofiber-like structures. The nanofiber-like morphology of the powdered material was distinctly different of the morphologies of the parent materials. The electrochemical reactivity of PANI/LiCoO₂ composites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ (1:4) composite materials exhibited the best electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The first discharge capacity of PANI/LiCoO₂ (1:4) was 167 mAh/g, while that of LiCoO₂ was136 mAh/g.     

On the coalescence of sessile drops with miscible liquids

Sessile drops sitting on highly wettable solid substrates fuse in qualitatively different ways after contact, depending on the surface tension gradients between the mixing droplets. In early time evolution the drop coalescence can be fast or delayed (intermittent). In long time evolution a secondary drop formation can occur. We study numerically droplet dynamics during coalescence in two and three spatial dimensions, within a phase field approach. We discuss criteria to distinguish different coalescence regimes. A comparison with recent experiments will be done.     

Microexplosion of an emulsion droplet during Leidenfrost burning

An experimental study has been made of the microexplosion of an emulsion droplet on a hot surface during Leidenfrost burning. Photographic observation is used to study how the emulsion droplet behaves and what happens inside the droplet and to measure the waiting time for the onset of microexplosion. Weibull analysis was used to obtain the distribution function of the waiting time for the onset of microexplosion and to derive the formula for the rate of microexplosion as a function of water volume and emulsion temperature. The base fuels employed were n-decane, n-dodecane, n-tetradecane, and n-hexadecane. The results show that the increase in emulsion temperature with lapse of time results in the agglomeration and coalescence of microdroplets of base fuel dispersed in the continuous phase of water inside the emulsion droplet, terminated by the complete separation of the two phases. At the end of the phase separation process, an opaque water droplet is formed in the central core and is enveloped by the transparent shell of base fuel. Preferential evaporation of the base fuel occurs after the phase separation. The volume of the base fuel decreases while the water volume remains constant. The onset of the microexplosion of an emulsion droplet burning on the hot surface is classified by the wearout type of the Weibull distribution. The waiting time for the onset of the microexplosion decreases with increases in the normal boiling point of base fuel, initial water content, ambient pressure, and test surface temperature. The rate of microexplosion increases with the lapse of time and with increased normal boiling point of the base fuel. The rate of microexplosion increases linearly with increasing water volume in the emulsion droplet and decreases exponentially with the inverse of emulsion temperature.     

Absorption and velocity dispersion due to crystallization and melting of emulsion droplets

The influence of droplet crystallization and melting on the ultrasonic properties of oil-in-water emulsions has been investigated. The ultrasonic velocity and attenuation were measured in a series of 3 wt% n-hexadecane-in-water emulsions as a function of frequency (0.3–4 MHz), droplet diameter (0.4 and 1 μm) and temperature (0–25°C). The emulsified n-hexadecane crystallized at about 5°C due to supercooling effects and melted at about 18°C. As solid and liquid n-hexadecane have significantly different ultrasonic properties, an appreciable change in the velocity and attenuation is observed during the phase transition. This behaviour is modified significantly in systems where the emulsion droplets are partially crystalline because the temperature fluctuations associated with the ultrasonic wave can perturb the phase equilibria solid liquid causing excess attenuation and velocity dispersion. The magnitude of this effect depends on the ultrasonic frequency and the average droplet size.     

The foam/emulsion analogy in structure and drainage

The often quoted analogy between foams and emulsions is experimentally tested by studying properties after settling and under forced drainage of oil-in-water emulsions of drop size similar as for bubbles generally used in foam experiments. Observations with regard to structure, water fraction and drainage wave properties confirm the expected similarity in the low flow rate range. However, while for foams a convective circulation on the scale of the container sets in for values of water fraction exceeding about 0.2, no such convection is found in emulsions. Here instabilities are only encountered at water fractions of about 0.4, close to the void fraction of random packings of spheres. These take on the form of descending pulses of increased water fraction and lead to the transition from a frozen to a locally agitated structure.Received: 12 December 2003, Published online: 24 August 2004PACS: 82.70.-y Disperse systems; complex fluids - 47.20.-k Hydrodynamic stability - 47.55.Dz Drops and bubbles     

Decompressing emulsion droplets favors coalescence

The destabilization process of an emulsion under flow is investigated in a microfluidic device. The experimental approach enables us to generate a periodic train of droplet pairs, and thus to isolate and analyze the basic step of the destabilization, namely, the coalescence of two droplets which collide. We demonstrate a counterintuitive phenomenon: coalescence occurs during the separation phase and not during the impact. Separation induces the formation of two facing nipples in the contact area that hastens the connection of the interfaces prior to fusion. Moreover, droplet pairs initially stabilized by surfactants can be destabilized by forcing the separation. Finally, we note that the fusion mechanism is responsible for a cascade of coalescence events in a compact system of droplets where the separation is driven by surface tension.     

Thermodynamically stable pickering emulsions

We show that under appropriate conditions, mixtures of oil, water, and nanoparticles form thermodynamically stable oil-in-water emulsions with monodisperse droplet diameters in the range of 30-150 nm. This observation challenges current wisdom that so-called Pickering emulsions are at most metastable and points to a new class of mesoscopic equilibrium structures. Thermodynamic stability is demonstrated by the spontaneous evolution of binary droplet mixtures towards one intermediate size distribution. Equilibrium interfacial curvature due to an asymmetric charge distribution induced by adsorbed colloids explains the growth of emulsion droplets upon salt addition. Moreover, the existence of a minimal radius of curvature with a concomitant expulsion of excess oil is in close analogy with microemulsions.     

Techno-economic comparative assessment of the ultrasound,electrostatic and microwave supported coalescence of binary water droplets in crude oil

In this study, comparative assessment of the technical performance, energy usage and economic impact of ultrasound, electrostatics and microwave on the coalescence of binary water droplets in crude oil was conducted. The effect of different oil properties such as crude oil viscosity (10.6–106 mPa s) and interfacial tension (IFT) (20–250 mN/m) on the coalescence time and energy consumption was examined. In addition, operation conditions such as inlet emulsion flow velocity (10–100 mm/s), electric field type, ultrasound frequency and applied voltage amplitude (0–30 kV) were evaluated. The numerical models showed good agreement with experimental findings in the literature. Moreover, the process time of the dewatering process increased with rising inlet flow velocities. The elevation of the coalescence time with velocity can be attributed to the increasing effect of flow disturbance, and the reduction of the emulsion residence time. As regards the IFT, the coalescence time reduced as the IFT was increased. This can be associated with the improved stability of emulsions formed at lowered IFT. As the maximum droplet size is directly proportional to the IFT, lowering the IFT reduces the peak diameter of the droplets that are present in the emulsion. Moreover, the coalescence time followed the order: ultrasound < microwave < electrostatics approaches under varying IFT. The coalescence energy increased from ∼15 J, ∼90 J and ∼25 mJ to ∼61 J, ∼235 J and ∼26 mJ for microwave, electrostatics and ultrasound techniques, respectively, as the viscosity was raised from 10.6 to 106 mPa s. Ultrasound coalescence showed significant energy and economic savings in comparison to microwave and electro-coalescence. Hence, ultrasound coalescence would be a potential method for standalone or integrated demulsification over the two other techniques. However, there are indications that beyond a viscosity of 300 mPa s, the effect of ultrasound becomes weak with significant hindrance to droplet movement and accumulation. This analysis provides fundamental insights on the comparative behavior of the three emulsion separation techniques.     

The droplet breakup model and characteristics of pH-shifted peanut protein isolate-high methoxyl pectin stabilised emulsions under ultrasound

The effect of pH on the occurrence states of peanut protein isolate (PPI) and high methoxyl pectin (HMP), and droplet breakup model of the emulsions under ultrasound were studied. Particle size distribution and scanning electron microscopy results showed that PPI-HMP existed a soluble complex at pH 5.0, had no interaction at pH 7.0, and was co-soluble at pH 9.0. Droplet breakup model results revealed that the characteristics of emulsion stabilised by PPI-HMP treated at pH 5.0 was different from that at pH 7.0 and 9.0. The average diameter of the droplet well satisfied the model. According to rheological properties, interface tension, and microstructure, the formation mechanism and characteristics of emulsion stabilised by PPI-HMP treated at pH 5.0 was different from that at pH 7.0 and pH 9.0. The research provided a reference for constructing emulsions using pH-shifted PPI-HMP under ultrasound.     

Spatially resolved emulsion droplet sizing using inverse Abel transforms

Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) is well established as a tool for determining emulsion droplet-size distributions via measurement of restricted self-diffusion. Most measurements made to date have not been spatially resolved, but have measured an average size distribution for a certain volume of emulsion. This paper demonstrates a rapid method of performing spatially resolved, restricted diffusion measurements, which enables emulsion droplet sizing to be spatially resolved as a function of radius in cylindrical geometries or pipes. This is achieved by the use of an Abel transform. The technique is demonstrated in various annular systems containing two emulsions, with different droplet-size distributions, and/or a pure fluid. It is also shown that by modifying the pulse sequence by the inclusion of flow-compensating magnetic field gradients, the technique can measure spatially resolved droplet-size distributions in flowing emulsions, with potential applications in spatially resolved on-line droplet-size analysis.     

Emulsion droplet sizing using low-field NMR with chemical shift resolution and the block gradient pulse method

Pulsed Field Gradient (PFG) measurements are commonly used to determine emulsion droplet size distributions based on restricted self-diffusion within the emulsion droplets. Such measurement capability is readily available on commercial NMR bench-top apparatus. A significant limitation is the requirement to selectively detect signal from the liquid phase within the emulsion droplets; this is currently achieved using either relaxation or self-diffusion contrast. Here we demonstrate the use of a 1.1 T bench-top NMR magnet, which when coupled with an rf micro-coil, is able to provide sufficient chemical shift resolution such that unambiguous signal selection is achieved from the dispersed droplet phase. We also improve the accuracy of the numerical inversion process required to produce the emulsion droplet size distribution, by employing the Block Gradient Pulse (bgp) method, which partially relaxes the assumptions of a Gaussian phase distribution or infinitely short gradient pulse application inherent in current application. The techniques are successfully applied to size 3 different emulsions.     

Mobile polymer connectors

We study the junction between two solid objects, formed by polymer connectors which are supposed to freely explore the two grafting surfaces. We focus on the sphere-plane and sphere-sphere geometries. Because the chains are mobile, they are able to adapt both the local grafting density and their conformation to the position of the surfaces. Using a scaling approach, we show that, in chemical equilibrium, local grafting density is non-monotonic, and the junction can be divided into two different regions: the center, where connectors are compressed and exert a repulsive force between the objects (high excluded-volume interactions) and an external corona, where chains are stretched and attract the two objects. The relative importance of these regions varies for different separations and depends on surface geometries. When an external force is applied, this spatially inhomogeneous constraint exerted by the junction leads to specific force-distance profiles, which differ from profiles in the case of fixed connectors. An effective interaction potential and the adhesion energy are computed, showing a strong dependence on the geometry of surfaces.Received: 5 March 2003, Published online: 8 July 2003PACS: 36.20.Ey Conformations (statistics and dynamics) - 82.35.Gh Polymers on surfaces; adhesion - 82.70.Dd Colloids M. Manghi: Present address: Theorie, Sektion Physik, Ludwig Maximilian University, Theresienstr. 37, 80333 Munich, Germany     

Characterization of Y<Subscript>2</Subscript>BaCuO<Subscript>5</Subscript> nanoparticles synthesized by nano-emulsion method

Nanoscale yttrium–barium–copper oxide (Y₂BaCuO₅, Y211) particles were synthesized using the emulsion method and the solution method. The basic water-in-oil (w/o) emulsion system consisted of n-octane (continuous oil phase), cetyltrimethylammonium bromide (cationic surfactant), butanol (cosurfactant) and water. The composition of the emulsion system was varied and characterized by measuring the conductivity of the solutions and droplet size. The droplet size of emulsion was determined by using the dynamic light scattering method. The water content, cosurfactant content, and surfactant/n-octane ratio affected the droplet size which was in the range of 3–8 nm, and hence the w/o emulsion system was referred to as a nano-emulsion system. A model was used to verify the droplet size. The influence of salt (Y₂(NO₃)₃) content on the droplet size was investigated and the addition of salt reduced the droplet size. The effects of reaction time and temperature on the Y211 particle sizes were also investigated. The particles were characterized using the TEM, SEM, and XRD. Nanoparticles produced by the nano-emulsion method were calcined at 850°C to form the Y211 phase as compared to solid state processing temperature of 1050°C. Based on the TEM analysis, the average diameter of the Y211 particles produced using the nano-emulsion method was in the range of 30–100 nm. The effect of adding 15% Y211 nanoparticles to the superconductor YBCO-123 as flux pinning centers, was investigated, and the transition temperature was reduced by 3 K.     

Impurity mediated nucleation in hexadecane-in-water emulsions

We report detailed nucleation studies on the liquid-to-solid transition of hexadecane using nearly monodisperse hexadecane-in-water emulsions. A careful consideration of the kinetics of isothermal and nonisothermal freezing shows deviations from predictions of classical nucleation theory, if one assumes that the emulsion droplet population is homogeneous. Similar deviations have been observed previously (3). As an explanation, we propose an argument based on the dynamic generation of droplet heterogeneity mediated by mobile impurities. This proposal is in good agreement with existing data.