Effect of Emulsifier Type on the Characterization of O/W Emulsions Using a Spectroscopy Technique

The droplet size distribution (DSD) of emulsions is the result of two competitive effects that take place during emulsification process, i.e., drop breakup and drop coalescence, and it is influenced by the formulation and composition variables, i.e., nature and amount of emulsifier, mixing characteristics, and emulsion preparation, all of which affect the emulsion stability. The aim of this study is to characterize oil-in-water (O/W) emulsions (droplet size and stability) in terms of surfactant concentration and surfactant composition (sodium dodecyl benzene sulphonate (SDBS)/Tween 80 mixture). Ultraviolet-visible (UV-vis) transmission spectroscopy has been applied to obtain droplet size and stability of the emulsions and the verification of emulsion stability with the relative cleared volume technique (time required for a certain amount of emulsion to separate as a cleared phase). It is demonstrated that the DSD of the emulsions is a function of the oil concentration and the surfactant composition with higher stability for emulsions prepared with higher SDBS ratio and lower relative cleared volume with the time. Results also show that smaller oil droplets are generated with increasing Tween 80 ratio and emulsifier concentration.     

A combined CFD modeling with population balance equation to predict pressure drop in venturi scrubbers

A venturi scrubber is one of the most important devices for air pollution control. Although there are different models for predicting the pressure drop in venturi scrubbers, most of them have some defects and cannot predict the pressure drop correctly. In this study, for the first time, an Eulerian–Eulerian computational fluid dynamics (CFD) model is combined with a population balance equation to predict the pressure drop in venturi scrubbers. This simulation takes into account a multiple size group model for droplet dispersion and droplet size distribution, which is based on a population balance equation. Flow field has been calculated by solving the time averaged continuity and Navier–Stokes equations along with the standard k–ε turbulence model. The equations included drag, turbulent dispersion, and buoyancy forces. The calculated pressure drop with and without considering the population balance equation was compared with the experimental data to evaluate the accuracy of the CFD modeling. The size distribution of droplets in the venturi scrubber was studied at different points for different liquid to gas ratios and throat gas velocities. The results show that the maximum break-up of droplets happens at the liquid injection point. Finally, the effects of nozzle diameter and nozzle arrangement on pressure drop in venturi scrubbers were investigated.     

Time evolution of the drop size distribution for liquid–liquid dispersion in an agitated tank

Agitating two immiscible liquids or a solid–liquid suspension is an operation frequently performed in the chemical and metallurgical industries, for example, in suspension/emulsion polymerization, heterogeneous/phase-transfer catalytic chemical reactions, and hydrometallurgical solvent extraction. For emulsification, suspension polymerization, solid particle dispersion, and crystallization, it is essential to be able to predict the mean drop/particle size and the drop/particle size distribution. A simple model was proposed for predicting the time evolution of drop size distribution during drop breaking, and was successfully tested on data published by Ruiz and Padilla (Hydrometallurgy 72:245–258, 2004) and by Sathyagal et al. (Chem Eng Sci 51: 1377–1391, 1996) and on our own data. The time evolution of DSD was investigated in a baffled tank agitated by a Rushton turbine for a liquid–liquid dispersion. The tests were carried out on a silicone oil–water dispersion (oil in water) with a dispersed-phase fraction of 0.00047. The drop sizes were determined by image analysis.     

NMR studies of emulsions

Application of NMR techniques to characterize colloidal systems has rendered many unique and valuable insights. Here we consider NMR's ability to quantify an emulsion droplet size distribution (DSD) via its ability to measure restricted molecular self-diffusion. The methodology is described along with the advantages and limitations of the technique. Recent highlights and typical applications are then elucidated.     

Roles of interfacial properties on the stability of emulsified bitumen droplets

Because of the deformable nature of emulsion droplets, it is imperative to consider the inter-droplet pressure in assessing the stability of a liquid-liquid dispersion. In a novel methodology, the pressure generated between droplets in axial compression is estimated through considerations of equilibrium shape mechanics. The applied compressive pressure is compared to the disjoining pressure, induced by the surface charges, resisting droplet-droplet interaction. The stability of bitumen droplets, emulsified in aqueous media, is assessed from surface mechanical and electrostatic perspectives. In support of the analysis, the tensions at, and zeta potentials near, the bitumen droplet surfaces are measured. The predicted trends of stability against coalescence are confirmed by novel droplet interaction experiments: Individual emulsified bitumen droplets, manipulated by suction micropipettes, are compressed against one another along a mutual axis at up to 100 nN force. The force is measured via the deflection of a sensitive microcantilever. Because of the statistical nature of the experimental observations, a probability of coalescence is quantified. The water chemistry dramatically influences bitumen droplet coalescence, which is enhanced in acidic environments and at high ionic strength.     

Simultaneous generation of multiple aqueous droplets in a microfluidic device

This paper describes a microfluidic platform for the on-demand generation of multiple aqueous droplets, with varying chemical contents or chemical concentrations, for use in droplet based experiments. This generation technique was developed as a complement to existing techniques of continuous-flow (streaming) and discrete-droplet generation by enabling the formation of multiple discrete droplets simultaneously. Here sets of droplets with varying chemical contents can be generated without running the risk of cross-contamination due to the isolated nature of each supply inlet. The use of pressure pulses to generate droplets in parallel is described, and the effect of droplet size is examined in the context of flow rates and surfactant concentrations. To illustrate this technique, an array of different dye-containing droplets was generated, as well as a set of droplets that displayed a concentration gradient of a fluorescent dye.     

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     

流动聚焦型微流控体系中的液滴的图案化排列和转变模式

流体在微流通道中形成剪切流场（低雷诺数）．不同于宏观体系,由于剪切力和表面张力的竞争作用,产生的液滴在微尺度下的微流通道中形成特殊的排列现象---周期性类似“晶格”排列现象．设计了新型流动聚焦型微流控芯片,分析研究在微流体系中液滴周期性图案化排列和转变机理性,液滴排列模式受两方面因素影响：水油两相的流速比值和微通道尺寸．当微通道宽度为250或300 μm时,液滴形成单层分散,双层和单层挤压排列．当微通道宽度为350 μm 时,液滴会形成单层分散到三层排列到双层挤压最后到单层挤压排列．当出口通道宽度增加到400 μm时,甚至出现了液滴四层排列的现象．同时研究了各个液滴排列模式的“转变点”.     

High-throughput droplet analysis and multiplex DNA detection in the microfluidic platform equipped with a robust sample-introduction technique

In this work, a simple, flexible and low-cost sample-introduction technique was developed and integrated with droplet platform. The sample-introduction strategy was realized based on connecting the components of positive pressure input device, sample container and microfluidic chip through the tygon tubing with homemade polydimethylsiloxane (PDMS) adaptor, so the sample was delivered into the microchip from the sample container under the driving of positive pressure. This sample-introduction technique is so robust and compatible that could be integrated with T-junction, flow-focus or valve-assisted droplet microchips. By choosing the PDMS adaptor with proper dimension, the microchip could be flexibly equipped with various types of familiar sample containers, makes the sampling more straightforward without trivial sample transfer or loading. And the convenient sample changing was easily achieved by positioning the adaptor from one sample container to another. Benefiting from the proposed technique, the time-dependent concentration gradient was generated and applied for quantum dot (QD)-based fluorescence barcoding within droplet chip. High-throughput droplet screening was preliminarily demonstrated through the investigation of the quenching efficiency of ruthenium complex to the fluorescence of QD. More importantly, multiplex DNA assay was successfully carried out in the integrated system, which shows the practicability and potentials in high-throughput biosensing.     

Experimental study of the relative effect of pressure drop and flow rate on the droplet size downstream of a pipe restriction

An experimental setup consisting of a 100?mm inner diameter pipeline, a butterfly valve with inner diameter of 100?mm, and oil and water pumping capacities of up to 20?m³/h were used to study droplet breakup in two-phase oil–water flow. The tests were performed at atmospheric pressure and under ambient temperatures. A particle-sizing camera was used to quantify droplet sizes. Combinations of different flow rates, water cuts, and pressure drops were tested to determine the relative effects of flow rate and pressure drop over a valve on the droplet breakup process. The test matrix was designed so that it should be possible to determine if the droplet sizes produced were independent of the flow rate. The fluid system consisted of a water phase and a mineral oil with viscosity of 4?mPa?·?s. Two different droplet breakup models were compared against the measured droplet sizes. The two models considered turbulence and droplet acceleration through the restriction respectively as the main contributor for droplet breakup.     

Formation of droplets and bubbles in a microfluidic T-junction-scaling and mechanism of break-up

This article describes the process of formation of droplets and bubbles in microfluidic T-junction geometries. At low capillary numbers break-up is not dominated by shear stresses: experimental results support the assertion that the dominant contribution to the dynamics of break-up arises from the pressure drop across the emerging droplet or bubble. This pressure drop results from the high resistance to flow of the continuous (carrier) fluid in the thin films that separate the droplet from the walls of the microchannel when the droplet fills almost the entire cross-section of the channel. A simple scaling relation, based on this assertion, predicts the size of droplets and bubbles produced in the T-junctions over a range of rates of flow of the two immiscible phases, the viscosity of the continuous phase, the interfacial tension, and the geometrical dimensions of the device.     

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.     

The potential of micromixers for contacting of disperse liquid phases

The dispersion of two immiscible fluids in a static micromixer comprising interdigital channels with corrugated walls was investigated using silicon oil dispersed in dyed as well as pure water as test systems. Silicon oil and water flow rates between 20 mL/h to 500 mL/h and 150 mL/h to 700 mL/h were used, respectively. The experiments revealed the dependence of the average droplet size and size distribution on geometrical parameters of the micromixer and operating conditions. Dispersions with average droplet sizes as small as 5.6 μm and monomodal size distributions having small standard deviations of the droplet size down to 3.6 μm could be generated using the micromixer. The droplet size decreased with increasing total flow and ratio of the flow rates of the two liquids. In addition, a decrease of the droplet size was found when decreasing the channel width of the mixing device. Generally, the silicon oil – dyed water dispersion showed smaller average droplet sizes and were more stable compared to the dispersions based on silicon oil and pure water. Received: 5 January 1999 / Revised: 10 February 1999 / Accepted: 13 February 1999     

Design of microfluidic channel geometries for the control of droplet volume, chemical concentration, and sorting

Passive microfluidic channel geometries for control of droplet fission, fusion and sorting are designed, fabricated, and tested. In droplet fission, the inlet width of the bifurcating junction is used to control the range of breakable droplet sizes and the relative resistances of the daughter channels were used to control the volume of the daughter droplets. Droplet fission is shown to produce concentration differences in the daughter droplets generated from a primary drop with an incompletely mixed chemical gradient, and for droplets in each of the bifurcated channels, droplets were found to be monodispersed with a less than 2% variation in size. Droplet fusion is demonstrated using a flow rectifying design that can fuse multiple droplets of same or different sizes generated at various frequencies. Droplet sorting is achieved using a bifurcating flow design that allows droplets to be separated base on their sizes by controlling the widths of the daughter channels. Using this sorting design, submicron satellite droplets are separated from the larger droplets.     

Influence of dynamic interfacial tension on droplet formation during membrane emulsification

Membrane emulsification is a promising and relatively new technique for producing emulsions. The purpose of this study was to better understand the influence of interfacial tension on droplet formation during membrane emulsification. Droplet formation experiments were carried out with a microengineered membrane; the droplet diameter and droplet formation time were studied as a function of the surfactant concentration in the continuous phase. These experiments confirm that the interfacial tension influences the process of droplet formation; higher surfactant concentrations lead to smaller droplets and shorter droplet formation times (until 10 ms). From drop volume tensiometer experiments we can predict the interfacial tension during droplet formation. However, the strong influence of the rate of flow of the to-be-dispersed phase on the droplet size cannot be explained by the predicted values. This large influence of the oil rate of flow is clarified by the hypothesis that snap-off is rather slow in the studied regime of very fast droplet formation.     

An Image-Based Technique for Measuring Droplet Size Distribution: The Use of CNN Algorithm

A challenging task in measuring droplet size is the ability to perform in-situ droplet size distribution analysis on multiphase fluids in their native states in the undisturbed environment. In this study, an inline two-dimensional low cost–high accuracy technique is presented for continuous measurement of spherical or non-spherical droplets in emulsions using image processing. The characteristic of the droplets is evaluated and the describe drop size distributions in different ranges is determined. This droplet size determination algorithm is based on both cellular neural networks and linear matrix inequality. Our main work focuses on the performance of the proposed methodology for exploring the dynamical evolution of such droplet size distributions by in-situ measurement. Moreover, the results were compared with those obtained using laser diffraction analyzer technique. It was proved that this method can efficiently characterize the quality of dispersed phase by determining droplet size distribution.     

Modeling of droplet traffic in interconnected microfluidic ladder devices

The problem of controlling the droplet motion in multiphase flows on the microscale has gained increasing attention because the droplet-based microfluidic devices provide great potentials for chemical and biological applications. It is critical to understand the relevant physics on droplet hydrodynamics and thus control the generation, motion, splitting, and coalescence of droplets in complex microfluidic networks. Numerical simulations using the volume of fluid algorithm are conducted to investigate the time-dependent dynamics of droplets in gas-liquid multiphase devices. An analytical model based on the electronic-hydraulic analogy is developed to describe the hydrodynamic behavior of the droplets in interconnected microfluidic ladder devices. It is found that the pressure drop caused by the droplets plays a critical role in the droplet synchronization. A fitted formula for pressure drops in the presence of surfactant is achieved by using numerical simulations. Both the numerical and the theoretical results agree well with the corresponding experimental results.     

Contact angle hysteresis on polymer substrates established with various experimental techniques, its interpretation, and quantitative characterization

The effect of contact angle hysteresis (CAH) was studied on various polymer substrates with traditional and new experimental techniques. The new experimental technique presented in the article is based on the slow deformation of the droplet, thus CAH is studied under the constant volume of the drop in contrast to existing techniques when the volume of the drop is changed under the measurement. The energy of hysteresis was calculated in the framework of the improved Extrand approach. The advancing contact angle established with a new technique is in a good agreement with that measured with the needle-syringe method. The receding angles measured with three experimental techniques demonstrated a very significant discrepancy. The force pinning the triple line responsible for hysteresis was calculated.     

Interfacial profiles in fluid/liquid systems: a description based on the storing of elastic energy

The formation and stability of drops in the presence of nanoparticles was studied in a microfluidic device to directly observe the early stages of Pickering emulsification (low interfacial coverage). We observed several key differences between oil droplet necking and rupture in aqueous phases of nanoparticles (methylated silica) and well-characterised surfactant systems. The presence of particles did not influence drop formation dynamics and thus the size of the drops generated. In addition, observations of in-channel drop stability shortly after formation (several milliseconds) indicated that particles in the aqueous phase slow film thinning processes, but do not prevent coalescence. In contrast, downstream collection and densification (at the microchannel outlet), showed that particle-stabilised drops do not coalesce for several weeks, above a critical particle concentration. The implications of our results for droplet microfluidics and our understanding of conventional emulsification systems are discussed.