Formation of Microdroplets in Liquids Utilizing Active Pneumatic Choppers on a Microfluidic Chip

Monodispersed emulsions are of great significance for a variety of applications. The current study reports a new microfluidic system capable of formation of microdroplets in liquids for emulsification applications. This new emulsion chip can precisely generate uniform droplets using a novel combination of hydrodynamic-focusing and liquid-chopping techniques. Experimental data show that microdroplets with diameters ranging from 6 to 100 mum with a variation less than 3% can be precisely generated. The size of the droplets is tunable using three approaches including adjusting the relative sheath/sample flow velocity ratios, the applied air pressure and the applied chopping frequency. Moreover, focusing and chopping of multiple flows has been demonstrated to increase the emulsion process throughput     

On-demand double emulsification utilizing pneumatically actuated,selectively surface-modified PDMS micro-devices

This article presents an active, two-step emulsification scheme that is capable of producing double emulsions with desired geometries and compositions on demand. Three-layer PDMS micro-devices with pneumatically actuated membrane-valves constructed on top of specially designed fluidic-channels are utilized to meter and shape immiscible fluids into double emulsions. By intermittently squeezing a fluid into another one, controlled emulsification is realized, and successive emulsification steps result in the formation of multiple emulsions. In the prototype demonstration, a three-layer PDMS molding and bonding process was employed to fabricate the proposed microfluidic devices, whose channel surfaces were selectively modified into hydrophilic by a photo-grafting process. A governing computer program cooperating with a set of control hardware was employed to coordinate the actuation of the prototype system. It has been demonstrated that: (1) both water-in-oil-in-oil and water-in-oil-in-water double emulsions can be produced; (2) the sizes of inner aqueous droplets and outer oil drops can be controlled independently; and (3) adjacent oil drops with varying overall sizes, and both diameters and numbers of inner aqueous droplets can be produced on demand. As such, the demonstrated emulsification scheme could potentially fulfill the real-time controllability on emulsion formation, which is desired for a variety of chemical and biological applications.     

Production of uniform droplets using membrane, microchannel and microfluidic emulsification devices

This review provides an overview of major microengineering emulsification techniques for production of monodispersed droplets. The main emphasis has been put on membrane emulsification using Shirasu Porous Glass and microsieve membrane, microchannel emulsification using grooved-type and straight-through microchannel plates, microfluidic junctions and flow focusing microfluidic devices. Microfabrication methods for production of planar and 3D poly(dimethylsiloxane) devices, glass capillary microfluidic devices and single-crystal silicon microchannel array devices have been described including soft lithography, glass capillary pulling and microforging, hot embossing, anisotropic wet etching and deep reactive ion etching. In addition, fabrication methods for SPG and microseive membranes have been outlined, such as spinodal decomposition, reactive ion etching and ultraviolet LIGA (Lithography, Electroplating, and Moulding) process. The most widespread application of micromachined emulsification devices is in the synthesis of monodispersed particles and vesicles, such as polymeric particles, microgels, solid lipid particles, Janus particles, and functional vesicles (liposomes, polymersomes and colloidosomes). Glass capillary microfluidic devices are very suitable for production of core/shell drops of controllable shell thickness and multiple emulsions containing a controlled number of inner droplets and/or inner droplets of two or more distinct phases. Microchannel emulsification is a very promising technique for production of monodispersed droplets with droplet throughputs of up to 100?l?h^?1.     

Guiding of emulsion droplets in microfluidic chips along shallow tracks defined by laser ablation

We demonstrate controlled guiding of nanoliter emulsion droplets of polar liquids suspended in oil along shallow hydrophilic tracks fabricated at the base of microchannels located within microfluidic chips. The tracks for droplet guiding are generated by exposing the glass surface of polydimethylsiloxane (PDMS)-coated microscope slides via femtosecond laser ablation. The difference in wettability of glass and PDMS surfaces together with the shallow step-like transverse topographical profile of the ablated tracks allows polar droplets wetting preferentially the glass surface to follow the track. In this study, we investigate guiding of droplets of two different polar liquids (water/ethylene glycol) with and without surfactant suspended in an oil medium along surface tracks of different depths of 1, 1.5, and 2 \(\upmu\)m. The results of experiments are also verified with computational fluid dynamics simulations. Guiding of droplets along the tracks as a function of the droplet composition and size and the surface profile depth is evaluated by analyzing the trajectories of moving droplets with respect to the track central axis, and conditions for stable guiding are identified. The experiments and numerical simulations indicate that while the track topography plays a role in droplet guiding using 1.5- and 2-\(\upmu\)m deep tracks, for the case of the smallest track depth of 1 \(\upmu\)m, droplet guiding is mainly caused by surface energy modification along the track rather than the presence of a topographical step on the surface. Our results can be exploited to sort passively different microdroplets mixed in the same microfluidic chip, based on their inherent wetting properties, and they can also pave the way for guiding of droplets along reconfigurable tracks defined by surface energy modifications obtained using other external control mechanisms such as electric field or light.     

A droplet-based microfluidic system capable of droplet formation and manipulation

Formation of emulsion droplets is crucial for a variety of industrial and scientific applications. This study presents a new droplet-based microfluidic system capable of generating tunable and uniform-sized droplets and subsequently deflecting these droplets at various inclination angles using a combination of flow-focusing and moving-wall structures. A pneumatic air chamber was used to activate the moving-wall structures, located nearby the outlet of the flow-focusing microchannels, such that the sheath flows can be locally accelerated. With this approach, the size of the droplets can be fine-tuned and sorted without adjusting the syringe pumps. Experimental data showed that droplets with diameters ranging from 31.4 to 146.2 μm with a variation of less than 5.39% can be generated. Besides, droplets can be sorted upwards or backwards with an inclination angle ranging from 0° to 53.5°. The development of this emulsion system may be promising for the formation and collection of emulsion products for applications in the pharmaceutical, cosmetics and food industries.     

A facile on-demand droplet microfluidic system for lab-on-a-chip applications

We present a facile microfluidic droplet-on-demand (DOD) system in which a pulsed pressure generated by a high-speed solenoid valve is used to control the formation and movement of water-in-oil emulsion droplets in a T-junction microchannel. We investigated the working principle of the DOD system and established a scaling model for the droplet volume in terms of the amplitude and duration of the pulse and the hydraulic resistance of the injection channel. The droplet formation was characterized in three designs at various pressure pulses. The experimental results support our scaling model very well. In the DOD system we developed, nanoliter-volume droplets with a throughput of a few droplets per second were on-demand generated. Moreover, we examined the applicable scope of the DOD system. As examples of practical applications of the DOD system, we demonstrated a digital display module to show droplets formed at a prescribed time and a droplet array with a concentration gradient to show droplets formed with a precise volume. We expect our work can provide design guidelines for a robust DOD system and improve the capabilities of droplet-based microfluidics in ‘lab-on-a-chip’ systems.     

Emulsification in a microfluidic flow-focusing device: effect of the viscosities of the liquids

We report the results of a comparative study of microfluidic emulsification of liquids with different viscosities. Depending on the properties of the fluids and their rates of flow, emulsification occurred in the dripping and jetting regimes. We studied the characteristic features and typical dependence of the size and of the size distribution of droplets in each regime. For each liquid, we identified a range of hydrodynamic conditions promoting generation of highly monodisperse droplets. Viscosity played an important role in emulsification: highly viscous liquids were emulsified into larger droplets with lower polydispersity. Although it was not possible to provide a unified scaling for the volumes of the droplets, our results suggest that the break-up dynamics of the lower viscosity fluids resembles the rate-of-flow-controlled break-up, as reported earlier for the formation of bubbles in flow-focusing geometries [Garstecki P, Stone HA, Whitesides GM (2005) Phys Rev Lett 94:164501]. The results of this study can be helpful for a rationalized selection of liquids for the controlled formation of droplets with a predetermined size and with a narrow distribution of sizes.     

Surface modification of a glass microchannel for the formation of multiple emulsion droplets

We herein report a method for the preparation of a glass microchannel capable of forming multiple emulsion droplets (i.e., water-in-oil-in-water and oil-in-water-in-oil) by locally controlling the wettability of the glass microchannel. Production of multiple emulsion droplets using a glass microchannel requires partial control of its wettability using a method that consists of two steps: (1) hydrophobization of a whole glass microchannel by filling the microchannel with octadecyltrichlorosilane (OTS) solution, and (2) local hydrophilization of the OTS-treated glass microchannel by exposure to ultraviolet light through a mask. However, conditions for the preparation of OTS-SAMs for controlling microchannel wettability and subsequent multiple emulsion droplet formation have not yet been reported. In this study, we investigated the conditions required to form multiple emulsion droplets and demonstrated formation of multiple emulsion droplets using a treated glass microchannel with multiple junctions. The glass microchannel prepared according to this method was able to form various aqueous and organic droplets due to its resistance to swelling.     

Microchannel emulsification for mass production of uniform fine droplets: integration of microchannel arrays on a chip

We present a novel microchannel emulsification (MCE) system for mass-producing uniform fine droplets. A 60 × 60-mm MCE chip made of single-crystal silicon has 14 microchannel (MC) arrays and 1.2 × 10⁴ MCs, and each MC array consists of many parallel MCs and a terrace. A holder with two inlet through-holes and one outlet through-hole was also developed for simply infusing each liquid and collecting emulsion products. The MCE chip was sealed well by physically attaching it to a flat glass plate in the holder during emulsification. Uniform fine droplets of soybean oil with an average diameter of 10 μm were reliably generated from all the MC arrays. The size of the resultant fine droplets was almost independent of the dispersed-phase flow rate below a critical value. The continuous-phase flow rate was unimportant for both the droplet generation and the droplet size. The MCE chip enabled mass-producing uniform fine droplets at 1.5 ml h⁻¹ and 1.9 × 10⁹ h⁻¹, which could be further increased using a dispersed phase of low viscosity.     

Droplet mixing using electrically tunable superhydrophobic nanostructured surfaces

We demonstrate effective mixing of microliter droplets using electrically tunable superhydrophobic nanostructured surfaces. By applying electrical voltage and current, droplets can be reversibly switched from a wetting to a non-wetting state, which induces fluid motion within the droplet. This mixing concept was verified using a DNA hybridization assay, in which a single droplet reversibility accelerated the hybridization reaction by an order of magnitude as compared to mixing by passive diffusion. This work offers a new method to effectively mix droplets for a variety of microfluidics applications.     

Formation of fully closed microcapsules as microsensors by microfluidic double emulsion

Microcapsules templated from microfluidic double emulsions attract a great attention due to their broad new potential applications. We present a method to form transparent polymer microcapsules in small sizes of ~30 μm with aqueous cores and fully closed shells. We controlled the size ratio of the aqueous core to the polymer shell not only by flow rates of the double emulsions, but also by synergetic interaction between surfactants at the interface of immiscible fluids. We also found that fully closed shells can be formed by generating the double emulsion droplets in a jetting regime, in which the aqueous cores are confined centrally in the double emulsion droplets. We demonstrated the formation of barcodes in these microcapsules for multiplexed bioassays. These transparent microcapsules also have wide and high potentials for the development of various microsensors by functionalizing the liquid-state cores with compounds sensitive and responsive to temperature, light or electromagnetic field.     

Nanodroplets on a solid plane: wetting and spreading in a Monte Carlo simulation

The wetting behavior and spreading dynamics of small polymer melt droplets in the course of transition from partial to complete wetting conditions on a flat structureless solid substrate have been studied by dynamic Monte Carlo simulation. From the density profiles of the drops we determine the contact angles at varying strength of the van der Waals surface forces in the whole interval of partial wetting. The validity of Young's equation is then tested whereby the surface tension of the melt/vapor interface is derived independently from interfacial fluctuation analysis, and the surface free energy of the melt at the substrate—from the anisotropy of the local pressure at the wall. The bending rigidity of the melt/vapor interface turns out negative, as recently predicted for short-range interactions.We carry out computer experiments which show that Tanner's law for the kinetics of drop spreading holds also on nanoscopic scales. The observed density profiles of spreading droplets confirm earlier predictions that the central cap-shaped region of the droplets shrinks at the expense of a transition region (“foot”) surrounded by a precursor film which is roughly one monolayer thick. At later times the precursor film breaks into individual polymer chains and advances in typically diffusive manner as found in laboratory experiments.Eventually we investigate the impact of line tension on nanodroplets behavior at varying strength of adhesion and demonstrate that the Gretz equation which incorporates line tension into Young's rule holds even on nanoscale and predicts important properties of the drops subject to droplet size.     

Controlled preparation of giant vesicles from uniform water droplets obtained by microchannel emulsification with bilayer-forming lipids as emulsifiers

We investigated a preparation method of giant vesicles using monodisperse water-in-oil (W/O) emulsions stabilized by bilayer-forming emulsifiers. A mixture of phosphatidylcholine, cholesterol and stearylamine was used both to stabilize the water droplets formed in the emulsion and to form the vesicles. Using this lipid mixture, we obtained monodisperse W/O emulsions with mean droplet diameters of 10–40 μm and coefficients of variation as small as ca 5% by means of the microchannel (MC) emulsification technique. Utilization of an asymmetric straight-through MC array device enabled a monodisperse droplet productivity of up to 80 ml/h. The obtained water droplets were converted to giant vesicles via evaporative removal of the continuous-phase solvent followed by addition of an aqueous buffer solution. The resulting vesicles were similar in size to their starting water droplets, and a hydrophilic fluorescent marker was entrapped inside the vesicles.     

Scale-up and control of droplet production in coupled microfluidic flow-focusing geometries

A single microfluidic chip consisting of six microfluidic flow-focusing devices operating in parallel was developed to investigate the feasibility of scaling microfluidic droplet generation up to production rates of hundreds of milliliters per hour. The design utilizes a single inlet channel for both the dispersed aqueous phase and the continuous oil phase from which the fluids were distributed to all six flow-focusing devices. The exit tubing for each of the six flow-focusing devices is separate and individually plumbed to each device. Within each flow-focusing device, the droplet size was monodisperse, but some droplet size variations were observed across devices. We show that by modifying the flow resistance in the outlet channel of an individual flow-focusing device it is possible to control both the droplet size and frequency of droplet production. This can be achieved through the use of valves or, as is done in this study, by changing the length of the exit tubing plumbed to the outlet of the each device. Longer exit tubing and larger flow resistance is found to lead to larger droplets and higher production frequencies. The devices can thus be individually tuned to create a monodisperse emulsion or an emulsion with a specific drop size distribution.     

Y- and T-junction microfluidic devices: effect of fluids and interface properties and operating conditions

Water-in-oil emulsions were produced in microchannels with Y- and T-junction geometries by individual droplet generation. For each microchannel configuration, the effect of the fluids and interface properties as well as of the process conditions was evaluated. The size of the droplets depended mainly on the relative velocity between continuous and dispersed phases and the relative fluid viscosity between phases. Those variables were related to the shear stress between the phases, which caused the droplet detachment. In addition, the interfacial forces played a minor role in Y-junction, and they had no effect in the droplets formation in T-junction microchannels. In Y-junction, a large variation in the droplet size was observed, depending on the system composition and the operating conditions. At low relative velocity and fluid viscosity, no droplets were generated. In contrast, the process in T-junction resulted in a lower variation of droplets size and the droplets were formed even at less favorable conditions. Such results indicate that the knowledge of the mechanism of droplets generation in each microchannel geometry makes it possible to choose the appropriate configuration according to the type of fluid, and the operating conditions can be adjusted to obtain the desired final emulsion.     

Droplet Formation Utilizing Controllable Moving-Wall Structures for Double-Emulsion Applications

The formation of microscale single- and double-emulsion droplets with various sizes is crucial for a variety of industrial applications. In this paper, we report a new microfluidic device which can actively fine-tune the size of single- and double-emulsion droplets in liquids by utilizing controllable moving-wall structures. Moreover, various sizes of external and internal droplets for double emulsions are also successfully formed by using this device. Three pneumatic side chambers are placed at a T-junction and flow-focusing channels to construct the controllable moving-wall structures. When compressed air is applied to the pneumatic side chambers, the controllable moving-wall structures are activated, thus physically changing the width of the microchannels. The size of the internal droplets at the intersection of the T-junction channel is then fine-tuned due to the increase in the shear force. Then, the internal droplets are focused into a narrow stream hydrodynamically and finally chopped into double-emulsion droplets using another pair of moving-wall structures downstream. For single emulsions, oil-in-water droplets can be actively fine-tuned from 50.07 to 21.80 under applied air pressures from 10 to 25 psi with a variation of less than 3.53%. For a water-in-oil single emulsion, droplets range from 50.32 to 14.76 with a variation of less than 4.62% under the same applied air pressures. For double emulsions, the sizes of the external and internal droplets can be fine-tuned with external/internal droplet diameter ratios ranging from 1.69 to 2.75. The development of this microfluidic device is promising for a variety of applications in the pharmaceutical, cosmetics, and food industries.     

Centrifugal generation and manipulation of droplet emulsions

This work for the first time describes a centrifugal technique for the production and manipulation of highly monodisperse water droplets (CV of droplet diameter below 2%) immersed in a continuous flow of immiscible oil. Within a given working range, droplet volumes (5–22 nL) and their mutual spacing is governed by the channel geometry and the frequency of rotation. Different regimes of liquid–liquid flows are presented. We also demonstrate capabilities like droplet splitting and sedimentation as well as the production of two colored droplets, thus setting the stage for a novel centrifugal platform for multiphase flows.     

Dry-spot nucleation in thin liquid films on chemically patterned surfaces

We systematically study the influence of chemical patterning on the instability of thin liquid films induced by chemical heterogeneities on a flat, horizontal, and partially wetting substrate. We consider common geometric shapes like wedges, circles, and stripes and determine the time required for nucleation of a dry-spot as a function of film thickness, contact angle, pattern dimensions, and geometry. Moreover, we characterized the resulting liquid distribution and identified conditions that avoid the formation of residual droplets on the less wettable regions, which is usually undesirable in technological applications.     

A simple method for the formation of water-in-oil-in-water (W/O/W) double emulsions

A simple, low-cost and reliable method for the formation of double emulsions is proposed and demonstrated experimentally. The formation process consists of two steps: (1) the formation of water-in-oil droplets at a co-flowing structure formed by a syringe needle and a flexible microtubing, and (2) the formation of water-in-oil-in-water compound droplets at the tip of the microtubing by buoyancy. Since the droplets flow directly from the first step to the second step in the tubing without any disturbance, problems such as droplet coalescence, breakup, leakage and contamination can be avoided automatically. The breakup processes of the core droplets and the compound droplets are analyzed. The sizes of the core and the shell droplets and the volume fraction in the compound droplets are controlled by adjusting the corresponding flow rates. Scaling relationships for the number of cores and the size of the compound droplets are proposed. Due to the simplicity of this method and the flexibility in controlling the properties of the double emulsions, this method shows great potential in the relevant applications .     

土壤改良剂-乳化沥青的实验室制备方法的改进

乳化沥青制备的基本步骤可分为熔料、皂化、乳化三步 ,其中尤以皂化和乳化为重要。通过分别测定液体油品和液体油品 -沥青混合物酸值的方法 ,测定了沥青和液体油品的酸值 ,准确计算了皂化过程的加碱量。在乳化阶段 ,将混合物中加入乳化剂的同时 ,在未搅动条件下 ,分阶段在混合物中加入少量的水 ,通过观察混合物在水中的溶解性 ,确定了适宜的乳化剂 -脂肪醇聚氧乙烯醚 [RO(CH2 O) 3 5H ) ,R =C12 -18脂肪醇 ,以下简称平平加 ]的用量。在此基础上 ,我们以沥青、豆油为主要原料 ,制成了乳化沥青