Microfluidic and optical systems for the on-demand generation and manipulation of single femtoliter-volume aqueous droplets

This paper describes a fluidic and optical platform for the generation and manipulation of single femtoliter-volume aqueous droplets. Individual droplets were generated on-demand using a microfluidic chamber that confers environmental flow stability. Optical vortex traps were implemented to manipulate and transport the generated droplets, which have a lower refractive index than the immiscible medium in which the droplets are immersed and thus cannot be trapped using conventional optical tweezers. We also demonstrated the ability to shrink and increase the refractive index of the generated droplet, thereby permitting its facile fusion with another droplet using an optical tweezer. To illustrate the versatility of this platform, we have performed both fast (<1 s) and slow (>1 h) chemical reactions in these femtoliter-volume aqueous droplets.     

MONODISPERSE DROPLET GENERATION BY SPONTANEOUS CONDENSATION OF STEAM FLOW IN NOZZLES

Spontaneous Condensation (also called homogeneous Condensation)of steam flow in one dimensional nozzle has been numerically modeled. The classical (Frenkel and Volmer) and Deich's nucleation theories were used. Unlike the classical theory, Deich's theory also accounts for the critical droplet size dependence upon the expansion rate in the nozzle. Pressure ratio, mean droplet size and droplet size distributions were obtained along the axial length for various nozzles. Comparisons with experimental data were made. The agreement between the numerical results and the experimental data was good. Both theories predicted the pressure ratio properly but the classical theory tended to underestimate the droplet sizes. Deich's theory is preferred for analyzing and designing new nozzles. The classical theory cannot be used for obtaining a correlation for surface tension ratio, thereby limiting its usage for new nozzles. Effects of Inlet conditions and nozzle expansion rates on mean droplet size and droplet size distributions were examined. The spontaneous condensation process results in relatively monodisperse droplets. The numerical model and the results are discussed in this paper.     

MONODISPERSE DROPLET GENERATION BY SPONTANEOUS CONDENSATION OF STEAM FLOW IN NOZZLES

ABSTRACT

Spontaneous Condensation (also called homogeneous Condensation)of steam flow in one dimensional nozzle has been numerically modeled. The classical (Frenkel and Volmer) and Deich's nucleation theories were used. Unlike the classical theory, Deich's theory also accounts for the critical droplet size dependence upon the expansion rate in the nozzle. Pressure ratio, mean droplet size and droplet size distributions were obtained along the axial length for various nozzles. Comparisons with experimental data were made. The agreement between the numerical results and the experimental data was good. Both theories predicted the pressure ratio properly but the classical theory tended to underestimate the droplet sizes. Deich's theory is preferred for analyzing and designing new nozzles. The classical theory cannot be used for obtaining a correlation for surface tension ratio, thereby limiting its usage for new nozzles. Effects of Inlet conditions and nozzle expansion rates on mean droplet size and droplet size distributions were examined. The spontaneous condensation process results in relatively monodisperse droplets. The numerical model and the results are discussed in this paper.     

A new measuring method to detect the emissions of metal working fluid mist

During metal machining the rotating machine tool or grinding wheel is generating fine droplets and vapor which can cause occupational health problems. A new continuous measuring method was developed to detect both droplets and vapor of metalworking fluid mist and to provide information about the droplet size distribution. According to this method, an air sample of the metalworking fluid mist is segregated by impactors of different cut sizes, carried out in several successive passes. In each pass the droplets that are not collected in the impactor are fed into an evaporator that immediately evaporates all droplets, and subsequently the sample is analyzed in-line by a Flame Ionization Detector (FID). By subtraction of the value measured at the respectively next smaller fraction, the oil amount of the metalworking fluid mist found in a certain droplet size range is obtained. The metalworking fluid mist is thus segregated according to the droplet size, and a definite cut size between droplet and vapor can be defined, below which we can say "vapor". This method was calibrated with Di-2-Ethylhexyl-Sebacat (DEHS) as equivalence substance for further measurements applied on various metalworking fluids.     

Effect of droplet size distribution on spray drying kinetics

A comparison is made between the processes of adiabatic evaporation of a polydisperse system of droplets and a monodisperse system with droplets equal in size to the largest droplet of the polydisperse system. The process takes place in air with the same initial and final parameters in both cases.     

Interferometric laser imaging for droplet sizing: a method for droplet-size measurement in sparse spray systems

A full-field, time-resolved interferometric method for the characterization of sparse, polydisperse spray systems is reported. The method makes use of the angular intensity oscillations in the wide-angle forward-scatter region. A pulsed laser is used to illuminate a planar sheet through the spray, which is imaged, out of focus, from the 45°direction. The image consists of a set of out-of-focus spots, each of which represents an individual droplet, and superimposed on which is a set of fringes corresponding to the angular intensity oscillations of that droplet. Macrophotographic recording with high-resolution digitization for image analysis provides a full-field capability. The spatial frequency of fringes on each spot in the image plane is dependent on the diameter of the corresponding droplet in the object plane, and a simple geometric analysis is shown to be appropriate for the calculation of the spatial frequency of fringes as a function of droplet size. Images are analyzed automatically by a software suite that uses Gaussian blur, Canny edge detection, and Hough transforms to locate individual droplets in the image field. Fringe spatial frequency is then determined by least-squares fitting to a Chirp function. The method is applicable to droplets with diameters in the range of several millimeters to several hundred millimeters and number densities of up to 10(3) to 10(4). The accuracy of the method for droplet-size determination has been evaluated by measurements of monodisperse aerosols of known droplet size, and measurements of droplet-size distribution in a polydisperse aerosol produced by a gasoline fuel injector are also presented. An extension of the method, using high-speed photography to measure two components of velocity in addition to size and position, is discussed. A two-wavelength approach may also offer the capability to measure the concentration of model fuel additives in droplets, and the results of a feasibility study are described.     

Rapid generation of protein aerosols and nanoparticles via surface acoustic wave atomization

We describe the fabrication of a surface acoustic wave (SAW) atomizer and show its ability to generate monodisperse aerosols and particles for drug delivery applications. In particular, we demonstrate the generation of insulin liquid aerosols for pulmonary delivery and solid protein nanoparticles for transdermal and gastrointestinal delivery routes using 20?MHz SAW devices. Insulin droplets around 3?μm were obtained, matching the optimum range for maximizing absorption in the alveolar region. A new approach is provided to explain these atomized droplet diameters by returning to fundamental physical analysis and considering viscous-capillary and inertial-capillary force balance rather than employing modifications to the Kelvin equation under the assumption of parametric forcing that has been extended to these frequencies in past investigations. In addition, we consider possible mechanisms by which the droplet ejections take place with the aid of high-speed flow visualization. Finally, we show that nanoscale protein particles (50-100?nm in diameter) were obtained through an evaporative process of the initial aerosol, the final size of which could be controlled merely by modifying the initial protein concentration. These results illustrate the feasibility of using SAW as a novel method for rapidly producing particles and droplets with a controlled and narrow size distribution.     

On-chip, real-time, single-copy polymerase chain reaction in picoliter droplets

The first lab-on-chip system for picoliter droplet generation and PCR amplification with real-time fluorescence detection has performed PCR in isolated droplets at volumes 106 smaller than commercial real-time PCR instruments. The system utilized a shearing T-junction in a silicon device to generate a stream of monodisperse picoliter droplets that were isolated from the microfluidic channel walls and each other by the oil-phase carrier. An off-chip valving system stopped the droplets on-chip, allowing them to be thermally cycled through the PCR protocol without droplet motion. With this system, a 10-pL droplet, encapsulating less than one copy of viral genomic DNA through Poisson statistics, showed real-time PCR amplification curves with a cycle threshold of approximately 18, 20 cycles earlier than commercial instruments. This combination of the established real-time PCR assay with digital microfluidics is ideal for isolating single-copy nucleic acids in a complex environment.     

Method to reduce errors of droplet sizing based on the ratio of fluorescent and scattered light intensities (laser-induced fluorescence/Mie technique)

The droplet sizing accuracy of the laser technique, based on the ratio of laser-induced fluorescence (LIF) and scattered light (Mie) intensities from droplets, is examined. We develop an analytical model of the ratio of fluorescent to scattered light intensities of droplets, which shows that the LIF/Mie technique is susceptible to sizing errors that depend on the mean droplet size and the spread of the droplet size distribution. The sizing uncertainty due to the oscillations of the scattered light intensity as a function of droplet size is first quantified. Then, a new data processing method is proposed that can improve the sizing uncertainty of the technique for the sprays that were examined in this study by more than 5% by accounting for the size spread of the measured droplets, while improvements of 25% are possible when accounting for the mean droplet size. The sizing accuracy of the technique is evaluated in terms of the refractive index of liquid, scattering angle, and dye concentration in the liquid. It is found that the proposed approach leads to sizing uncertainty of less than 14% when combined with light collection at forward scattering angles close to 60° and the lowest fluorescent dye concentration in the liquid for all refractive indices.     

Particle Formation in the Emulsion‐Solvent Evaporation Process

The mechanism of particle formation from submicrometer emulsion droplets by solvent evaporation is revisited. A combination of dynamic light scattering, fluorescence resonance energy transfer, zeta potential measurements, and fluorescence cross‐correlation spectroscopy is used to analyze the colloids during the evaporation process. It is shown that a combination of different methods yields reliable and quantitative data for describing the fate of the droplets during the process. The results indicate that coalescence plays a minor role during the process; the relatively large size distribution of the obtained polymer colloids can be explained by the droplet distribution after their formation.     

Review on modelling of corrosion under droplet electrolyte for predicting atmospheric corrosion rate

Atmospheric corrosion of metals is the most common type of corrosion which has a significant impact on the environment and operational safety in various situations of everyday life.Some of the common examples can be observed in land,water and air transportation systems,electronic circuit boards,urban and offshore infrastructures.The dew drops formed on metal surface due to condensation of atmospheric moisture facilitates corrosion as an electrolyte.The corrosion mechanisms under these droplets are different from classically known bulk electrolyte corrosion.Due to thin and non-uniform geometric thickness of the droplet electrolyte,the atmospheric oxygen requires a shorter diffusion path to reach the metal surface.The corrosion under a droplet is driven by the depletion of oxygen in the center of the droplet compared to the edge,known as differential aeration.In case of a larger droplet,differential aeration leads to preferential cathodic activity at the edge and is controlled by the droplet geometry.Whereas,for a smaller droplet,the oxygen concentration remains uniform and hence cathodic activity is not controlled by droplet geometry.The geometry of condensed droplets varies dynamically with changing environmental parameters,influencing corrosion mechanisms as the droplets evolve in size.In this review,various modelling approaches used to simulate the corrosion under droplet electrolytes are presented.In the efforts of developing a comprehensive model to estimate corrosion rates,it has been noted from this review that the influence of geometric evolution of the droplet due to condensation/evaporation processes on corrosion mechanisms are yet to be modelled.Dynamically varying external factors like environmental temperature,relative humidity,presence of hygroscopic salts and pollutants influence the evolution of droplet electrolyte,making it a complex phenomenon to investigate.Therefore,an overview of available dropwise condensation and evaporation models which describes the formation and the evolution of droplet geometry are also presented from an atmo s pheric corrosion viewpoint.     

Evaporation and discharge dynamics of highly charged droplets of heptane,octane, and p-xylene generated by electrospray ionization

We report studies of the evaporation and discharge dynamics of highly charged droplets generated by electrospray ionization from n-heptane, n-octane, and p-xylene doped with Stadis-450, a conductivity-enhancing agent. A phase Doppler anemometer (PDA) characterizes individual droplets moving through the uniform electric field within an ion mobility cell according to size, velocity, and charge. Repeated reversal of the electric field allows multiple PDA measurements on selected droplets with diameters ranging from 3 to 60 microm and up to 10(7) elementary positive charges. This "ping-pong" technique provides individual droplet histories from which we determine the dynamics of solvent evaporation and charge loss. On average, n-heptane discharges at 101% of the Rayleigh limit of charge, while n-octane and p-xylene droplets discharge at 87% and 89% of their respective limits. Discharge events release an average of 19% of the charge in n-heptane and 17% of the charge in both n-octane and p-xylene. Within the limits of the measurements, no detectable change in droplet diameter accompanies observed discharge events, indicating the loss of a relatively small fraction of the total volume. We compare these results to previous experiments, theoretical models for droplet evaporation and discharge, and predictions from the Rayleigh model. We report both Stadis-450 and triethylamine mass spectra in octane and discuss issues regarding the use of hydrocarbon solvents in electrospray mass spectrometry.     

Microstructure Evolution of Cu-Pb Monotectic Alloys Processed in Drop Tube

Rapid solidification of Cu-Pb monotectic alloys has been accomplished during free fall in a 3m drop tube.Both macrosegregated and uniformly dispersed structures are observed in Cu-40wt pct Pb alloy droplets,whereas droplets of composition Cu-64wt pct Pb exhibit only macrosegregation morphologies.The microstructures are strongly dependent on droplet size.The higher undercooling tends to facilitate liquid phase separation and results in more extensive macrosegregation in smaller droplets.There exists a pronounced tendency for the Pb-rich liquid to occupy the surface of the droplets of both compositions,resulting from the quite lower surface tension of the Pb-rich phase and cauing a Pb-rich layer at the surface of the solidified droplet.The nucleation of monotectic cells in the Cu-40 wt pct Pb droplets with dispersed structures preferentially occurs at the droplet surface.A single nucleation event takes place more frequently as droplet size is reduced.     

Co-flowing of partially miscible liquids for the generation of monodisperse microparticles

Liquid templating is a well-established method for the fabrication of monodisperse microparticles. Nearly all liquid templating methods use totally immiscible liquids for the generation of monodisperse liquid droplets. With this approach, it is difficult to mass produce monodisperse droplets in the submicron range. The approach also suffers from some common difficulties associated with the use of small openings or channels required for the generation of small sized droplets including high back pressures and frequent blockage of the flow channels. Aimed at overcoming these difficulties, this paper presents a new co-flowing method that uses partially miscible liquids for the generation of a monodisperse liquid template. The results show that addition of a co-solvent in the inner phase that makes the liquid systems partially miscible changes the bulk and interfacial properties of the liquids that facilitate the generation of smaller droplets. They also confirm that the co-solvent concentration in the inner phase can be used as an additional tool to manipulate the mean size of the resultant droplets and solid particles.     

On‐Chip Production of Size‐Controllable Liquid Metal Microdroplets Using Acoustic Waves

Micro‐ to nanosized droplets of liquid metals, such as eutectic gallium indium (EGaIn) and Galinstan, have been used for developing a variety of applications in flexible electronics, sensors, catalysts, and drug delivery systems. Currently used methods for producing micro‐ to nanosized droplets of such liquid metals possess one or several drawbacks, including the lack in ability to control the size of the produced droplets, mass produce droplets, produce smaller droplet sizes, and miniaturize the system. Here, a novel method is introduced using acoustic wave‐induced forces for on‐chip production of EGaIn liquid‐metal microdroplets with controllable size. The size distribution of liquid metal microdroplets is tuned by controlling the interfacial tension of the metal using either electrochemistry or electrocapillarity in the acoustic field. The developed platform is then used for heavy metal ion detection utilizing the produced liquid metal microdroplets as the working electrode. It is also demonstrated that a significant enhancement of the sensing performance is achieved by introducing acoustic streaming during the electrochemical experiments. The demonstrated technique can be used for developing liquid‐metal‐based systems for a wide range of applications.     

操作参数对双蜗壳式旋流分离器气液分离性能的影响

为了研究操作参数对双蜗壳式旋风分离器分离性能的影响,本文采用试验方法测量了液滴粒径、液滴浓度不同时旋风管的分离效率。结果表明：旋风管对小粒径液滴的分离效率较低,当入口液滴的中位粒径从19．02μm升高到37．28μm,旋风管的分离效率升高了接近20％。喷雾液滴的浓度升高时,旋风管的分离效率也随之升高,但影响程度较粒度较小。     

Characterization and verification of astigmatic interferometric particle imaging for volumetric droplet 3D position and size measurement

Sprays generated by atomization processes have been used in a wide range of fields. The size and spatial distribution of volumetric droplets in a spray are critical parameters in industrial applications. Astigmatic interferometric particle imaging (AIPI), an extension of the traditional interferometric particle imaging (IPI), is developed to simultaneously measure the size and 3D position of volumetric droplets in a sparse spray. Based on the generalized Huygens–Fresnel integral and the transfer matrix, the size and depth position of droplet can be respectively extracted from the fringe spacing and orientation of interferogram in AIPI. An AIPI setup is established to characterize droplets in a sparse spray generated by a nozzle with the AIPI calibration procedure adopted. The measured parameters by AIPI are compared with those obtained synchronously by digital inline holography, which is regarded as a standard measurement technique. Results show that the average deviation values of droplet size and depth position are respectively 3.8% and 6.8%. AIPI has been demonstrated with high accuracy in simultaneous 3D positions and size measurements.     

Mechanism of stabilization of location of a droplet cluster above the liquid-gas interface

We studied the influence of sizes of droplets, forming the ??droplet cluster?? dissipative structure, on their levitation height in the vapor-air flow, which appears when free surface of horizontal water layer is locally heated. A sharp decrease in the velocity of the vapor-air flow takes place at a distance from the surface comparable with the droplet diameter. Allowing for the aerodynamic nature of the droplet levitation, this peculiarity of the flow determines the high stability of location of the droplet cluster above the interface. Existence of droplets that are anomalously heavy in the slope of the Stokes levitation mechanism is described.     

High-throughput single copy DNA amplification and cell analysis in engineered nanoliter droplets

A high-throughput single copy genetic amplification (SCGA) process is developed that utilizes a microfabricated droplet generator (microDG) to rapidly encapsulate individual DNA molecules or cells together with primer functionalized microbeads in uniform PCR mix droplets. The nanoliter volume droplets uniquely enable quantitative high-yield amplification of DNA targets suitable for long-range sequencing and genetic analysis. A hybrid glass-polydimethylsiloxane (PDMS) microdevice assembly is used to integrate a micropump into the microDG that provides uniform droplet size, controlled generation frequency, and effective bead incorporation. After bulk PCR amplification, the droplets are lysed and the beads are recovered and rapidly analyzed via flow cytometry. DNA targets ranging in size from 380 to 1139 bp at single molecule concentrations are quantitatively amplified using SCGA. Long-range sequencing results from beads each carrying approximately 100 amol of a 624 bp product demonstrate that these amplicons are competent for achieving attomole-scale Sanger sequencing from a single bead and for advancing pyrosequencing read-lengths. Successful single cell analysis of the glyceraldehyde 3 phosphate dehydrogenase (GAPDH) gene in human lymphocyte cells and of the gyr B gene in bacterial Escherichia coli K12 cells establishes that SCGA will also be valuable for performing high-throughput genetic analysis on single cells.     

Chemical transfection of cells in picoliter aqueous droplets in fluorocarbon oil

The manipulation of cells inside water-in-oil droplets is essential for high-throughput screening of cell-based assays using droplet microfluidics. Cell transfection inside droplets is a critical step involved in functional genomics studies that examine in situ functions of genes using the droplet platform. Conventional water-in-hydrocarbon oil droplets are not compatible with chemical transfection due to its damage to cell viability and extraction of organic transfection reagents from the aqueous phase. In this work, we studied chemical transfection of cells encapsulated in picoliter droplets in fluorocarbon oil. The use of fluorocarbon oil permitted high cell viability and little loss of the transfection reagent into the oil phase. We varied the incubation time inside droplets, the DNA concentration, and the droplet size. After optimization, we were able to achieve similar transfection efficiency in droplets to that in the bulk solution. Interestingly, the transfection efficiency increased with smaller droplets, suggesting effects from either the microscale confinement or the surface-to-volume ratio.