Investigation of concentrically and eccentrically layered droplets by light scattering

Two pairs of immiscible liquid compounds are chosen to prepare levitated layered droplets with and without density difference between core and layer phases. The droplets are examined by light scattering along two orthogonal directions. A layered droplet without phase density difference is unambiguously identified as a concentric sphere by matching the observed scattering spectra with those calculated from the Aden-Kerker extension of Mie theory. For layered droplets with phase density difference, only the scattering spectrum from one of the scattering directions can be matched theoretically. These observations suggest that a static layered droplet is predominantly eccentric even though the embedded core is large by volume, as predicted from fluid mechanics. The consistency of the light-scattering characterization with the diffusion theory governing the evaporation of concentrically and eccentrically layered droplets is also established.     

Fiber-optic fluorescence correlation spectrometer

Fluorescence correlation spectroscopy (FCS) is a sensitive technique used to probe size, concentration, flow velocity, and reaction kinetics in a dilute solution. Conventional FCS spectrometers achieve this sensitivity at the cost of using bulky optics. We demonstrate a technique that utilizes a single-mode optical fiber of 3.3 microm mode field diameter to perform FCS measurements. We demonstrate that the technique has adequate sensitivity to perform FCS measurements on fluorescent beads of 13 nm radius, and that the results agree with theoretical predictions. Our method potentially allows FCS to be extended to remote and in vivo applications.     

Spatial mapping of droplet velocity and size for direct and indirect nebulization in plasma spectrometry

Two novel laser-based imaging techniques centered on particle image velocimetry and optical patternation are used to map and contrast the size and velocity distributions for indirect and direct pneumatic nebulizations in plasma spectrometry. The flow field of droplets is illuminated by two pulses from a thin laser sheet with a known time difference. The scattering of the laser light from droplets is captured by a charge-coupled device (CCD), providing two instantaneous images of the particles. Pointwise cross-correlation of the corresponding images yields a two-dimensional velocity map of the aerosol velocity field. For droplet size distribution studies, the solution is doped with a fluorescent dye and both laser-induced florescence (LIF) and Mie scattering images are captured simultaneously by two CCDs with the same field of view. The ratio of the LIF/Mie images provides relative droplet size information, which is then scaled by a point calibration method via a phase Doppler particle analyzer. Two major findings are realized for three nebulization systems: (1) a direct injection high-efficiency nebulizer (DIHEN); (2) a large-bore DIHEN; and (3) a PFA microflow nebulizer with a PFA Scott-type spray chamber. First, the central region of the aerosol cone from the direct injection nebulizers and the nebulizer-spray chamber arrangement consists of fast (>13 and >8 m/s, respectively) and fine (<10 and <5 microm, respectively) droplets as compared to slow (<4 m/s) and large (>25 microm) droplets in the fringes. Second, the spray chamber acts as a momentum separator, rather than a droplet size selector, as it removes droplets having larger sizes or velocities. The concepts and results presented in this research may be used to develop smart-tunable nebulizers, for example, by using the measured momentum as a feedback control for adjusting the nebulizer, i.e., its operating conditions, its critical dimensions, or both.     

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.     

Light scattering from deformed droplets and droplets with inclusions. I. Experimental results

We provide experimental results from the scattering of light by deformed liquid droplets and droplets with inclusions. The characterization of droplet deformation could lead to improved measurement of droplet size as measured by commercial aerodynamic particle-sizing instruments. The characterization of droplets with inclusions can be of importance in some industrial, occupational, and military aerosol monitoring situations. The nozzle assembly from a TSI Aerodynamic Particle Sizer was used to provide the accelerating flow conditions in which experimental data were recorded. A helium-neon laser was employed to generate the light-scattering data, and an externally triggered, pulsed copper vapor laser provided illumination for a droplet imaging system arranged orthogonal to the He-Ne scattering axis. The observed droplet deformation correlates well over a limited acceleration range with theoretical predictions derived from an analytical solution of the Navier-Stokes equation.     

Simulating glories and cloudbows in color

Glories and cloudbows are simulated in color by use of the Mie scattering theory of light upwelling from small-droplet clouds of finite optical thickness embedded in a Rayleigh scattering atmosphere. Glories are generally more distinct for clouds of droplets of as much as approximately 10 microm in radius. As droplet radius increases, the glory shrinks and becomes less prominent, whereas the cloudbow becomes more distinct and eventually colorful. Cloudbows typically consist of a broad, almost white band with a slightly orange outer edge and a dark inner band. Multiple light and dark bands that are related to supernumerary rainbows first appear inside the cloudbow as droplet radius increases above approximately 10 microm and gradually become more prominent when all droplets are the same size. Bright glories with multiple rings and high color purity are simulated when all droplets are the same size and every light beam is scattered just once. Color purity decreases and outer rings fade as the range of droplet sizes widens and when skylight, reflected light from the ground or background, and multiply scattered light from the cloud are included. Consequently, the brightest and most colorful glories and bows are seen when the observer is near a cloud or a rain swath with optical thickness of approximately 0.25 that consists of uniform-sized drops and when a dark or shaded background lies a short distance behind the cloud.     

Monodisperse, Submicrometer Droplets via Condensation of Microfluidic-Generated Gas Bubbles

Microfluidics (MFs) can produce monodisperse droplets with precise size control. However, the synthesis of monodisperse droplets much smaller than the minimum feature size of the microfluidic device (MFD) remains challenging, thus limiting the production of submicrometer droplets. To overcome the minimum micrometer-scale droplet sizes that can be generated using typical MFDs, the droplet material is heated above its boiling point (bp), and then MFs is used to produce monodisperse micrometer-scale bubbles (MBs) that are easily formed in the size regime where standard MFDs have excellent size control. After MBs are formed, they are cooled, condensing into dramatically smaller droplets that are beyond the size limit achievable using the original MFD, with a size decrease corresponding to the density difference between the gas and liquid phases of the droplet material. Herein, it is shown experimentally that monodisperse, submicrometer droplets of predictable sizes can be condensed from a monodisperse population of MBs as generated by MFs. Using perfluoropentane (PFP) as a representative solvent due to its low bp (29.2 °C), it is demonstrated that monodisperse PFP MBs can be produced at MFD temperatures >3.6 °C above the bp of PFP over a wide range of sizes (i.e., diameters from 2 to 200 μm). Independent of initial size, the generated MBs shrink rapidly in size from about 3 to 0 °C above the bp of PFP, corresponding to a phase change from gas to liquid, after which they shrink more slowly to form fully condensed droplets with diameters 5.0 ± 0.1 times smaller than the initial size of the MBs, even in the submicrometer size regime. This new method is versatile and flexible, and may be applied to any type of low-bp solvent for the manufacture of different submicrometer droplets for which precisely controlled dimensions are required.     

Analysis of time-dependent scattering spectra for studying processes associated with microdroplets

Techniques are presented for analysis of time-dependent scattering spectra from single droplets undergoing physical changes. Times of appearance of resonances in experimental spectra are aligned with theoretical resonances, and the size and refractive index of a droplet as functions of time are determined from the minimum errors in alignment between observed and theoretical resonances. The techniques have been applied to time-dependent elastic scattering spectra obtained from single droplets evaporating under quasi-steady conditions and during unsteady growth. The results of quasi-steady evaporation data show that size and refractive index can be determined with relative errors of 1 x 10(-4). The quasi-steady evaporation data of a droplet are used to identify the resonances observed during the unsteady growth of the same droplet, and the size and refractive index at each resonance are calculated from the identity of the resonance.     

Sizing subcellular organelles and nanoparticles confined within aqueous droplets

This article describes two complementary techniques, single-particle tracking and correlation spectroscopy, for accurately sizing nanoparticles confined within picoliter volume aqueous droplets. Single-particle tracking works well with bright particles that can be continuously illuminated and imaged, and we demonstrated this approach for sizing single fluorescent beads. Fluorescence correlation spectroscopy detects small intensity bursts from particles or molecules diffusing through the confocal probe volume, which works well with dim and rapidly diffusing particles or molecules; we demonstrated FCS for sizing synaptic vesicles confined in aqueous droplets. In combination with recent advances in droplet manipulations and analysis, we anticipate this capability to size single nanoparticles and molecules in free solution will complement existing tools for probing cellular systems, subcellular organelles, and nanoparticles.     

The Control on Size and Density of InAs QDs by Droplet Epitaxy (April 2009)

We report on the ability to grow InAs quantum dots (QDs) by droplet epitaxy (DE) using solid-source molecular beam epitaxy (MBE). In particular, the control of the size and density of InAs QDs at near room temperatures are achieved as a function of substrate temperature and crystallization condition. For a typical range of QD density ( ~10⁹ to 10¹⁰ cm^-2), the growth window is revealed to be fairly narrow ( ~20degC). In droplets are extremely sensitive to surface diffusion and arsenic background pressure even at near room temperatures. As a result, a very careful fabrication procedure is required to crystallize In droplets in order to fabricate desired shape of InAs QDs. For this purpose, we developed a double-step crystallization process, in which As background recovery and high-temperature crystallization are introduced. In addition, the results by DE are compared with QDs fabricated by Stranski-Krastanow (S-K) growth approach in terms of size and density. The results can find applications in optoelectronics as the fabrication of QDs by DE approach has more flexibility over S-K approach, i.e., more freedom of size and density control.     

Influence of Two Salicylate Components on the Particle Size of an Oil-in-Water Emulsion with Nonionic Surfactants

This paper reports a study undertaken using techniques of static and dynamic light scattering to investigate the influence of sodium salicylate and methyl salicylate on droplet size of oil-in-water emulsions. The rates of changes were measured by determining the size and distribution of the oil droplet in the material. All emulsions showed a bimodal size distribution; the mean diameters and polydispersity were calculated from intensity. These data were analyzed with nonlinear regressions and bootstrap methodology. An amount of methyl salicylate component induced a decrease of mean diameter and standard deviation. On the contrary, sodium salicylate entailed the growth of all droplet populations and coalescence for the highest concentration.     

Light Scattering from Deformed Droplets and Droplets with Inclusions. II. Theoretical Treatment

We provide theoretical results from the scattering of light by deformed liquid droplets and droplets with inclusions. With improved instrumentation and computer technologies available, researchers are able to employ two-dimensional angular optical scattering as a tool for analyzing such particle systems and which then could be applied in industrial, occupational, and military aerosol measurement. We present numerically calculated spatial light-scattering data from various droplet morphologies. We describe characteristic features of the theoretical data and compare these with the experimental results.     

Self-regulated, droplet-based sample chopper for microfluidic absorbance detection

Akin to optical beam chopping, we demonstrate that formation and routing of aqueous droplets in oil can chop a fluidic sample to permit phase sensitive detection. This hand-operated microfluidic sample chopper (μChopper) greatly reduces the detection limit of molecular absorbance in a 27 μm optical path. With direct dependence on path length, absorbance is fundamentally incompatible with microfluidics. While other microfluidic absorbance approaches use complex additions to fabrication, such as fiber coupling and increased optical paths, this self-regulated μChopper uses opposing droplet generators to passively alternate sample and reference droplets at ~10 Hz each. Each droplet's identity is automatically locked-in to its generator, allowing downstream lock-in analysis to nearly eliminate large signal drift or 1/f noise. With a lock-in time constant of 1.9 s and total interrogated volume of 59 nL (122 droplets), a detection limit of 3.0 × 10(-4) absorbance units or 500 nM bromophenol blue (BPB) (29 fmol) was achieved using only an optical microscope and a standard, single-depth (27 μm) microfluidic device. The system was further applied to nanoliter pH sensing and validated with a spectrophotometer. The μChopper represents a fluidic analog to an optical beam chopper, and the self-regulated sample/reference droplet alternation promotes ease of use.     

Nanowires enabling signal-enhanced nanoscale Raman spectroscopy

Silicon nanowires grown by the vapor-liquid-solid (VLS) mechanism catalyzed by gold show gold caps (droplets) approximately 20-500 nm in diameter with a half spherical towards almost spherical shape. These gold droplets are well suited to exploit the surface-enhanced Raman scattering (SERS) effect and could be used for tip-enhanced Raman spectroscopy (TERS). The gold droplet of a nanowire attached to an atomic force microscopy (AFM) tip could locally enhance the Raman signal and increase the spatial resolution. Used as a SERS template, an ensemble of self-organizing nanowires grown bottom up on a silicon substrate could allow highly sensitive signal-enhanced Raman spectroscopy of materials that show a characteristic Raman signature. A combination of a nanowire-based TERS probe and a nanowire-based SERS substrate promises optimized signal enhancement so that the detection of highly dilute species, even single molecules or single bacteria or DNA strands, and other soft matter is within reach. Potential applications of this novel nanowire-based SERS and TERS solution lie in the fields of biomedical and life sciences, as well as security and solid-state research such as silicon technology.     

Determination of the optical properties of two-layer turbid media by use of a frequency-domain hybrid monte carlo diffusion model

The general two-layer inverse problem in biomedical photon migration is to estimate the absorption and scattering coefficients of each layer as well as the top-layer thickness. We attempted to solve this problem, using experimental and simulated spatially resolved frequency-domain (FD) reflectance for optical properties typical of skin overlying muscle or skin overlying fat in the near infrared. Two forward models of light propagation were used: a two-layer diffusion solution [Appl. Opt. 37, 779 (1998)] and a hybrid Monte Carlo (MC) diffusion model [Appl. Opt. 37, 7401 (1998)]. MC-simulated FD reflectance data were fitted as relative measurements to the hybrid and the pure diffusion models. It was found that the hybrid model could determine all the optical properties of the two-layer media studied to ~5%. Also, the same accuracy could be achieved by means of fitting MC-simulated cw reflectance data as absolute measurements, but fitting them as relative ones is an ill-posed problem. In contrast, two-layer diffusion could not retrieve the top-layer optical properties as accurately for FD data and was ill-posed for both relative and absolute cw data. The hybrid and the pure diffusion models were also fitted to experimental FD reflectance measurements from two-layer tissue-simulating phantoms representative of skin-on-fat and skin-on-muscle baseline optical properties. Both the hybrid and the diffusion models could determine the optical properties of the lower layer. The hybrid model demonstrated its potential to retrieve quantitatively the transport scattering coefficient of skin (the upper layer), which was not possible with the pure diffusion model. Systematic discrepancies between model and experiment may compromise the accuracy of the deduced top-layer optical properties. Identifying and eliminating such discrepancies is critical to practical application of the method.     

Confined diffusion in tubular structures analyzed by fluorescence correlation spectroscopy on a mirror

In fluorescence correlation spectroscopy (FCS) analysis it is generally assumed that molecular species diffuse freely in volumes much larger than the three-dimensional FCS observation volume. However, this standard assumption is not valid in many measurement conditions, particularly in tubular structures with diameters in the micrometer range, such as those found in living cells (organelles, dendrites) and microfluidic devices (capillaries, reaction chambers). As a result the measured autocorrelation functions (ACFs) deviate from those predicted for free diffusion, and this can shift the measured diffusion coefficient by as much as ~50% when the tube diameter is comparable with the axial extension of the FCS observation volume. We show that the range of validity of the FCS measurements can be drastically improved if the tubular structures are located in the close vicinity of a mirror on which FCS is performed. In this case a new fluctuation time in the ACF, arising from the diffusion of fluorescent probes in optical fringes, permits measurement of the real diffusion coefficient within the tubular structure without assumptions about either the confined geometry or the FCS observation volume geometry. We show that such a measurement can be done when the tubular structure contains at least one pair of dark and bright fringes resulting from interference between the incoming and the reflected excitation beams on the mirror surface. Measurement of the diffusion coefficient of the enhanced green fluorescent protein (EGFP) and IscS-EGFP in the cytoplasm of living Escherichia coli illustrates the capabilities of the technique.     

Aerosol Synthesis of Inhalation Particles via a Droplet-to-Particle Method

Inhalation powders with consistent particle properties, including particle size, size distribution, and shape were produced with an aerosol synthesis method. Compared to conventional spray drying, the aerosol method provides better control of the thermal history and residence time of each droplet and product particle due to the laminar flow in the heated zone of the reactor where the droplet drying and particle formation take place. A corticosteroid, beclomethasone dipropionate, generally used for asthma treatment was chosen as a representative material to demonstrate the process. Spherical particles were produced with a droplet-to-particle method from an ethanolic precursor solution. The droplets produced with an ultrasonic nebulizer were carried to a heated zone of the reactor at 50-150°C where the solvent was evaporated and dry particles formed. The mass mean diameter of the particles were well within the respirable size range (approximately 2 μm). The geometric standard deviation (GSD) of produced particles was approximately 2. The particle surface structure varied from smooth to rough depending on the degree of particle crystallinity and was affected by the thermal history of the particle. Amorphous particles with smooth surface were most likely obtained due to the rapid evaporation of the solvent from the droplet combined with the slow diffusion of the beclomethasone dipropionate molecule. The amorphous particles were transformed slowly to crystalline particles in the open atmosphere. In addition, the particle surface structure changed from smooth to rough during storage. The process was accelerated by thermal post-annealing. However, additional heating also increased particle sintering. By optimizing the reactor parameters, and thus increasing the molecular diffusion, stable, crystalline particles were produced at 150°C.     

Small angle neutron scattering and photoluminescence property of wet chemistry process synthesised ZnO nanoparticles

We report the synthesis of zinc oxide (ZnO) nanoparticles from aqueous solution at 25°C and subsequent heating of the solution at 115°C by the suitable selection of the solution chemistry and the control of the alkaline conditions. The structure of the synthesised ZnO particles was studied by X-ray diffraction (XRD), confirming the formation of Wurtzite structure. The optical property of synthesised ZnO nanoparticles is investigated through room temperature photoluminescence (PL) measurement. The PL of ZnO nanoparticles shows a strong UV emission band at approximately 385 nm, a blue–green band at approximately 473 nm and a very weak green band at approximately 554 nm, although polydispersity of the sample shows no presence on the PL spectrum. Small angle neutron scattering is used to determine the size and the size distribution of ZnO nanoparticles. The SANS data analysis and model fitting predict the size as about 18–20 nm, which is closely matched with XRD and transmission electron microscopy results with Gaussian distribution.     

Influence of Two Salicylate Components on the Particle Size of an Oil-in-Water Emulsion with Nonionic Surfactants

Abstract

This paper reports a study undertaken using techniques of static and dynamic light scattering to investigate the influence of sodium salicylate and methyl salicylate on droplet size of oil-in-water emulsions. The rates of changes were measured by determining the size and distribution of the oil droplet in the material. All emulsions showed a bimodal size distribution; the mean diameters and polydispersity were calculated from intensity. These data were analyzed with nonlinear regressions and bootstrap methodology. An amount of methyl salicylate component induced a decrease of mean diameter and standard deviation. On the contrary, sodium salicylate entailed the growth of all droplet populations and coalescence for the highest concentration.     

Study on ice slurry production by water spray

A theoretical and experimental study was performed to examine the water spray method of ice slurry production. First, the conditions for the formation of ice particles were investigated theoretically by the diffusion-controlled evaporation model. The prediction of the model was proved to agree relatively well with experiments in which we examined the conditions for a droplet of initial temperature 20°C and size 50 μm to change into an ice particle in a chamber of height 1.33 m. Second, the production of cold storage heat will increase almost proportionally to the number of spray nozzles because no substantial difference was found in the Sauter Mean Diameter (SMD) of sprays from single and twin nozzle. Third, an ice slurry was experimentally obtained by spraying droplets of 7% ethylene glycol aqueous solution in a vacuum chamber where pressure is maintained below the freezing point of the solution. Finally, based on the theoretical and experimental results, we propose an optimizing chart for providing the operating conditions to make ice slurry using the relations of the staying time of the droplet in the chamber, the injection pressure, the spray droplet size and the chamber pressure.