Growth and motion of heterogeneous water droplets in laminar diffusion chambers: 2. High nanoparticle concentrations

The heterogeneous condensation of water vapor on nanoparticles and the growth of formed droplets are numerically studied under conditions of laminar diffusion chamber (LDC) of a new type with a hot porous wall. The main attention is focused on the growth of heterogeneous droplets in the gas flow at high number densities of nanoparticles exceeding 10⁸ droplet/m³. Under these conditions, there is an interrelation between the growth of droplets and processes of heat and mass transfer in LDC due to vapor depletion and the release of latent heat of phase transition on growing droplets. The efficiency of the coverage of nanoparticles with water film is studied under LDC nonuniform conditions. It is shown that, at initial number densities of nanoparticles (N _d > 10¹¹ droplet/m³), heterogeneous droplets do not grow to optically detected sizes.     

Reactions of Microsolvated Organic Compounds at Ambient Surfaces: Droplet Velocity,Charge State,and Solvent Effects

The exposure of charged microdroplets containing organic ions to solid-phase reagents at ambient surfaces results in heterogeneous ion/surface reactions. The electrosprayed droplets were driven pneumatically in ambient air and then electrically directed onto a surface coated with reagent. Using this reactive soft landing approach, acid-catalyzed Girard condensation was achieved at an ambient surface by directing droplets containing Girard T ions onto a dry keto-steroid. The charged droplet/surface reaction was much more efficient than the corresponding bulk solution-phase reaction performed on the same scale. The increase in product yield is ascribed to solvent evaporation, which causes moderate pH values in the starting droplet to reach extreme values and increases reagent concentrations. Comparisons are made with an experiment in which the droplets were pneumatically accelerated onto the ambient surface (reactive desorption electrospray ionization, DESI). The same reaction products were observed but differences in spatial distribution were seen associated with the “splash” of the high velocity DESI droplets. In a third type of experiment, the reactions of charged droplets with vapor phase reagents were examined by allowing electrosprayed droplets containing a reagent to intercept the headspace vapor of an analyte. Deposition onto a collector surface and mass analysis showed that samples in the vapor phase were captured by the electrospray droplets, and that instantaneous derivatization of the captured sample is possible in the open air. The systems examined under this condition included the derivatization of cortisone vapor with Girard T and that of 4-phenylpyridine N-oxide and 2-phenylacetophenone vapors with ethanolamine.     

Kinetics of droplet condensation through a double free-energy barrier

Results are presented for the kinetics of nucleation of liquid droplets from a one-component vapor phase on a planar lyophobic substrate patterned with a large number of easily wettable (lyophilic) circular domains. If the wettability of these lyophilic domains is characterized by a contact angle smaller than pi2, for intermediate values of the supersaturation, the condensation of a droplet on a lyophilic domain occurs through a free-energy barrier with two maxima, that is, through a double barrier. A simple model is proposed for the kinetics of droplet condensation through a double barrier that combines Kramers's [Physica (Utrecht) 7, 284 (1940)] transition rate theory with known results of nucleation theory. In the framework of this model, the solution is derived for the steady-state limit of the nucleation process. The number of lyophilic domains available for droplet condensation reduces with time as domains are occupied by droplets. The problem of droplet condensation through a double barrier is solved taking into account the effect of the time-dependent depletion in the number of available lyophilic domains.     

Study of the volume condensation process in supersaturated vapor by the direct numerical solution of the kinetic equation for the droplet size distribution function

The volume condensation of supersaturated vapor is investigated by the direct numerical solution of the basic kinetic equation for the droplet size distribution function by analogy with the corresponding solution of the Boltzmann kinetic equation. The proposed consideration of the condensation growth of droplets is applicable at any Knudsen number. The method is tested by the example of vapor condensation under the conditions of the rapid development of supersaturation in a vapor-gas mixture as a result of its adiabatic expansion. In a wide range of Knudsen numbers, the results of the modeling are compared with those obtained by the moment method.     

Master curves for elastic and plastic properties of highly concentrated emulsions

Critical comparison of dependences of elastic and plastic properties of highly concentrated emulsions (so-called “compressed” emulsions) on the concentration and droplet sizes is performed. The studied emulsions of water-in-oil type are so-called “liquid explosives.” They are characterized by different mean sizes and different droplet size distributions of the dispersed phase. Different average values (D _av, D ₃₂, and D ₄₃) are used as characteristics of droplet sizes. Experiments are carried out with emulsions of two concentrations. Aqueous phase (dispersed droplets) is presented by supercooled solutions of inorganic salt in water in a metastable state. The concentration limit of the existence of highly concentrated emulsions is determined by the condition of the closest packing of liquid droplets, which lies in the φ* = 0.77–0.80 range. In addition, there is a limiting value of the maximal size of droplets. This limiting value depends on the concentration and meets the requirement that droplets should be small enough for the solution to exist in a supercooled state. The elastic modulus and the yield stress of emulsions studied are proportional to the square of the reciprocal linear size of droplets, which contradicts some theoretical models, according to which these parameter should be proportional to the reciprocal size of droplets. Using the obtained experimental data, we constructed generalized dependences of the elastic modulus and the yield stress on the concentration and size of droplets. These characteristics are in good agreement with the experimental data.     

Stochastic diffusion interactions and coarsening in a system of droplets growing from a supersaturated gas mixture

In this work we study diffusion interactions among liquid droplets growing in stochastic population by condensation from supersaturated binary gas mixture. During the postnucleation transient regime collective growth of liquid droplets competing for the available water vapor decreases local supersaturation leading to the increase of critical radius and the onset of coarsening process. In coarsening regime the growth of larger droplets is prevailing noticeably broadening the droplet size-distribution function when the condensation process becomes more intensive than the supersaturation yield. Modifications in the kinetic equation are discussed and formulated for a stochastic population of liquid droplets when diffusional interactions among droplets become noteworthy. The kinetic equation for the droplet size-distribution function is solved together with field equations for the mass fraction of disperse liquid phase, mass fraction of water vapor component of moist air, and temperature during diffusion-dominated regime of droplet coarsening. The droplet size and mass distributions are found as functions of the liquid volume fraction, showing considerable broadening of droplet spectra. It is demonstrated that the effect of latent heat of condensation considerably changes coarsening process. The coarsening rate constant, the droplet density (number of droplets per unit volume), the screening length, the mean droplet size, and mass are determined as functions of the temperature, pressure, and liquid volume fraction.     

Temperature induced formation of particle coated non-spherical droplets

Herein we offer a simple method to produce non-spherical emulsion droplets stabilized by freshly formed Mg(OH)(2) nanoparticles (MPs). The non-spherical degree of droplets as a function of experiment conditions was investiged and the origins of the presence of non-spherical droplets were discussed. The results of optical microscope images show that stable spherical droplets can be fused into non-spherical at given aging temperature. It is also recognized that particle concentration, oil/water ratio and aging time significantly affect droplet fusion and excess particles that are not adsorbed on the oil/water interface are helpful in restraining droplet fusion. Based on the TEM, XRD and Fluorescence confocal microscopy results, the origins of droplet fusion are inferred from the presence of vacant holes in the particle layer. Because of Oswald ripening, particles on droplet surfaces grow larger than the freshly precipitated ones under a given aging temperature. The growth of particles results in the reduction of total cover area of particle layer and thus creates vacant holes in the particle layer which would cause partial coalescence of droplets once they collide. Thus, these findings can offer a simple alternative to obtain a large amount of non-spherical emulsion droplets but also can help the preparation of non-spherical colloid particles.     

Microemulsions as reaction media for the synthesis of Pt nanoparticles

For the synthesis of Pt nanoparticles we used water-in-oil droplet microemulsions as templates. The focus was on the correlation between the size of the microemulsion droplets and that of the resulting Pt particles. To study this correlation in a systematic way, all particles were synthesized at the water emulsification failure boundaries where the microemulsion droplets are spherical and where their size can easily be tuned by the amount of added water. The metallic particles were synthesized by mixing two microemulsions one of which contains the metal salt H(2)PtCl(6) and the other the reducing agent NaBH(4). The size and structure of the microemulsion droplets was studied via small-angle X-ray scattering, while the Pt particles were characterized by high-resolution transmission electron microscopy in combination with energy-dispersive X-ray spectroscopy and selected area electron diffraction. The clear correlation between droplet and particle size was further supported by accompanying Monte Carlo simulations.     

Homogeneous nucleation at high supersaturation and heterogeneous nucleation on microscopic wettable particles: A hybrid thermodynamic/density-functional theory

Homogeneous nucleation at high supersaturation of vapor and heterogeneous nucleation on microscopic wettable particles are studied on the basis of Lennard-Jones model system. A hybrid classical thermodynamics and density-functional theory (DFT) approach is undertaken to treat the nucleation problems. Local-density approximation and weighted-density approximation are employed within the framework of DFT. Special attention is given to the disjoining pressure of small liquid droplets, which is dependent on the thickness of wetting film and radius of the wettable particle. Different contributions to the disjoining pressure are examined using both analytical estimations and numerical DFT calculation. It is shown that van der Waals interaction results in negative contribution to the disjoining pressure. The presence of wettable particles results in positive contribution to the disjoining pressure, which plays the key role in the heterogeneous nucleation. Several definitions of the surface tension of liquid droplets are discussed. Curvature dependence of the surface tension of small liquid droplets is computed. The important characteristics of nucleation, including the formation free energy of the droplet and nucleation barrier height, are obtained.     

The effect of different stabilizers on the formation of self‐assembled porous film via the breath‐figure technique

The Breath‐Figure technique was employed to imprint honeycomb structures in the polymer films via the condensation of water vapor on the surface of an evaporating polymer solution. Generally, the condensed water droplets can be stabilized by an end‐functional polymer or by particles added to the polymer solution. In this study, we carried out a systematic experiment on the effect of different stabilizers on the porous honeycomb structure under identical physical conditions. The end‐functional polymer produced a large area of regular spherical bubbles, whereas adding particles to the polymer solution leads to smaller arrays of the flattened bottom bubbles. The separation length between pores was larger for polymer/particle sample than that of the end‐functional polymer films. In the regular area of polymer/particle film many bubbles were not decorated by particles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1430–1436, 2011     

Sticking coefficient and processing of water vapor on organic-coated nanoaerosols

Organic-based aerosols may play an unexpectedly important role in the atmospheric processing of water vapor. In this paper, we report results of a molecular dynamics (MD) study on the sticking coefficient of water vapor on a coated particle (water droplet coated with fatty acid of radius approximately 4 nm). The sticking coefficient was found to be almost a constant (11-16%) for incident speeds around the most probable speed as opposed to 100% for water vapor incident on a pure water droplet. The sticking coefficient was found to increase with the size of the water cluster (water-Nmer) impinging the surface of the particle and was seen to approach 1 for impinging water clusters consisting of 10 molecules or more. We also computed the average energy transferred per collision for monomers impinging the surface of the coated particle and found the value to be 4.4581 kJ/mol. Most important perhaps was the fact that despite the lower sticking coefficient, the equilibrium vapor pressure of water over these inverted micelles was considerably lower due to the surface tension effects of the fatty acid layer. As such, these coated particles act as effective substrates for water vapor condensation and may play a role as cloud condensation nuclei.     

Insights into the Mechanism of Protein Electrospray Ionization From Salt Adduction Measurements

The mechanisms whereby protein ions are liberated from charged droplets during electrospray ionization (ESI) remain under investigation. Compact conformers electrosprayed from aqueous solution in positive ion mode likely follow the charged residue model (CRM), which envisions analyte release after solvent evaporation to dryness. The concentration of nonvolatile salts such as NaCl increases sharply within vanishing CRM droplets, promoting nonspecific pairing of Cl^- and Na⁺ with charged groups on the protein surface. For unfolded proteins, it has been proposed that ion formation occurs via the chain ejection model (CEM). During the CEM proteins are expelled from the droplet long before complete solvent evaporation has taken place. Here we examine whether salt adduction levels support the view that folded and unfolded proteins follow different ESI mechanisms. Solvent evaporation during the CEM is expected to be less extensive and, hence, the salt concentration at the point of protein release should be substantially lower than for the CRM. CEM ions should therefore exhibit lower adduction levels than CRM species. We explore the adduction behavior of several proteins that were chosen to allow comparative studies on folded and unfolded structures in the same solution. In-source activation eliminates chloride adducts via HCl release, generating protein ions that are heterogeneously charged because of sodiation and protonation. Sodiation levels measured under such conditions provide estimates of the salt adduction behavior experienced by the “nascent” analyte ions. Sodiation levels are significantly reduced for unfolded proteins, supporting the view that these species are indeed formed via the CEM.

Nanoparticles of varying hydrophobicity at the emulsion droplet-water interface: adsorption and coalescence stability

The coalescence stability of poly(dimethylsiloxane) emulsion droplets in the presence of silica nanoparticles ( approximately 50 nm) of varying contact angles has been investigated. Nanoparticle adsorption isotherms were determined by depletion from solution. The coalescence kinetics (determined under coagulation conditions at high salt concentration) and the physical structure of coalesced droplets were determined from optical microscopy. Fully hydrated silica nanoparticles adsorb with low affinity, reaching a maximum surface coverage that corresponds to a close packed monolayer, based on the effective particle radius and controlled by the salt concentration. Adsorbed layers of hydrophilic nanoparticles introduce a barrier to coalescence of approximately 1 kT, only slightly reduce the coalescence kinetics, and form kinetically unstable networks at high salt concentrations. Chemically hydrophobized silica nanoparticles, over a wide range of contact angles (25 to >90 degrees ), adsorb at the droplet interface with high affinity and to coverages equivalent to close-packed multilayers. Adsorption isotherms are independent of the contact angle, suggesting that hydrophobic attraction overcomes electrostatic repulsion in all cases. The highly structured and rigid adsorbed layers significantly reduce coalescence kinetics: at or above monolayer surface coverage, stable flocculated networks of droplets form and, regardless of their wettability, particles are not detached from the interface during coalescence. At sub-monolayer nanoparticle coverages, limited coalescence is observed and interfacial saturation restricts the droplet size increase. When the nanoparticle interfacial coverage is >0.7 and <1.0, mesophase-like microstructures have been noted, the physical form and stability of which depends on the contact angle. Adsorbed nanoparticle layers at monolayer coverage and composed of a mixture of nanoparticles with different hydrophobisation levels form stable networks of droplets, whereas mixtures of hydrophobized and hydrophilic nanoparticles do not effectively stabilize emulsion droplets.     

New approach to the kinetics of heterogeneous unary nucleation on liquid aerosols of a binary solution

The formation of a droplet on a hygroscopic center may occur either in a barrierless way via Kohler activation or via nucleation by overcoming a free energy barrier. Unlike the former, the latter mechanism of this process has been studied very little and only in the framework of the classical nucleation theory based on the capillarity approximation whereby a nucleating droplet behaves like a bulk liquid. In this paper the authors apply another approach to the kinetics of heterogeneous nucleation on liquid binary aerosols, based on a first passage time analysis which avoids the concept of surface tension for tiny droplets involved in nucleation. Liquid aerosols of a binary solution containing a nonvolatile solute are considered. In addition to modeling aerosols formed through the deliquescence of solid soluble particles, the considered aerosols constitute a rough model of "processed" marine aerosols. The theoretical results are illustrated by numerical calculations for the condensation of water vapor on binary aqueous aerosols with nonvolatile nondissociating solute molecules using Lennard-Jones potentials for the molecular interactions.     

Formation of carbon nanoparticles by the condensation of supersaturated atomic vapor obtained by the laser photolysis of C3O2

A new technique is suggested for obtaining nanoparticles from highly supersaturated vapor resulting from the laser photolysis of volatile compounds. The growth of carbon nanoparticles resulting from C₃O₂ photolysis has been studied in detail. Absorbing UV quanta (from an Ar-F excimer laser), C₃O₂ molecules decompose to yield atomic carbon vapor with precisely known and readily controllable parameters. This is followed by the condensation of supersaturated carbon vapor and the formation of carbon nanoparticles. These processes have been investigated by the laser extinction and laser-induced incandescence (LII) methods in wide ranges of experimental conditions (carbon vapor concentration, nature of the diluent gas, and gas pressure). The current and ultimate particle sizes and the kinetic parameters of particle growth have been determined. The characteristic time of particle growth ranges between 20 and 1000 μs, depending on photolysis conditions. The ultimate particle size determined by electron microscopy is 5–12 nm for all experimental conditions. It increases with increasing total gas pressure and carbon vapor partial pressure and depends on the diluent gas. The translational energy accommodation coefficients for the Ar, He, CO, and C₃O₂ molecules interacting with the carbon particle surface have been determined by comparing the LII and electron microscopic particle sizes. A simple model has been constructed to describe the condensation of carbon nanoparticles from supersaturated atomic vapor. According to this model, the main process in nanoparticle formation is surface growth through the addition of separate atoms to the nucleation cluster. The nucleus concentrations for various condensation parameters have been determined by comparing experimental and calculated data.     

Nonstationary evolution of the size,composition, and temperature of microdroplets of nonideal two- and three-component aqueous solutions

Results of numerical solution have been presented for a set of equations describing the nonstationary and nonisothermal growth or evaporation of microdroplets consisting of ethanol and water, sulfuric acid and water, and sulfuric and nitric acids and water. Time dependences of droplet size, temperature, and composition have been determined at low concentrations of a condensable vapor, as compared with the concentration of a carrier gas in an ambient vapor–gas mixture. The calculations have been performed using different initial conditions and approximations for the dependences of saturation vapor pressures, activity coefficients, and partial heats of condensation of the components, as well as average volumes per molecule on droplet composition and temperature. By the examples of ethanol–water and sulfuric acid–water droplets, it has been shown that nonmonotonic variations in the droplet radius are possible. Regimes of nonmonotonic variations in the temperature of a droplet that precede the onset of its stationary growth or evaporation have been revealed for all systems under consideration.     

Evidence of Molecular Fragmentation inside the Charged Droplets Produced by Electrospray Process

The behavior of the analyte molecules inside the neutral core of the charged droplet produced by the electrospray (ES) process is not unambiguously known to date. We have identified interesting molecular transformations of two suitably chosen analytes inside the ES droplets. The highly stable Ni(II) complex of 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane (1) that consists of a positive charge at the metal center, and the allyl pendant armed tertiary amine containing macrocycle 3,4,5:12,13,14-dipyridine-2,6,11,15-tetramethyl-1,7,10,16-tetraallyl-1,4,7,10,13,16-hexaazacyclooctadeca-3,13-diene (M _4p ) have been studied by ESI mass spectrometry as the model analytes. We have shown that these two molecules are not representatively transferred from solution to gas phase by ESI; rather, they undergo fragmentation inside the charged droplets. The results indicated that a charged analyte such as 1 was possibly unstable inside the neutral core of the ES droplet and undergoes fragmentation due to the Coulombic repulsion imparted by the surface protons. Brownian motion of the neutral analyte such as M _4p inside the droplet, on the other hand, may lead to proton attachment on interaction with the charged surface causing destabilization that leads to fragmentation of M _4p and release of resonance stabilized allyl cations from the core of the droplet. Detailed solvent dependence and collision-induced dissociation (CID) studies provided compelling evidences that the fragmentation of the analytes indeed occurs inside the charged ES droplets. A viable model of molecular transformations inside the ES droplet was proposed based on these results to rationalize the behavior of the analyte molecules inside the charged ES droplets.     

Evaporation of two solution droplets and a droplet located near a flat liquid surface

The mutual influence of two moderate-sized droplets of a dilute nonvolatile substance solution on the processes of their evaporation or condensation is theoretically analyzed under the assumption of a uniform concentration distribution inside the droplets. The conditions for the applicability of this approach are revealed. The evaporation or condensation of a droplet near a flat liquid surface is considered as a limiting case. The fluxes of water molecules to and from the surface of aqueous glycerol solution droplets occurring in air are numerically estimated depending on the droplet radii, distances between their surfaces, and air humidity. Analogous estimates are obtained for an aqueous glycerol solution droplet growing near a flat water surface.     

Sub-micrometer dropwise condensation under superheated and rarefied vapor condition

Phase change accompanying conversion of a saturated or superheated vapor in the presence of subcooled surfaces is one of the most common occurring phenomena in nature. The mode of phase change that follows such a transformation is dependent upon surface properties such as contact angle and thermodynamic conditions of the system. In present studies, an experimental approach is used to study the physics behind droplet growth on a partially wet surface. Superheated vapor at low pressures of 4-5 Torr was condensed on subcooled silicon surface with a static contact angle of 60° in the absence of noncondensable gases, and the condensation process was monitored using environmental scanning electron microscopy (ESEM) with sub-microscopic spatial resolution. The condensation process was analyzed in the form of size growth of isolated droplets before a coalescence event ended the regime of single droplet growth. Droplet growth obtained as a function of time reveals that the rate of growth decreases as the droplet increases in size. This behavior is indicative of an overall droplet growth law existing over larger time scales for which the current observations in their brief time intervals could be fitted. A theoretical model based on kinetic theory further support the experimental observations indicating a mechanism where growth occurs by interfacial mass transport directly on condensing droplet surface. Evidence was also found that establishes the presence of sub-microscopic droplets nucleating and growing between microscopic droplets for the partially wetting case.