Measurement of Activity Coefficients from Unsteady State Evaporation and Growth of Microdroplets

Techniques are presented for determination of activity coefficients of binary systems from unsteady state evaporation and growth of single microdroplets in controlled environments. A high-precision light scattering method based on resonances observed in light scattering by microdroplets was used to determine the size and composition of a microdroplet as functions of time. The techniques were validated through data on growth of glycerol microdroplets in slowly developing water vapor concentration fields and evaporation of microdroplets, containing volatile dimethylphthalate (DMP) and nonvolatile dioctylphthalate (DOP), in vapor-free atmospheres. When the water vapor concentration in the surrounding gas changes slowly a glycerol droplet maintains a dynamic equilibrium with the water vapor; thus the activity coefficient of water was determined from knowledge of the droplet composition and the water vapor saturation ratio in the gas phase. The activity coefficients of DMP were determined on the basis that the instantaneous evaporation rate of a DMP-DOP microdroplet in a vapor-free atmosphere is equal to the product of the activity of DMP and the evaporation rate of a pure DMP droplet. The activity coefficient values obtained from microdroplet experiments are highly reproducible and agree with data available in the literature.     

气溶胶微滴的蒸发及界面现象

用电动平衡仪和光散射技术研究气溶胶微滴蒸发及其伴随的界面现象.研究的系统有缓慢蒸发的有机物微滴、快速蒸发的水滴和含表面活性剂的水滴.实验结果表明:蒸发速率影响着微滴的温度;表面活性剂显著地降低了水滴的蒸发速率;表面电荷密度的增加会导致微滴的分裂.这些研究结论对控制工业装置中液滴的蒸发和燃烧过程有着重要意义.     

用激光散射技术测定硝酸铵微滴的分解

在常温常压下,一个初始半径为5～30μm的硝酸铵水溶液微滴被悬浮在电动平衡仪内,同时该微滴受到一束激光的照射.在34.5°～68.4°散射角内使用一个512点线性光电列阵,测定不同时间里硝酸铵微滴的光散射强度变化.借助于计算机上Mie理论计算,可以容易地比较出硝酸铵微滴的尺寸.根据这种方法,可以精确地测定硝酸铵微滴在分解蒸发过程的尺寸变化.在实验基础上,提出了一个扩散控制的表面反应模型以描述硝酸铵微滴的分解蒸发过程,并得到硝酸铵微滴在25℃、26℃和27℃时的平衡压力.     

Thermodynamic and kinetic behavior of glycerol aerosol

Glycerol and propylene glycol mixtures are common carrier solutions in electronic cigarettes. Aerosols produced from these mixtures will evaporate quickly in a dry environment due to their high volatility. In a humid environment, such as the lungs, the kinetics of evaporation and hygroscopic growth determine the evolution of aerosol plume glycerol. Here, we apply a temperature and relative humidity-controlled hygroscopicity/volatility tandem differential mobility analyzer system to study the growth and evaporation kinetics of glycerol aerosol over a wide range of temperature, relative humidity, and residence times. Results show that at dry conditions glycerol aerosols evaporate within seconds at temperatures warmer than 20°C and that the accommodation coefficient of glycerol vapor on dry glycerol particles is 0.8. Under humidified conditions, the mutual depression of vapor pressures of the aqueous glycerol/water solution slows the glycerol evaporation rate consistent with thermodynamic and kinetic model predictions. Model calculations show that water vapor aided condensation of glycerol can occur at high relative humidity for glycerol vapor concentrations that result in glycerol particle evaporation under dry conditions. The combined results will help with constraining computational modules that model the evolution of glycerol-containing aerosols along a prescribed thermodynamic trajectory.

Copyright © 2016 American Association for Aerosol Research     

影响水平管降膜蒸发传热性能的因素

影响水平管降膜蒸发传热性能的因素齐和发，沈吟秋（大连理工大学化工学院）关键词水平管降膜；传热膜系数；浓度１引言水平管降膜蒸发器是二十余年发展起来的一种高效节能型蒸发器。目前，这种蒸发器已广泛应用于海水淡化、医药、食品、化工和致冷等工业中［１］。影响水...     

Growth Rate Measurements for Single Suspended Droplets Using the Optical Resonance Method

An experimental technique described with which the growth rate of a single solution droplet by water vapor condensation can be repeatedly measured with high precision. The technique involves the use of an electrodynamic cell to suspend a NaCl solution droplet in water vapor and a CO₂ laser to momentarily perturb the droplet-vapor equilibrium. The droplet size change during condensational growth is monitored with a tunable dye laser for a particular optical resonance due to Mie scattering. A consideration of the coupled heat and mass transfer processes during droplet growth indicates that the best agreement between theory and the experimental results is obtained with a condensation coefficient close to unity.     

喷嘴雾化特性及脱硫废水蒸发数值模拟

利用相位多普勒粒度分析仪（PDA）实验台测量了双流体喷嘴出口速度与粒径分布,利用得到的速度与粒径数据对江苏某生物质电厂进行小水量脱硫废水蒸发的数值模拟,着重研究了液滴粒径以及烟气中水蒸气的体积分数对液滴蒸发过程的影响。PDA实验结果表明,该双流体喷嘴在特定气液比条件下出口粒径均小于100μm。应用离散相模型与随机轨道模型,利用Rosin-Rammler分布模拟喷雾液滴分布范围（0～100μm）。模拟结果表明,粒径低于100μm的液滴能够完全蒸发,液滴粒径越小,完全蒸发时间越短,液滴经历的平稳吸热时间越短。随着粒径的增加,液滴完全蒸发时间增幅变大。随着烟气中水蒸气体积分数增加,液滴蒸发速率变缓,液滴开始蒸发的时间延长,且体积分数越大,出口未蒸发完全的液滴直径越大,但出口液滴粒径增大的幅度在减小。     

Phase behavior of a fragrance compound system: Water/phenethyl alcohol/laureth 4/glycerol

The phase diagram of the system water/phenethyl alcohol (PEA)/Laureth 4 (L4)/glycerol was determined using visual observation, optical microscopy, small-angle X-ray diffractometry, and the vapor pressure of phenethyl alcohol measured by gas chromatographic analysis of headspace vapor at equilibrium. The phase diagram was shown to be dominated by three narrow isotropic liquid solubility regions along the water/glycerol, glycerol/PEA, and PEA/L4 axes. Vapor pressure measurements and tie-line determinations showed the final state of formulations after evaporation of water to be emulsions of glycerol/PEA-in-L4/PEA or L4/PEA-in-glycerol/PEA. PEA was predominantly dissolved in the L4/PEA phase because the chemical potential of PEA in glycerol was high, even at modest concentrations.     

Droplet evaporation and solute precipitation during spray pyrolysis

The process of spray pyrolysis was investigated theoretically using a model that describes the evolution of the droplet size, solvent vapor concentration in the carrier gas, and both droplet and gas temperatures along the reactor axis. The model also accounts for solute concentration profiles and solute precipitation in the solution droplets. The model was used to describe the evaporation of sodium chloride aqueous solution droplets in diffusion dryers and hot-wall reactors as a function of reactor residence time, droplet size (a few microns), solution molality (up to 2 M), droplet concentration (10⁶–10⁷ cm⁻³), relative humidity of the carrier gas (0–50%) and reactor wall conditions. Decreasing initial droplet size and solution molality accelerated droplet evaporation and resulted in smaller droplets at the onset of solute nucleation. Decreasing droplet concentration and carrier gas inlet relative humidity as well as increasing wall temperature (up to 350°C) or axial wall temperature gradient (up to 100°C cm⁻¹) increased the droplet evaporation rate, but did not change appreciably the droplet size at the point of precipitation for a given droplet size and solute concentration. Thus, control of droplet size at the onset of solute nucleation by varying process parameters other than the solution concentration and initial droplet size is limited.     

The separation of two different sized particles in an evaporating droplet

The separation of two different sized particles during evaporation of a dilute droplet is examined both computationally and experimentally. A transport model of the evaporating droplet system was solved using the finite element method to determine the fluid velocity, pressure, vapor concentration surrounding the droplet, temperature, and both particle concentrations. Experimentally, 1 μm and 3 μm polystyrene particles were used during the evaporation of a sessile water droplet. It was determined that to accurately model particle deposition, thermal effects need to be considered. The Marangoni currents in evaporating droplets keep particles suspended in the droplet until the end of the evaporation. Previous models of particle deposition during droplet evaporation have rapid accumulation of particles at the contact line. Our experiments and the experiments of others demonstrate that this is not accurate physically. In addition, to model the separation of two different sized particles the consideration of thermal effects is essential. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3547–3556, 2015     

IN SITUMEASUREMENT OF PHOTOCHEMICAL REACTIONS IN MICRODROPLETS

A technique based on fluorescence scattering by microdroplets has been shown to be capable of measuring instantaneous rates of photochemical reactions in microdroplets. The technique has been applied to study trans -to-cis photoisomerization of thioindigo dye in single solution droplets suspended in an electrodynamic balance. Through an analysis it is shown that the concentration distributions of isomers remain uniform in a droplet under the experimental conditions; thus, the scattered fluorescence intensity from the droplet is proportional to the concentration of solely fluorescent trans isomer molecules. The steady-state scattered fluorescence intensity versus incident laser power data have been used to interpret the kinetics of the reaction. The results show that the rate constants can be determined from the scattered fluorescence intensity versus time data. The technique is particularly suitable when only one species fluoresces in the photo-reactive wavelength range while other species present in a droplet do not.     

Nonisothermal Droplet Growth in the Free Molecular Regime

The growth rates of nonane and D₂O nanodroplets produced in supersonic expansions are characterized using small angle X-ray scattering (SAXS) and pressure trace measurements (PTM). The experimental growth rates are compared to the predictions of a Hertz–Knudsen model that assumes either isothermal or nonisothermal droplet growth in the free molecular regime. For nonane, the predicted growth rates are insensitive to both droplet temperature and the evaporation coefficient, and agree well with the experimentally measured growth rates assuming a condensation coefficient of 1. For D₂O, droplet growth rates are quite sensitive to droplet temperature, and the best agreement between experiments and theory are achieved for a condensation coefficient of 1 and an evaporation coefficient in the range from 0.5 to 1. Under our experimental conditions, incorporating coagulation is important to match the measured D₂O growth rates but not those of nonane.

Copyright 2013 American Association for Aerosol Research     

Vibrating Orifice Droplet Generator for Studying Fast Processes Associated with Microdroplets

ABSTRACT

A light scattering technique, based on resonances, has been applied to a linear stream of highly monodisperse droplets generated by a modified vibrating orifice aerosol generator to study evaporation of ethanol droplets. The residence time of droplets was varied by altering the distance between the orifice and a laser beam. Frequencies at which intensity peaks (i.e., resonances) appear in elastic and Raman scattered light were determined by varying the frequency of droplet generation. The absolute droplet size and refractive index were determined by matching the observed resonances with theoretical resonances that minimize the difference between the observed and calculated resonance frequencies. The size and refractive index changes between two successive residence time observations were determined from the frequency shifts of the resonances. These procedures permit determination of size and refractive index with a precision of 2 parts in 10⁴, and their changes within 1 part in 10⁴ of the absolute values. For the examined residence time of 650 μs the evaporation process was unsteady. The evaporation rate as well as droplet temperature estimated from the refractive index was found to decrease with time. The experimental technique can be applied to study any fast process associated with microdroplets where observable changes occur over microsecond level time scales.     

考虑结壳现象的液滴干燥过程数值模拟

为更清楚地了解液滴的干燥过程,文中综合考虑溶剂扩散系数与溶液质量分数,溶液质量分数与液滴表面蒸汽压和滴径变化与传热传质之间的耦合关系,建立了包含液滴内部径向热传导方程,液滴内部的传质方程及液滴质量变化方程的液滴蒸发的完整模型。用所建模型对不同操作工况下液滴的挥发过程进行了模拟,描述了干燥过程中液滴质量损失,滴径的变化及液滴表面到中心的溶液组分变化,并对影响液滴干燥速度的重要因素进行了分析。模型模拟结果跟实验结论比较一致。     

Effects of plasticization conditions on the structures and properties of cellulose packaging films from ionic liquid [BMIM]Cl

By using natural softwood pulp with higher degree of polymerization (DP = 1460) as cellulose source, 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid as solvent and glycerol as plasticizer, a novel cellulose packaging film was prepared. The effects of plasticization conditions on the structures, mechanical properties, permeability for oxygen and water vapor were measured by Wide-angle X-ray scattering, thermogravimetric analysis, scanning electron microscopy (SEM), and other techniques. The investigations suggested that the glycerol concentration and plasticizing time had great effect on the properties of the regenerated cellulose films. The crystal transformation of cellulose I to cellulose II occurred during the dissolution and regeneration process, combining with the decrease of thermal stability. The tensile strength decreased rapidly with the addition of glycerol and prolongation of plasticizing time. However, elongation at break of the regenerated cellulose films increased at first and then decreased with increasing of glycerol concentration and plasticizing time. The morphologies for the fracture surface obtained from SEM images showed transformation of typical brittle fracture to plastic deformation with increasing of glycerol concentrations. It was also found that both water vapor permeability and oxygen permeability of the regenerated cellulose films decreased slowly with increasing of glycerol concentrations and plasticizing time, but water vapor permeability and oxygen permeability presented an almost opposite trend. The films prepared by using ionic liquid technology would be used in food packaging or other fields as a kind of green packaging material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

乙醇溶液液滴降压蒸发过程传热传质特性

针对单个乙醇溶液液滴在降压环境下蒸发的传热传质过程建立了数学模型。模型基于液相的能量守恒和 传质扩散理论,利用经典拓展模型计算液滴的质量蒸发率,并引入活度系数考虑液滴表面的蒸气分压。采用液 滴悬挂法进行实验,分别记录了乙醇溶液液滴和乙酸溶液液滴在降压蒸发过程中的液滴内温度变化。将实验数 据与计算结果对比,验证了模型的有效性。通过模型计算获得了液滴内部温度分布以及浓度分布随时间的变化。 结果表明:快速降压阶段空气流动较快,加之乙醇工质易挥发,液滴表面温度下降迅速,液滴内部温差和乙醇 浓度梯度较大;压力稳定后,空气流速为零,液滴内部温差和乙醇浓度梯度逐渐减小。由于液滴内部的热扩散 速率大于传质扩散系数,内部温度随时间的变化比浓度随时间的变化更快。     

Gas analysis of the CVD process for high yield growth of carbon nanotubes over metal-supported catalysts

Changes in the gas composition during the methane chemical vapor deposition growth of single- and double-walled carbon nanotubes over metal-supported MgO catalysts were investigated in an attempt to increase the nanotube yield. Monitoring the gas composition by gas chromatography as a function of the reaction time provides information on the activity and lifetime of the catalyst. The degree of methane decomposition, i.e., the C-H bond dissociation, was closely related to the nanotube yield, and the Fe-Mo binary catalyst exhibited a high activity. The effects of water vapor on the catalytic nanotube growth were also studied by introducing water vapor in the inlet gas. An appropriate amount of water prolonged the lifetime of the catalyst and increased the nanotube yield by 35%.     

低剂量超吸水树脂溶液微滴中甲烷水合物生成动力学

高储气密度水合物的快速生成对气体水合物技术应用至关重要。将水与疏水性气相纳米二氧化硅和低剂量［0.1%~1.0%（质量）］的超吸水树脂在搅拌器中高速混合分散，制备出一种超吸水树脂改性的干水。该改性干水实质上是由高分子聚合物支撑且可自由流动的分散微滴堆。在8.0 MPa和274.2 K条件下，研究该改性微滴中甲烷水合物生成动力学特性。结果表明，松散的聚合物微滴极大地改善了液相连续水比表面积，为气体扩散至微滴表面提供了丰富的通道。水合物在聚合物微滴中快速生成，储气速率可达5.15~8.78 cm³·g^-1·min^-1，储气量高达158.0~175.0 cm³·g^-1。质量分数为0.3%的微滴表现出最快储存速率和最高储气量，且其循环水合储气过程中前6次储气量均超过120 cm³·g^-1。研究结果对水合物储运天然气技术规模化应用有一定的参考价值。     

低剂量超吸水树脂溶液微滴中甲烷水合物生成动力学

高储气密度水合物的快速生成对气体水合物技术应用至关重要。将水与疏水性气相纳米二氧化硅和低剂量［0.1%~1.0%（质量）］的超吸水树脂在搅拌器中高速混合分散,制备出一种超吸水树脂改性的干水。该改性干水实质上是由高分子聚合物支撑且可自由流动的分散微滴堆。在8.0 MPa和274.2 K条件下,研究该改性微滴中甲烷水合物生成动力学特性。结果表明,松散的聚合物微滴极大地改善了液相连续水比表面积,为气体扩散至微滴表面提供了丰富的通道。水合物在聚合物微滴中快速生成,储气速率可达5.15~8.78 cm³·g^-1·min^-1,储气量高达158.0~175.0 cm³·g^-1。质量分数为0.3%的微滴表现出最快储存速率和最高储气量,且其循环水合储气过程中前6次储气量均超过120 cm³·g^-1。研究结果对水合物储运天然气技术规模化应用有一定的参考价值。