Analysis of supersaturation and nucleation in a moving solution droplet with flowing supercritical carbon dioxide

A supercritical antisolvent (SAS) process is employed for production of solid nanoparticles from atomized droplets of dilute solution in a flowing supercritical carbon dioxide (SC CO₂) stream by attaining extremely high, very rapid, and uniform supersaturation. This is facilitated by a two‐way mass transfer of CO₂ and solvent, to and from the droplet respectively, rendering rapid reduction in equilibrium solubility of the solid solute in the ternary solution. The present work analyses the degree of supersaturation and nucleation kinetics in a single droplet of cholesterol solution in acetone during its flight in a flowing SC CO₂ stream. Both temperature and composition are assumed to be uniform within the droplet, and their variations with time are calculated by balancing the heat and mass transfer fluxes to and from the droplet. The equilibrium solubility of cholesterol with CO₂ dissolution has been predicted as being directly proportional to the Partial Molar Volume Fraction (PMVF) of acetone in the binary (CO₂–acetone) system. The degree of supersaturation has been simulated up to the time required to attain almost zero cholesterol solubility in the droplet for evaluating the rate of nucleation and the size of the stable critical nuclei formed. The effects of process parameters have been analysed in the pressure range of 7.1–35.0 MPa, temperature range of 313–333 K, SC CO₂ flow rate of 0.1136–1.136 mol s^?1, the ratio of the volumetric flow rates of CO₂‐to‐solution in the range of 100–1000, and the initial mole fraction of cholesterol in acetone solution in the range of 0.0025–0.010. The results confirm an extremely high and rapid increase in degree of supersaturation, very high nucleation rates and stable critical nucleus diameter of the order of a nanometre. Copyright © 2005 Society of Chemical Industry     

Microemulsion polymerization kinetics and mechanisms

The mechanisms of microemulsion polymerizations stabilized by sodium dodecyl sulfate in combination with pentanol were investigated with a water‐insoluble dye as the probe. The major parameters chosen for study were the types of initiators [water‐soluble sodium persulfate (SPS) vs oil‐soluble 2,2′‐azobisisobutyronitrile (AIBN)] and the polarity of the monomers [relatively hydrophobic styrene (ST) vs relatively hydrophilic methyl methacrylate (MMA)]. Both continuous particle nucleation and limited particle flocculation had a significant influence on the polymerization kinetics. For the polymerizations investigated in this work, the relatively low initiation efficiency of AIBN resulted in a reaction system showing a quite different particle nucleation mechanism than that of the ST polymerization with SPS. The formation of particle nuclei in water was suppressed to some extent, and microemulsion droplet nucleation predominated in the ST polymerization initiated by AIBN. Homogeneous nucleation played an important role, and a mixed mode of particle nucleation (microemulsion droplet nucleation and homogeneous nucleation) was operative in the MMA polymerization. The MMA polymerization experienced stronger particle flocculation than its ST counterpart. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2005–2013, 2005     

A new mechanistic model to predict gas–liquid interface shape of gas–liquid flow through pipes with low liquid loading

Devising a new mechanistic method to predict gas–liquid interface shape in horizontal pipes is concerned in this article. An experiment was conducted to find the pressure gradients of air–water flow through a 1‐in. pipe diameter. Comparing results of model with some experimental data available in the literature demonstrates that the model provides quite better predictions than existed models do. This model also predicts flow regime transition from stratified to annular flow better than Apparent Rough Surface and Modified Apparent Rough Surface models for both 1‐ and 2‐in. pipe diameters. The model also leads to reliable predictions of wetted wall fraction experimental data. Although one parameter of new model was evaluated based on air–water flow pressure loss experimental data for 1 in. pipe, it was considerably successful to predict pressure drop, liquid holdup, stratified‐annular transition and wetted wall fraction for other gas–liquid systems and pipe diameters. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1043–1053, 2015     

Microcellular extrusion of PLA utilizing solid‐state nucleation in the gas‐saturated pellet extrusion process

In this study, we explore the use of solid‐state nucleation in polymer pellets as a means to create microcellular PLA foams in extrusion. This is achieved by using gas‐saturated PLA pellets as input to the extruder. Foam density, bubble size, and bubble density is reported and compared with microcellular foams created in the gas‐injection extrusion process. PLA pellet gas concentrations between 17 and 29 mg CO₂/g PLA was found to produce quality microcellular foams in this process. Gas concentrations within this range were achieved by varying methods that included partial saturation, desorption from full saturation, and blending saturated with unsaturated pellets. This gas concentration window that produced microcellular foams was found to be independent of the saturation and desorption process used to achieve the desired concentration. We further compare the pressure drop and pressure drop rate of the gas‐saturated pellet extrusion process showing that similar foams can be produced at pressures orders of magnitude lower than the alternative gas‐injection extrusion processes. Investigations into extrusion pressures support the hypothesis that the gas‐saturated pellet extrusion process utilizes solid‐state nucleation in the feed section of the extruder to achieve high bubble density foams. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Identification of cell‐nucleation mechanism in foam injection molding with gas‐counter pressure via mold visualization

The mechanisms of cell nucleation and growth are investigated in foam injection molding (FIM) using gas‐counter pressure (GCP). An in‐situ mold visualization technique is employed. The application of GCP suppresses cell nucleation, and prevents the blowing agent from escaping during mold‐filling. The inherent structural heterogeneity in the regular FIM can be improved because of the uniform cavity pressure when employing GCP. The cavity pressure profiles show much faster pressure‐drop rates using GCP, because the single‐phase polymer/gas mixture has a lower compressibility than the two‐phase polymer/bubble mixture. Therefore, both the cell nucleation and growth rates are significantly increased through a higher pressure‐drop rate on the removal of the GCP. The effect of GCP magnitude on the cell morphology is explored. When the GCP is lower than the solubility pressure, bimodal foaming occurs. As the GCP increases above the solubility pressure, the cell density increases because of the higher pressure‐drop rate. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4035–4046, 2016     

采用增大凝结液滴方法的锥芯超音速旋流分离装置性能研究

To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a method of droplet enlargement was applied. A series of experiments were carried out in the improved separation device under various conditions, using air-ethanol vapor as the medium and micro water droplets as nucleation centers. The effects of the inlet pressure, temperature and relative humidity, the swirling intensity, and mass flow rate of water on the separation performance were investigated. The separation was improved by increasing the inlet pressure and relative humidity. With the decrease of swirling intensity and mass flow rate of water, the separation efficiency increased first and then decreased. The inlet temperature had a slight effect on the separation. The results showed that the separation performance was effectively improved using the proposed structure and method, and the best separation in this study was obtained with the ethanol removal rate about 55% and dew point depression 27 K. The addition of water had little pollution to the air-ethanol vapor system since the water carry-over rate was within the range of %-0 in most cases.     

Identification of nucleation loci in emulsion polymerization processes. II. A systematic study of liquid–liquid emulsions

Identification of the main nucleation sites and characterizing them in terms of their size and composition is prime objective of this research effort. Different nucleation sites have been proposed as the most likely nucleation sites by various researchers. Recent advances in the development of the spectroscopic techniques enable comprehensive characterization of the emulsion at the beginning of the reaction. In this paper, we present the experimental evidence of the existence of a previously unidentified nano‐droplet population of size range 30 to 100 nm in diameter using spectroscopy. Presence of about seventy to eighty percent of the dispersed phase in the nano‐droplet population and large interfacial area make them the most probable particle nucleation loci in emulsion polymerization processes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2858–2866, 2006     

Radial pressure profiles in a cold‐flow gas‐solid vortex reactor

A unique normalized radial pressure profile characterizes the bed of a gas‐solid vortex reactor over a range of particle densities and sizes, solid capacities, and gas flow rates: 950–1240 kg/m³, 1–2 mm, 2 kg to maximum solids capacity, and 0.4–0.8 Nm³/s (corresponding to gas injection velocities of 55–110 m/s), respectively. The combined momentum conservation equations of both gas and solid phases predict this pressure profile when accounting for the corresponding measured particle velocities. The pressure profiles for a given type of particles and a given solids loading but for different gas injection velocities merge into a single curve when normalizing the pressures with the pressure value downstream of the bed. The normalized—with respect to the overall pressure drop—pressure profiles for different gas injection velocities in particle‐free flow merge in a unique profile. © 2015 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 61: 4114–4125, 2015     

Rewetting effects and droplet motion on partially wetted powder surfaces

In high shear mixer granulation, the powder is agitated in a vessel while liquid is sprayed onto the powder. Formation of “nuclei” can be predicted using a nucleation regime map. However, this approach assumes that only dry powder enters the spray zone. Industrial granulation processes commonly add 20–50 wt % fluid, and the partially wetted powder recirculates many times through the spray zone. The effect of partially wetted powder re‐entering the spray zone is not currently known. To investigate, droplets were added to a powder bed at controlled separation distances and time intervals. A strong correlation between drop penetration time and droplet motion on the powder bed surface was observed. For fast penetrating systems, nucleation was only slightly affected by the presence of the previous droplet. However, systems with long penetration times showed lateral droplet motion due to Laplace pressure differences. Implications for the nucleation regime map are discussed. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Investigation on the cell nucleation and cell growth in microcellular foaming by means of temperature quenching

The cell nucleation and real‐time cell growth with increasing cell growth time in microcellular foaming were investigated by means of temperature quenching in a supercritical CO₂ pressure‐quench process. Samples of uniform size and shape were saturated in a vessel under conditions of 100–180°C and 30 MPa, and then depressurized to the atmosphere in 10 s. After depressurization, these samples were removed from the vessel at prescribed intervals, and immediately immersed in an ice‐water slurry to obtain foamed samples with various cell growth times. It was found that the nucleation density is closely correlated to the gas absorption capacity of the polymer matrix, so that the final cell density should not be adopted as the nucleation density, as done commonly. The change of cell structure and mass density with increasing cell growth time was dominated by gas diffusion behavior, which was strongly influenced by the temperature. The final cell structure was mainly determined by the cell growth step, where gas diffusion played a key role. The final cell density was in direct proportion to the gas remaining in the substrate, which ranged from 6.0 × 10⁹ to 4.7 × 10⁶ cells/cm³. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 163–171, 2004     

Kinetics of miniemulsion polymerizations of ethylene glycol dimethacrylate and/or methyl methacrylate

Two types of reactive acrylic microgel particles of methyl methacrylate (MMA)/ethylene glycol dimethacrylate (EGDMA) (66.4/33.6 and 0/100 (mol/mol)) were prepared by miniemulsion polymerization with 2,2′‐azobisisobutyronitrile as the initiator in the temperature range 60–80 °C. Ostwald ripening occurred during the very early stage of polymerization. In addition to the predominant droplet nucleation, homogeneous nucleation was also observed. The polymerization rate for MMA/EGDMA miniemulsion was higher than that for EGDMA miniemulsion. By contrast, comparable apparent limiting conversions were observed for the polymerizations of MMA/EGDMA and EGDMA. The mole fractions of MMA and EGDMA units incorporated into the copolymer product were estimated to be 0.62 and 0.38, respectively, for the polymerization of MMA/EGDMA at 70 °C. The mole fraction of the EGDMA unit containing one ? C?C? within the MMA/EGDMA microgel particle product was estimated to be 0.23, which was comparable to that (0.22) of the EGDMA unit containing one ? C?C? within the EGDMA microgel particle product. © 2015 Society of Chemical Industry     

受限纳米通道内气泡核化的分子动力学模拟

采用分子动力学方法模拟研究受限纳米通道内液体在固体壁面上的核化生长过程,本文主要研究固体壁面润湿性对液体核化生长的影响并分析了气泡成核机理。结果表明：不同壁面润湿性对气泡核化生长产生较大影响。壁面润湿性强时,近壁面处会形成一层液膜,出现与池沸腾不同的现象,流体在液膜层发生均质核化,气泡核化生长速度较快;壁面润湿性较弱时,液体在近壁面处发生异质核化,气泡核化生长速度相对较慢;壁面润湿性最弱时,在近壁面处会形成一层气膜,热量通过气膜传递给流体,传热效果不佳,液体很难发生核化现象。形成这种现象的原因是壁面润湿性强,近壁面处会形成“类固体”层,热量由壁面经“类固体”层传给通道内流体,传热效果好,此外,“类固体”层越厚传热效果越好。壁面润湿性弱时,近壁面处没有“类固体”层,会形成一层气膜,降低传热效果,影响通道内流体核化生长。     

Gas/liquid/liquid three‐phase flow patterns and bubble/droplet size laws in a double T‐junction microchannel

The double T‐junction microchannel is a classical microstructured chemical device used to generate gas/liquid/liquid three‐phase microflows. An experimental study that focused on the three‐phase flow phenomena and bubble/droplet generation rules in a double T‐junction microchannel was introduced. Based on the published knowledge of gas/liquid and liquid/liquid two‐phase microflows, new flow patterns were carefully defined: bubble cutting flow, spontaneous break‐up and bubble cutting coupling flow, and bubble/droplet alternate break‐up flow. According to the classical correlations of bubble and droplet volumes and their generation frequency ratio, the operating criteria for creating different three‐phase flow patterns were established and a model for the dimensionless average bubble and droplet volumes in the three‐phase microflows was developed. These various three‐phase microflows have great application potential in material science and flow chemistry synthesis. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1722–1734, 2015     

改进的Dillmann-Meier自发凝结模型探讨

考虑单分子聚团间相互作用下,Dillmann-Meier模型冷凝成核率结果较为准确,然而该模型运算量较大,不能适应于含有凝结现象的流动过程分析中。文中在Dillmann-Meier模型基础上,给出了改进后的模型,将不同理论用于计算水和n-C9的成核率结果与所有理论模型和实验结果进行比较,表明改进后的MDM模型精度接近Dillmann-Meier模型但运算更快捷。通过对尺寸校正函数研究了不同温度、过饱和度对微观表面张力的影响,分析了造成不同理论计算成核率存在差别的主要原因。     

A simulation tool for aerosol formation during sulphuric acid absorption in a gas cleaning process

A simulation tool has been developed to predict sulphuric acid aerosol formation in typical industrial absorption processes for gas cleaning. The underlying model comprises homogeneous nucleation and the growth of a polydisperse droplet collective under the special circumstances of a gas–liquid contact device where heat and mass transfer processes between the bulk phases take place simultaneously. The model is applied to a hot flue gas (200 °C) with sulphuric acid concentrations between 5 and 100 mg m⁻³ (STP) (STP: standard temperature and pressure). The simulation yields high droplet number concentrations up to 10¹⁶ m⁻³ especially for low gas inlet concentrations of sulphuric acid (5 mg m⁻³ (STP)), and very small droplet sizes in the range 20–100 nm. The droplet number concentrations decrease and the droplet sizes increase with increasing sulphuric acid inlet concentrations. It is shown that small droplets (<20 nm) need relatively high supersaturation for growing. If the saturation in the absorption equipment is not high enough the droplets partially re-evaporate but do not vanish due to the extremely low vapor pressure of concentrated sulphuric acid. The resulting size distributions of the aerosol droplets are not very sensitive with respect to the nucleation model used. This is demonstrated by comparing nucleation models with and without hydrate formation. The new simulation tool allows an estimate of the true sulphuric acid removal efficiency of absorption processes which is often not more than 50% due to aerosol formation. In general, the simulation results enable a deeper insight in the mechanisms of aerosol formation and behavior in absorption processes.     

Characterizing cocoa butter seed crystals by the oil-in-water emulsion crystallization method

Unambiguous quantitative evidence for the catalytic action of seed crystals in cocoa butter is presented. We used an ultrasound velocity technique to determine the isothermal growth of solid fat content in cocoa butter oil-in-water emulsions, in which the probability of finding a seed crystal in any one droplet was around 0.37 at 14.2°C. The upper limit for the size of seed crystals in West African cocoa butter was around 0.09 μm, the Gibbs free energy for nucleation was 0.11 mj m⁻², and the concentration of seed crystals was in the range of 10¹⁶ to 10¹⁷ m⁻³. X-ray diffraction measurements showed that emulsified cocoa butter crystallizes in the α polymorph and does not appear to transform to the β′ form within the first 25 min of crystallization. Primary nucleation events in cocoa butter emulsions are accounted for by seed crystals. Collision-mediated nucleation, a secondary nucleation mechanism, in which solid droplets (containing seed crystals) catalyze nucleation in liquid droplets, is shown to account for subsequent crystallization. This secondary nucleation mechanism is enhanced by stirring.     

Driving force in first-order phase transitions and its application to gas hydrate nucleation from a single phase

Classical nucleation theories of general application are taken as starting point to analyze the driving force for multicomponent gas hydrate nucleation from a single homogeneous phase. It is shown that the ratio between the specific surface energy and the critical radius of nucleation has a single value irrespective of the analyzed driving force expression. From this result, two driving force expressions for multicomponent gas hydrate nucleation are derived in the context of the so-called generalized nucleation theory, and it is demonstrated that the driving force for gas hydrates can be estimated using the same information given for the determination of the incipient formation points of the dispersed phase from a saturated phase. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Dynamics of Emerging Water Droplet Subjected to Sidewall with Different Wettabilities in a Fuel Cell Cathode Channel

On‐site experiments on low temperature fuel cells revealed that water droplets tend to emerge into the gas channel at the corner. This motivates the present investigation on the effects of the location where water emerges from and the wettability of sidewall on the dynamic behaviour of liquid water in gas channel by numerical simulations that employ the volume‐of‐fluid method. A microchannel with a square cross‐section of 0.25 mm in width and a pore of 0.05 mm in diameter is adopted. The simulation results for different pore locations and wettabilities of sidewall show that the behaviour of water droplet only depends on the wettability of bottom wall when it emerges from the centreline without attaching to the sidewall and gains the highest pressure drop. When the emergence location shifts towards the corner, the water droplet unavoidably attaches to the sidewall and thus the wettability of sidewall is found to have significant effects on its dynamics: hydrophobic sidewall results in droplet detachment and fast removal with the highest pressure drop and the minimal water saturation, whereas hydrophilic sidewall leads to a water film and accumulation with the lowest pressure drop and the minimal water coverage on the bottom wall.     

Identification of nucleation loci in emulsion polymerization processes. I. New information from spectroscopy studies

Particle nucleation is the forcing function in emulsion polymerization reactions and as such it plays a significant role in the development of most of the properties of the final latex. The locus of nucleation in emulsion polymerization remains a contentious issue. Recent developments in the spectroscopy of emulsions strongly suggest that the locus of particle nucleation is a population of small nano‐droplets of size range between 30–100 nanometers in diameter. These nano‐droplets are generated independently of the rate of initiator decomposition and appear to be functions only of the emulsification conditions. In this paper the simulation studies leading to the identification of the nano‐droplet population are described. The theoretical evidence suggesting that the nano‐droplets are the main loci of particle nucleation is presented and along with the recommendations for the experimental work. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2847–2857, 2006     

微柱表面液滴定壁温沸腾实验研究

利用高速摄像技术对去离子水液滴撞击微柱结构表面后的蒸发及核化过程进行观测。实验测得不同壁面温度下液滴蒸干时间,获得液滴沸腾曲线;发现相对光滑表面,微柱表面在50、60、70、80、120℃强化相变换热,120℃时强化比例最大,达到35.71%;壁温为90、100、110℃时,微柱表面无强化作用。从液滴直径和厚度的变化可知微柱表面液滴蒸发分为两个阶段：第一阶段,液滴直径不变,厚度变化;第二阶段,液滴厚度接近微柱高度,直径减小。随壁温升高,第一阶段时长显著缩短。液滴内部核化点密度和气泡平均直径随壁面温度的升高均有明显增大的趋势。需指出的是,液滴冲击对微柱表面液滴内部核化点分布有重要影响,受微柱结构及滴落冲击作用液滴内部成核气泡沿液滴半径呈辐射状分布。