MECHANISM OF CRYSTALLIZATION IN AGITATED SOLUTIONS

A new concept of molecular cluster dynamics in turbulent flows is used to develop a physical model and mechanism of homogeneous and heterogeneous nucleation in solutions. The proposed physical model considers the motion of molecular clusters in centrifugal fields of free eddies induced in turbulent flows. The clusters are moved to an eddy boundary region where they are concentrated and aggregated to form critical nuclei.

It is shown theoretically that a critical fluid velocity exists, below which nuclei are not formed, and that its value depends upon the degree of solution supersaturation. The nucleation theory takes into account the hydrodynamic parameters of the process and permits calculation of the number of nuclei formed. Satisfactory agreement was obtained between calculated values and published experimental data.     

Mechanism of diamond epitaxial growth on silicon

According to this study and to our previously reported nucleation model, we can explain the mechanism of diamond heteroepitaxial growth as follows: microscopic nucleation sites, i.e. etching scars, bunching atomic steps, and grooves formed by growing SiC, are formed on the substrate surface at the beginning of the bias application and are related to the crystal orientation of the substrate. Carbon atoms that reach the substrate surface are trapped at the nucleation sites and form clusters. Since these clusters are in the embryonic form during ion irradiation, deformation, rotation and migration can easily take place to form clusters with shapes that correspond to the shapes of these sites. At the same time, the conversion from sp² to sp³ progresses, and diamond nuclei of critical sizes are thought to be formed. This phenomenon strongly suggests that the heteroepitaxial growth of diamond involves a graphoepitaxial process in the formation of a critical nucleus size. In this study, we examined in detail the effect of bias on substrates to clarify the mechanism of heteroepitaxial growth of diamond.     

十六烷/超临界CO2混合体系气泡成核的分子动力学模拟

研究了十六烷/超临界二氧化碳（CO2）混合体系的气泡成核过程。采用全原子分子动力学方法,选择等温-等压系统,使体系的粒子数、压力（P）和温度（T）保持不变,采用exp-6力场描述原子间的相互作用,采用距离判别法识别气泡核,根据气泡成核过程的分子位形跟踪气泡的形成过程。结果表明,降低十六烷/超临界CO2混合体系的P,首先形成了低密度的气泡核,然后CO2分子不断地进入气相,直至系统内部形成含有大量气相分子的气泡。     

Simulation of nucleation kinetics—an application to secondary nucleation

In order to study the effect of a disturbance on a supersaturated system (as occurs during secondary nucleation), the kinetics of the nucleation process has been simulated. During the process of secondary nucleation the currently accepted survival theory predicts that only clusters whose sizes are greater than the critical size will survive. This study has shown, however, that the critical size does not establish a sharp cutoff point. Rather, certain conditions can cause subcritical clusters (embryos) to survive and supercritical clusters (nuclei) to dissolve.     

A new hypothesis for cavitation nucleation in gas saturated solutions: Clustering of gas molecules lowers significantly the surface tension

Cavitation in water generally takes place at much lower negative pressure than predicted from theories. In this work, we try to stress the discrepancy from the influence of the dissolved gas on cavitation nucleation. By combining molecular dynamics simulation and thermodynamic analysis, we evaluated the lowering of surface tension as a function of density of gas molecules in gas clusters formed in aqueous solution. We found that the obtained surface tension of small gas clusters is much more substantially reduced than expected. The surface tension lowering and the non-ideality of gas molecules in the clusters are then taken into account in determining the nucleation of cavitation, and as a consequence, the required negative pressure for cavitation becomes comparable to experimental values. Thus, we give an alternative explanation for the discrepancy of cavitation pressure between experiment and theory, i.e., it is the substantially reduced surface tension for small gas nuclei, which have not been taken into account in theory, along with the ideal gas approxiamtion that induce its deviation from the experimental values.     

Analytical Approximation Schemes for Mean Nucleation Rate in Turbulent Flows

Nucleation rate is a very sensitive function of the temperature and vapor mole fraction. Analytical approximation schemes for the mean nucleation rate in turbulent flows are derived using Laplace’s approximation method. The schemes only require the derivative of the nucleation rate function and the probability density function (pdf) of the vapor mole fraction and/or temperature at the point of maximum nucleation rate. Based on the relation between the mole fraction and temperature, i.e., linearly correlated or not, different approximation schemes are developed. Numerical examples are constructed to investigate the accuracy of these approximation. In the examples, the pdfs of mole fraction and/or temperature in various turbulent flows are assumed to come from the beta distribution with five distinct forms. The mean nucleation rate of dibutyl phthalate (DBP) aerosol in these turbulent flows are calculated from the approximation schemes, and compared with exact numerical integration. The relative errors are less than 1% for cases when nucleation rate diminishes at the bounds of temperature fluctuations, and no more than 50% for all studied examples. Furthermore, the approximation schemes are not sensitive to the precise form of the pdfs. Hence, these developed approximation schemes can be used to estimate the mean nucleation rate in a broad range of turbulent flows conveniently.

Copyright 2014 American Association for Aerosol Research     

Modelling nucleation in wet granulation

Nucleation is the first stage in any granulation process where binder liquid first comes into contact with the powder. This paper investigates the nucleation process where binder liquid is added to a fine powder with a spray nozzle. The dimensionless spray flux approach of Hapgood et al. (Powder Technol. 141 (2004) 20) is extended to account for nonuniform spray patterns and allow for overlap of nuclei granules rather than spray drops. A dimensionless nuclei distribution function which describes the effects of the design and operating parameters of the nucleation process (binder spray characteristics, the nucleation area ratio between droplets and nuclei and the powder bed velocity) on the fractional surface area coverage of nuclei on a moving powder bed is developed. From this starting point, a Monte Carlo nucleation model that simulates full nuclei size distributions as a function of the design and operating parameters that were implemented in the dimensionless nuclei distribution function is developed. The nucleation model was then used to investigate the effects of the design and operating parameters on the formed nuclei size distributions and to correlate these effects to changes of the dimensionless nuclei distribution function. Model simulations also showed that it is possible to predict nuclei size distributions beyond the drop controlled nucleation regime in Hapgood's nucleation regime map. Qualitative comparison of model simulations and experimental nucleation data showed similar shapes of the nuclei size distributions. In its current form, the nucleation model can replace the nucleation term in one-dimensional population balance models describing wet granulation processes. Implementation of more sophisticated nucleation kinetics can make the model applicable to multi-dimensional population balance models.     

微孔塑料挤出成型中气泡成核的聚合物刷子模型

气泡成核是微孔塑料连续挤出成型中的关键步骤之一，临界气泡核直径是影响制品中泡孔直径的主要因素，成核密度则是影响制品泡孔密度的主要因素，但现有的成核理论大都是以经典成核理论为基础的，而经典成核理论虽然人出了临界气泡核及成核速率的计算公式，但并没有考虑到聚合物的物性参数，并且不能计算临界气泡核半径的具体数值，所以其应用有很大的局限性，从聚合物刷子模型出发建立气泡成核的刷子模型，从而得出临界气泡核半径的计算公式，并分析温度，压力，聚合物相对分子质量等对临界气泡核半径的影响。     

气固并流向上流动中颗粒聚集的机理

1 INTRODUCTION Cocurrent upward gas-solid flows are widely used in industrial situations such as circulating fluid- ized bed, fluid catalytic cracking and pneumatic transport. Due to its industrial relevance, many quan- titative experimental and numerical investigations have been carried out[1―4]. Investigations show that upward gas-solid flow always appears heterogenously structured and the distribution of particles is always non-uniform unless the solid phase is very dense or very dilut…     

气固并流向上流动中颗粒聚集的机理

Two-dimensional unsteady cocurrent upward gas-solid flows in the vertical channel are simulated and the mechanisms of particles accumulation are analyzed according to the simulation results. The gaseous turbulent flow is simulated using the large eddy simulation （LES） method and the solid phase is treated using the Lagrangian approach, and the motion of the gas and particles are coupled. The formation of clusters and the accumulation of particles near the wall in dense gas-solid flows are demonstrated even if the particle-particle collisions were ignored. It is found that a cluster grows up by capturing the particles in the dilute phase due to its lower vertical velocity. By this way the small size clusters can evolve to large-scale clusters. Due to the interaction of gas and particles, the large-scale vortices appear in the channel and the boundary layer separates from the wall, which results in very high particle concentration in the near wall region and a very large-scale cluster formed near the separation point.     

Electrochemical nucleation of mercury on platinum in the presence of organic additives

The electrochemical nucleation of mercury on a platinum electrode has been studied in the presence of some organic compounds used in the deposition of bright galvanic coatings. It is established that these organic additives do not effect the thermodynamics of the nucleation process but block the electrode surface, thus decreasing the rate of nucleus formation. It is found that the growth of the stable metal clusters is inhibited in the presence of the organic substances which leads to a marked increase of the maximal number of nuclei formed on the electrode surface.     

Fluctuation-assisted nucleation in the phase separation/crystallization of iPP/OBC blends

This work mainly focused on the nucleation behavior in iPP/OBC (isotactic polypropylene/polyolefin block copolymers) blends with two distinct OBCs. The influence of composition and molecular structure of the OBC component on the crystallization kinetics of the blends was investigated systematically with the aim to better understand the interplay between the two coupled phase transitions in the blends: macrophase separation and crystallization. The isothermal crystallization kinetics showed component and composition dependence in iPP/OBC blends. All the blends in the studied range have enhanced nucleation ability of iPP than the pure iPP under identical conditions. Furthermore, the distinct macrophase separation morphology resulting from the different compatibility between the various OBCs and iPP caused remarkable diversity between the blends: the nuclei density is qualitatively higher (or the nucleation rate is qualitatively faster) in the more compatible blends, and this enhancement of nucleation can be depressed by imposing a macrophase separation process before crystallization. The crystal nuclei from the phase separated matrix were preferentially formed at the interface of the phase domains, and then grew toward and into the iPP-rich phase. It is postulated that the increased nuclei density and/or nucleation rate followed the fluctuation-assisted nucleation mechanism: the enhanced concentration fluctuation at the interfacial area created by the spinodal decomposition played an important role in the nucleation behavior of iPP/OBC blends. The decreased interface areas with increased domain sizes after deeper phase separation, coupled with a more depressed concentration fluctuation, are responsible for lower nuclei density after long time annealing for phase separation.     

Homogeneous nucleation rate at various initial supersaturations in a closed system

The rate of formation of nuclei in a closed system is studied by numerical solution of kinetic equations at various supersaturations. Depletion of vapor (decrease of supersaturation) due to the phase transition process is taken into account. At a relatively low value of initial supersaturations, the decrease of supersaturation is negligible. At somewhat higher initial supersaturations, the phase transition process is more intense and the decrease of supersaturation plays an important role. As a consequence the nucleation rate after reaching a maximum decreases with time and for sufficiently long times only the nuclei of certain size are formed. At high initial supersaturation the nucleation rate for subcritical cluster sizes is negative, i.e. the number of subcritical clusters tends to get reduced. Critical size increases with time due to lowered supersaturation.     

A coupled CFD-Monte Carlo method for simulating complex aerosol dynamics in turbulent flows

A coupled computational fluid dynamics (CFD)-Monte Carlo method is presented to simulate complex aerosol dynamics in turbulent flows. A Lagrangian particle method-based probability density function (PDF) transport equation is formulated to solve the population balance equation (PBE) of aerosol particles. The formulated CFD-Monte Carlo method allows investigating the interaction between turbulence and aerosol dynamics and incorporating individual aerosol dynamic kernels as well as obtaining full particle size distribution (PSD). Several typical cases of aerosol dynamic processes including turbulent coagulation, nucleation and growth are studied and compared to the sectional method with excellent agreement. Coagulation in both laminar and turbulent flows is simulated and compared to demonstrate the effect of turbulence on aerosol dynamics. The effect of jet Reynolds (Re_j) number on aerosol dynamics in turbulent flows is fully investigated for each of the studied cases. The results demonstrate that Re_j number has significant impact on a single aerosol dynamic process (e.g., coagulation) and the simultaneous competitive aerosol dynamic processes in turbulent flows. This newly modified CFD-Monte Carlo/PDF method renders an efficient method for simulating complex aerosol dynamics in turbulent flows and provides a better insight into the interactions between turbulence and the full PSD of aerosol particles.

Copyright © 2017 American Association for Aerosol Research     

Numerical Simulation on Gas-Solid Two-Phase Turbulent Flow in FCC Riser Reactors(Ⅰ) Turbulent Gas-Solid Flow-Reaction Model

Gas-solid two-phase turbulent flows,mass transfer,heat transfer and catalytic cracking reactions areknown to exert interrelated influences in commercial fluid catalytic cracking(FCC)riser reactors.In the presentpaper,a three-dimensional turbulent gas-solid two-phase flow-reaction model for FCC riser reactors was devel-oped.The model took into account the gas-solid two-phase turbulent flows,inter-phase heat transfer,masstransfer,catalytic cracking reactions and their interrelated influence.The k-V-k_P two-phase turbulence modelwas employed and modified for the two-phase turbulent flow patterns with relatively high particle concentration.Boundary conditions for the flow-reaction model were given.Related numerical algorithm was formed and a nu-merical code was drawn up.Numerical modeling for commercial FCC riser reactors could be carried out with thepresented model.     

Aerosol Particle Removal and Re-entrainment in Turbulent Channel Flows - A Direct Numerical Simulation Approach

Aerosol particle removal and re-entrainment in turbulent channel flows are studied. The instantaneous fluid velocity field is generated by the direct numerical simulation (DNS) of the Navier - Stokes equation via a pseudospectral method. Particle removal mechanisms in turbulent channel flows are examined and the effects of hydrodynamic forces, torques and the near-wall coherent vorticity are discussed. The particle resuspension rates are evaluated, and the results are compared with the model of Reeks. The particle equation of motion used includes the hydrodynamic, the Brownian, the shearinduced lift and the gravitational forces. An ensemble of 8192 particles is used for particle resuspension and the subsequent trajectory analyses. It is found that large-size particles move away roughly perpendicular to the wall due to the action of the lift force. Small particles, however, follow the upward flows formed by the near-wall eddies in the low-speed streak regions. Thus, turbulent near-wall vortical structures play an important role in small particle resuspension, while the lift is an important factor for reentrainment of large particles. The simulation results suggests that small particles (with τ_p⁺ ≤ 0.023) primarily move away from the wall in the low-speed streaks, while larger particles (with τ_p⁺ ≥ 780) are mostly removed in the high-speed streaks.     

Parameterization for Atmospheric New-Particle Formation: Application to a System Involving Sulfuric Acid and Condensable Water-Soluble Organic Vapors

A new parameterization for atmospheric new-particle formation has been developed. The parameterization takes into account the early growth of nucleated clusters by condensation of sulfuric acid and water-soluble organic vapors, as well as the scavenging of the growing nuclei by coagulation into larger pre-existing particles. The main input parameters are the nucleation rate, the concentration of sulfuric acid and organic vapor(s) contributing to the nuclei growth, and the pre-existing particle size distribution. The resulting output quantity is the formation rate of particles at a desired size, typically a few nanometers of particle diameter. Comparisons to detailed numerical simulations demonstrated that the parameterization is relatively accurate when the nucleation rate, condensable vapor concentrations, and nuclei growth rate change sufficiently slowly with time, and when the nucleation rate is not very high. As such, the parameterization is most applicable to“regional nucleation events,”in which new-particle formation occurs over distances of tens to hundreds of kilometers. The main obstacle in applying the new parameterization is that organic vapors contributing to the early growth of nucleated clusters have not been identified so far. A couple of solutions to this problem are proposed.     

Effect of the Growth Treatment on Two-Stage Nucleation Experiments

Numerical simulations are presented that document the strong effect of a previously underappreciated portion of two-stage thermal treatments used in the study of nucleation processes: the "heat-up" process whereby samples are heated from "nucleation" conditions to "growth" conditions. The simulations indicate that two limiting regimes exist, dependent on (a) the cluster size distribution of as-quenched glasses, (b) the temperatures used for nucleation and growth, and (c) the rates of heating and cooling: (1) all clusters larger than the critical size at growth conditions ( n ^*_gr) will grow to macroscopic size (the "standard" case); and (2) all clusters larger than the critical size at nucleation conditions ( n ^*_nuc) will grow to macroscopic size. In addition, cases in which the "effective critical size" ( n ^*_eff) is intermediate between n ^*_gr and n ^*_nuc can also occur. Cases in which n ^*_eff < n ^*_gr is manifested during nucleation experiments as an abrupt boost in crystal number density during the heat-up from nucleation to growth conditions, as all clusters larger than n ^*_eff are rapidly "flushed" past n ^*_gr. For the system studied herein, this can lead to a 10⁶-fold increase in final number density within seconds to a few minutes. Finally, the importance of structural relaxation for this process is demonstrated by examining a case in which the nucleation temperature is below the nominal glass transition temperature.