Simulation of supersaturated vapor nucleation on molecular condensation nuclei

The results of model calculations of nucleation of di(2-ethylhexyl)sebacate (DEHS) supersatu-rated vapor on FeO molecules based of the simplest structural models of clusters are considered. The earlier conclusion that the allowance for the escape of a molecular condensation nucleus (MCN) from a cluster weakly affects the results of analysis of nucleation on a MCN is confirmed. It is found that the interaction of electric charges of the FeO molecule and the ester groups of the DEHS molecule plays the important role in the DEHS nucleation. The importance of the strength of the bond between the MCN and the first condensate molecule is established. The strength of this bond considerably affects the coefficient of conversion of the MCN into aerosol particles as well as the form of the dependence of this quantity on the spontaneous condensation background.     

Thermodynamics of supersaturated vapor nucleation on molecular condensation nuclei

A key problem in the theory of a supersaturated vapor nucleation on molecular condensation nuclei (namely, the work of formation and the equilibrium concentrations of clusters) is considered. To calculate these quantities using the structural models of clusters, which are better suited for this purpose than the classical droplet model, we derive the equation connecting the work of transfer of a molecular condensation nucleus from the gas phase to a homogeneous cluster with a change in the number of contacts between molecules, occurring in the course of this transfer, and with the work of rupture of individual contacts.     

可膨胀过热水系统多气核演化过程与临界过热度分析

使用分子动力学方法,研究过热水系统均质沸腾核化过程.采用Langevin 动力学方法控制体积可变系统的温度与压力,更好地模拟了沸腾实际物理过程.得到了液相系统体积连续膨胀、分子间距逐渐增大,最终稳定在汽相的现象学规律.当过热温度较高时,亚稳态液相系统可能在局部形成不同大小的近球形区域：气核,这些气核是不稳定的,处于不断演化之中.通过分析分子所受引力与斥力的共同作用,得到了气核形成与消亡以及多个气核融合的机理.比较了模拟结果与经典沸腾理论的差异,提出了气核生长是比气泡生长更为微观过程的认识.通过研究不同过热 关键词： 过热水系统 分子动力学 气核 临界过热度     

Sound amplification in a supersaturated vapor

A sound wave in supersaturated water vapor can produce the process of heat release caused by condensation, which occures to be in phase with sound. The resonance interaction of sound with modulated heat release provides the sound amplification and the spectra of raindrops changes.     

Liquid nucleation at superheated grain boundaries

Grain boundaries with relatively low energies can be superheated above the melting temperature and eventually melt by heterogeneous nucleation of liquid droplets. We propose a thermodynamic model of this process based on the sharp-interface approximation with a disjoining potential. The distinct feature of the model is its ability to predict the shape and size of the critical nucleus by using a variational approach. The model reduces to the classical nucleation theory in the limit of large nuclei but is more general and remains valid for small nuclei. Contrary to the classical nucleation theory, the model predicts the existence of a critical temperature of superheating and offers a simple formula for its calculation. The model is tested against molecular dynamic simulations in which liquid nuclei at a superheated boundary were obtained by an adiabatic trapping procedure. The simulation results demonstrate a reassuring consistency with the model.     

Computer simulation of water vapor nucleation on charged nanoparticles

The Monte Carlo method is applied to the study of the formation of condensed-phase nuclei from water vapor on electrically charged silver iodide nanocrystals. This study is a continuation of the investigations carried out earlier in [1] with electrically neutral nucleation centers. Nanoparticles with a size of up to 4 nm and flat nanoparticles with a size of up to 10 nm are investigated. The free energy, entropy, and the work of formation of nuclei with a size of up to 6729 molecules are calculated at the atomic level by the bicanonical statistical ensemble (BSE) method at a temperature of 260 K. Thermodynamic stability of nuclei is investigated depending on the size, shape, and charge of nanocrystal nucleation centers, as well as depending on the presence of crystal defects and the degree of spatial localization of charge on the surface of nanoparticles. The excess charge has a crucial effect on the work of formation of a nucleus only in the case of strong spatial localization of the latter near a point crystal defect; however, this effect is restricted to a relatively small size of the nuclei and therefore cannot substantially enhance the ice-forming activity of nanoparticles. A nucleus that grows on the surface of a nanoparticle evolves through three stages that differ in molecule retention mechanism and thermodynamic stability. The charge of a nanoparticle has a small effect on these factors. The leading factor that determines the ice-forming activity of ion nanocrystals is their intrinsic electric field due to the nonuniform distribution of charge within a unit cell of the crystal lattice.     

Numerical simulation of water vapor nucleation on electrically neutral nanoparticles

Atomic-level Monte Carlo simulations are performed to calculate the free energy, entropy, and work of nucleation for clusters of more than 6 × 10³ water molecules growing on silver iodide crystalline particles of size up to 4 nm at a temperature of 260 K. The Hamiltonian of the system includes explicit expressions for hydrogen bonding energy and Coulomb, dispersion, exchange, and polarization interactions. The work of nucleation exhibits complex behavior depending on the nucleation-site size. With increasing nanoparticle size, clusters become less stable and the probability of crystallization increases. Mutual polarization enhances the bonding between a cluster and a crystalline particle. Cluster growth on relatively large nanoparticles involves two stages characterized by two critical sizes: monolayer growth on the surface and growth normal to the surface. Spontaneous microdroplet polarization involving domain formation is found to occur at the crystal surface. The dependence of the ice-forming activity of an aerosol on particulate size observed in experiments is explained by combined effects of several competing factors, the dominant ones being the stabilizing and destabilizing effects of the nanoparticle electric field.     

Characteristics of acoustic emissions during nucleation of superheated droplets

Superheated droplet nucleation and subsequent bubble oscillation produces an acoustic pressure pulse that contains valuable information about the nucleation process. Spectral analysis of the pressure pulse indicates excitation of different modes of bubble oscillations in the nucleation process. In the present study it is observed that gamma induced droplet nucleation excites higher modal oscillations and also emits higher intensity acoustic emission compared to that of spontaneous nucleations.     

Water vapor condensation and the collapse of superheated water drops as possible causes of ball lightning

Ball lightning is modeled by the bulk of humid air heated to temperatures of 600–650 K and containing a multitude of charged drops and microbubbles of size 10⁻⁵ cm or less, as well as water vapor heated to a near-critical temperature. The condensation of the vapor in the microbubbles, followed by the cooling of resulting droplets, generates energy spent on the thermal radiation of ball lightning. The radiation of light and radio waves is explained by the motion of ions and electrons in the electric field of charged bubbles and droplets and by the thermal rotational motion of charged droplets. As a result of coagulation, the droplets overheat and tend to collapse. An external electric field, supersaturated water vapor condensation, and a number of other factors may contribute to the ball lightning explosion energy.     

Classical theory of homogeneous nucleation in superheated liquids and its experimental verification

This work summarizes the cycle of investigations devoted to determination of the character of superheated liquid boiling-up in a glass capillary at the boundary of the attainable superheating. The brief history of studies is followed by a brief introduction into the theory of homogeneous nucleation. The result of the targeted experiments determining stationarity of a random process of a supercritical embryo generation is considered. From the experiments it may be concluded that the process is unsteady. Based on a large selection of life spans of superheated liquids, the authors have made parametric and nonparametric evaluations of the functions of distribution and dependence of boiling-up frequency on time. The comparison of the obtained results with exponential distribution shows significant differences that also prove the nonstationarity of the studied random process. Special experiments and calculations for evaluation of homogeneity of the superheated liquid boilingup at the boundary of attainable superheating are considered. It is shown that in the experiments with glass capillary, the boiling-up occurs on the wall. As the most convincing evidence of heterogeneity of the superheated liquid boiling-up in a glass capillary the authors provide the results of high-speed video filming in a silylated and clean capillaries.     

过热液氦均匀核化速率的确定

预测不同压力下过热液氦的均匀核化速率是十分重要的,它与液氦的极限过热度密切相关。文中通过回顾动力学理论、分子聚集理论、涨落理论等研究液体均匀核化的方法,对过热液氦的均匀核化速率进行了计算,并且对各种方法进行了比较与分析。结果表明,用能量涨落理论来计算过热液氦的均匀核化速率是一种比较合理的方法。     

Pre-nucleation relaxation phenomenon in electric field induced nucleation in superheated liquids

Pre-nucleation relaxation phenomenon in electric field induced nucleation in liquids has been observed at subcritical fields. The relaxation times τ in the processes of the application of electric field and induced nucleation have been measured. τ is found to be function of the degree of superheat of the liquid.     

Breakdown of the superheated Meissner state and spontaneous vortex nucleation in type II superconductors

The theory of local stability of the superheated Meissner state presented in an earlier paper is supplemented by an investigation of global stability in two dimensions. We conclude that flux penetration cannot be delayed beyond the fieldH _s1 where local instability sets in. Various new two-dimensional Ginzburg-Landau solutions, obtained numerically, are discussed. These include the lowest saddle point separating the Meissner from the normal and vortex state and a solution resembling the “nascent vortex state” whose existence was postulated recently by Walton and Rosenblum. Using these solutions the process of spontaneous vortex nucleation is discussed.     

Boiling-up of superheated water and water solutions under ultrasound influence

Boiling-up kinetics of superheated distilled water and sodium chloride solution in a glass cell at atmospheric pressure and low superheating of 15–35 °C has been studied far from the boundary of attainable superheating in the area of heterogeneous nucleation. Temperature dependences of average waiting time of superheated liquids boiling-up have been studied experimentally under natural conditions and in the ultrasonic field Waiting time of boiling-up at these temperatures reaches 1000 s, and average time is 600 s. Empirical distribution functions have been found with the use of the waiting time samples obtained by the method of order statistics. Omega-square goodness-of-fit test has shown that they disagree with exponential distribution describing stationary random process of supercritical embryo generation separating the system to macroscopic phases. Thus, it is shown that this random process is not stationary, consequently, nucleation rate to be depending on time.     

Effect of diffusion on nucleation of 2D and 3D nanoclusters in supersaturated solutions

The effect of diffusion on the steady-state nucleation of 2D and 3D nanoclusters is described analytically. Proposed approach takes self-consistently into account coupling between the kinetics of monomers near the cluster boundary, their diffusion and annihilation at other clusters. It has been shown that due to this coupling the nucleation barriers can considerably differ from those predicted by the thermodynamic approach.     

Transient behavior of superheated water jets boiling

Superheated water flowing out from high-pressure chamber through short cylindrical and slot channel has been studied experimentally. Relation of vaporization mechanisms in superheated liquid (boiling in single, not interacting centers, intense heterogeneous vaporization, and homogeneous fluctuating nucleation) and respective forms of superheated water jets has been determined. Temperature intervals with transient behavior of boiling have been determined. It is shown that at transient behavior of boiling the amplitude of pulsations of jet parameters increases, and in the spectra of pulsation power, the low-frequency component 1/f appears.     

New criterion for comparison of classical theory of nucleation in superheated liquids with experimental data

We have obtained inequality $ 1 - {{\Delta \bar \tau } \mathord{\left/ {\vphantom {{\Delta \bar \tau } {\bar \tau }}} \right. \kern-\nulldelimiterspace} {\bar \tau }} < \left( {J \cdot V \cdot \bar \tau } \right)^{ - 1} < 1 + {{\Delta \bar \tau } \mathord{\left/ {\vphantom {{\Delta \bar \tau } {\bar \tau }}} \right. \kern-\nulldelimiterspace} {\bar \tau }} $ 1 - {{\Delta \bar \tau } \mathord{\left/ {\vphantom {{\Delta \bar \tau } {\bar \tau }}} \right. \kern-\nulldelimiterspace} {\bar \tau }} < \left( {J \cdot V \cdot \bar \tau } \right)^{ - 1} < 1 + {{\Delta \bar \tau } \mathord{\left/ {\vphantom {{\Delta \bar \tau } {\bar \tau }}} \right. \kern-\nulldelimiterspace} {\bar \tau }} , where J is the frequency of homogeneous nucleation, V and $ \bar \tau $ \bar \tau are, respectively, volume and average lifetime of the superheated liquid, and $ {{\Delta \bar \tau } \mathord{\left/ {\vphantom {{\Delta \bar \tau } {\bar \tau }}} \right. \kern-\nulldelimiterspace} {\bar \tau }} $ {{\Delta \bar \tau } \mathord{\left/ {\vphantom {{\Delta \bar \tau } {\bar \tau }}} \right. \kern-\nulldelimiterspace} {\bar \tau }} is relative statistical error $ \bar \tau $ \bar \tau . Inequality appears to be a consequence of nucleation homogeneity and stability used at its deduction and taken in the theory as initial and determinant assumption. Calculations with the use of experimental data for the boundaries of the attainable superheating show that inequality is not satisfied. Thus, experimental data can not be considered a proof of the theory fundamentals.