Transient binary nucleation from ethanol-hexanol vapour

We study condensation of ethanol-hexanol vapour by numerical solution of kinetic equations. The number of droplets formed in unit volume is computed within self-consistent classical model. It is shown that formation of ethanol-rich droplets prevails at the initial stage of nucleation process, but in the stationary state formation of droplets near the saddle point (on cluster formation energy surface) plays the dominant role. Presented at the 6th Joint Seminar “Development of Materials Science in Research and Education”, Karlštejn, Czech Republic, 17–19 September 1996. This work was supported by Grant No. A1010615 of the Grant Agency of the Academy of Sciences of the Czech Republic.     

Stages of homogeneous nucleation in solid isotopic helium mixtures

We have made pressure and NMR measurements during the evolution of phase separation in solid helium isotopic mixtures. Our observations indicate clearly all three stages of the homogeneous nucleation-growth process: (1) creation of nucleation sites; (2) growth of the new-phase component at these nucleation sites; and (3) coarsening: the dissolution of subcritical droplets with the consequent further late-stage growth of the supercritical droplets. The time exponent for the coarsening, a=1/3, is consistent with the conserved order parameter Lifshitz-Slezov evaporation-condensation mechanism.     

Activated instability of homogeneous bubble nucleation and growth

For the superheated Lennard-Jones liquid, the free energy of forming a bubble with a given particle number and volume is calculated using density-functional theory. As conjectured, a consequence of known properties of the critical cavity [S. N. Punnathanam and D. S. Corti, J. Chem. Phys. 119, 10 224 (2003), the free energy surface terminates at a locus of instability. These stability limits reside, however, unexpectedly close to the saddle point. A new picture of homogeneous bubble nucleation and growth emerges from our study, being more appropriately described as an "activated instability."     

均匀核化过程中凝结核分维数研究

运用分子动力学模拟方法,对水蒸汽均匀核化凝结过程进行了研究.采用分形理论分维数统计中的小盒计数法,对二维条件下凝结核的分维数的变化规律进行了统计计算.模拟结果表明,水蒸汽均匀核化过程中所形成的凝结核表面的分维数并非一过程量,凝结核表面分维数并不随凝结核的长大而变化,当凝结核长大到一定程度后,其表面分维数将达到一恒定值.本文对初始温度为500℃,密度分别为100和200 kg/m3的过热水蒸气冷却到20℃的过程进行了模拟,水蒸汽在二维均匀核化过程中所形成的凝结核表面分维数为1.79.     

Molecular dynamics simulation of homogeneous nucleation of KBr cluster

We perform molecular dynamics simulations to study the homogeneous nucleation in the freezing of molten potassium bromide clusters. The nucleation rates tend to decrease with increasing cluster size and temperature. The solid-liquid interfacial free energy σ_sl of 42.4-52.3 mJ/m² is close to the values predicted by Turnbull's relation and comparable to the experimental observation by Buckle and Ubbelohde. It is interesting to find that there is no cluster size effect on the critical nucleus size. Critical nucleus sizes inferred from classical nucleation theory are of 6.5-20.7 K⁺Br⁻ ionic pairs in the temperature range of 400-600 K. The critical nucleus size at bulk MD freezing temperature obtained by extrapolation is about 45 K⁺Br⁻ ionic pairs, which is comparable to the experimental value of NaCl.     

Non-steady state homogeneous nucleation in glass-forming systems: Dimensionless kinetic equation

The kinetic equation of the classical homogeneous nucleation theory is rewritten in dimensionless form and it is shown that the numerical computation of the dimensionless kinetic equation is approximately 20 times faster in comparison with the original kinetic equation. The results are compared with known analytical results and with previous numerical results in the case of the constant and variable temperature for the model Li₂O.2 SiO₂ melt. It is shown, e.g., that under non-isothermal conditions the nucleation rate is greater than the quasistationary nucleation rate and the cluster distribution function is greater than the corresponding quasiequilibrium cluster distribution function.     

Microstructure of the supersaturation field in homogeneous nucleation in a vapor-gas mixture

An explanation of a significant difference between the modern experimental data on nucleation rate and the results of the classical theory of nucleation is proposed on the basis of analysis of the mass transfer during the growth of dropletlets from clusters. The continuous operation devices, viz., a laminar diffusion chamber and a diffusion chamber, are considered.     

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。     

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.     

The kinetics of homogeneous nucleation of silver nanoparticles stabilized by polymers

The formation of Ag nanoparticles synthesized by homogeneous nucleation, stabilized by polymers (PVA and PVP) was monitored by UV–Vis spectrophotometry and transmission electron microscopy. Our aim was to differentiate between the two main phases of particle formation, i.e. nucleation and growth and to characterize their rates with the help of appropriate kinetic equations. Time resolved spectrophotometric measurements revealed that particle formation is an autocatalytic process: a slow, continuous nucleation phase (3–5 min) is followed by a rapid, autocatalytic growth phase where the maximal particle size is 5–7 nm. By freezing the reaction mixture, the process of particle growth can be followed from 5 to 40 min on TEM pictures. The first order rate constants were calculated and they are strongly depend on the polymer concentration. If the growing particles are attached by PEI to the surface of a solid support, the formation of silver nanoparticles can also be followed by atomic force microscopy (AFM) and we can control the particle growth on mica surface. The cross section analysis of the pictures show, that the particle growing process can be also monitored at solid–liquid interface.     

On the homogeneous nucleation and propagation of dislocations under shock compression

The dynamic response of crystalline materials subjected to extreme shock compression is not well understood. The interaction between the propagating shock wave and the material’s defect occurs at the sub-nanosecond timescale which makes in situ experimental measurements very challenging. Therefore, computer simulation coupled with theoretical modelling and available experimental data is useful to determine the underlying physics behind shock-induced plasticity. In this work, multiscale dislocation dynamics plasticity (MDDP) calculations are carried out to simulate the mechanical response of copper reported at ultra-high strain rates shock loading. We compare the value of threshold stress for homogeneous nucleation obtained from elastodynamic solution and standard nucleation theory with MDDP predictions for copper single crystals oriented in the [0 0 1]. MDDP homogeneous nucleation simulations are then carried out to investigate several aspects of shock-induced deformation such as; stress profile characteristics, plastic relaxation, dislocation microstructure evolution and temperature rise behind the wave front. The computation results show that the stresses exhibit an elastic overshoot followed by rapid relaxation such that the 1D state of strain is transformed into a 3D state of strain due to plastic flow. We demonstrate that MDDP computations of the dislocation density, peak pressure, dynamics yielding and flow stress are in good agreement with recent experimental findings and compare well with the predictions of several dislocation-based continuum models. MDDP-based models for dislocation density evolution, saturation dislocation density, temperature rise due to plastic work and strain rate hardening are proposed. Additionally, we demonstrated using MDDP computations along with recent experimental reports the breakdown of the fourth power law of Swegle and Grady in the homogeneous nucleation regime.     

From homogeneous to heterogeneous nucleation of chain molecules under nanoscopic cylindrical confinement

The crystallization of monodisperse linear polyethylene confined in nanoporous alumina is investigated with the calorimetric measurements. We observe a drastic change in crystallization behavior, specifically nucleation, with a decrease in the pore diameter. Crystallization in relatively larger pores with the diameters of 62 and 110 nm occurs at lower temperatures within a very narrow range, whereas crystallization in smaller pores with diameters of 15-48 nm occurs at a higher and broad range of temperatures. Nucleation and crystallization kinetics in nanopores is discussed based on classical nucleation theory as well as the Avrami theory.     

On the validity of the capillarity approximation in the rate theory of homogeneous nucleation

An Einstein model is used to calculate the internal vibrational free energy of approximately spherical fcc crystallites as a function of crystallite size at T/θ = 1. It is found that the free energy per surface atom does not become convergent until a size of about 3 × 10⁷ atoms is reached. The excess free energy at convergence is used to define the macroscopic surface tension for use in the capillarity approximation. The internal free energy of microcrystallites containing of the order of 100 atoms is fortuitously well described by the capillarity approximation. A good estimate of the total free energy of the microcrystallite (nucleus) is obtained from the capillarity approximation only by adding the contributions from free translation and rotation and the replacement partition function.     

Two families of analytic γ-plots and their influence upon homogeneous nucleation kinetics

The equilibrium shapes corresponding to two different families of γ-plots are constructed. One γ-plot family comprises continuous variations from a sphere to an oblate ellipsoid. This set of γ-plots yields a sharp edge in the corresponding equilibrium shape when its aspect ratio is less than $\text{1}\text{√2}$. The other family consists of nephroids of revolution, varied in cross-sectional form from two slightly overlapping near-circles to an ellipse-like morphology. This family exhibits a facet at one boundary orientation in the equilibrium shape. For the analytical expression of the equilibrium shape, the ξ-vector formalism of Cahn and Hoffman is used and found to give results identical to those from the Euler-Lagrange method. The effects of the variations in equilibrium shape within the two families treated upon the principal parameters in the general equation for the time-dependent rate of nucleation are assessed in order to ascertain their relative influence on nucleation kinetics.     

Extended (n/v)-Stillinger cluster for use in the theory of homogeneous nucleation

In this paper we develop a theory for an extended version of the (n/v)-Stillinger cluster that has been used in nucleation theory, where n means the number of particles constituting the cluster characterized by the volume v. The "extended cluster" incorporates some of the surrounding supersaturated vapor. This cluster, although requiring more extensive simulation than the original (n/v)-Stillinger cluster, is almost devoid of approximation. It maintains the non-ad-hoc nature of the original (n/v)-Stillinger cluster implicitly. The theory of the cluster is also applicable to clusters which avoid redundancy by some other means than the so-called "connectivity requirement." Simulation of the extended cluster is now being implemented and will be used in the theory of the homogeneous nucleation rate.     

界面形核时间对GaN薄膜晶体质量的影响

利用金属有机化学气相沉积技术系统研究了界面形核时间对c面蓝宝石衬底上外延生长GaN薄膜晶体质量的影响机理. 用原子力显微镜、扫描电子显微镜、高分辨X射线衍射仪以及光致发光光谱仪表征材料的晶体质量以及光学性质. 随着形核时间的延长, 退火后形成的形核岛密度减小、尺寸增大、均匀性变差, 使得形核岛合并过程中产生的界面数量先减小后增大, 导致GaN外延层的螺位错和刃位错密度先减小后增大, 这与室温光致发光光谱中得到的带边发光峰与黄带发光峰的比值先增大后降低一致. 研究结果表明, 外延生长过程中, 界面形核时间会对GaN薄膜中的位错演变施加巨大影响, 从而导致GaN外延层的晶体质量以及光学性质的差异.     

Quantum transport for Bloch electrons in homogeneous time dependent electric fields

Quantum Transport Equations for Bloch electrons interacting with randomly distributed impurities in the presence of a homogeneous electric field of arbitrary strength and time dependence are derived. The equations account for all possible quantum effects to lowest nonzero order in the scattering strength, including intra and interband scattering, interband Zener tunneling and non-linear transient transport, and contain effects previously not anticipated, such as coherent impurity scattering, and field and time dependent scattering matrix elements.