Simulations of spinodal nucleation in systems with elastic interactions

Systems with long-range interactions quenched into a metastable state near the pseudospinodal exhibit nucleation that is qualitatively different from classical nucleation near the coexistence curve. We observe nucleation droplets in Langevin simulations of a two-dimensional model of martensitic transformations and determine that the structure of the nucleating droplet differs from the stable martensite structure. Our results, together with experimental measurements of the phonon dispersion curve, allow us to predict the nature of the droplet. The results have implications for nucleation in many solid-solid transitions and the structure of the final state.     

Stochastic Theory of Nucleation in Nonequilibrium Bistable Reaction Systems

Nucleation is one of the fundamental types of forming stable dissipative nonequilibrium structures in metastable initial states. The nucleation process of a bistable chemical reaction system is investigated. First a microdroplet with radius R₀ of the new state imbedded in the parent one is formed by a local particle number fluctuation. The radius of the microdroplet R(t) fluctuates due to the interference of reaction and diffusion. If R(t) considerably exceeds a critical value R_k the droplet starts to grow deterministically. The mean nucleation time of one droplet in weakly supersaturated systems is calculated using the concept of the mean first passage time.     

Influence of a continuous quenching procedure on the initial stages of spinodal decomposition

Instead of the standard assumption in the theory of phase separation where an instantaneous quench from an initial equilibrium state to the final state in the two-phase region is assumed, we consider the more realistic situation that the change of the external control parameter (e.g. temperature) can only be performed with finite rates. During the initial stages of spinodal decomposition the system then has some memory of the states intermediate between the initial and the final one. This influence of the finite quench rate in continuous quenching procedures is studied within the linearized theory of spinodal decomposition, with the Langer-Baron-Miller decoupling, and with Monte Carlo simulations. Both the case of thermally activated mobilities (applicable to solid metallic alloys) and the case of nearly temperature-independent mobilities (applicable to fluid polymer mixtures) are treated, and possible experimental applications are discussed. We find drastic deviations from the standard instantaneous quench situations in all cases of experimental interest.     

亚稳相的高压暴露

 很久以前,便有人指出,气态冷凝成固态时,要连续经历液相及各种高温相,才达到平衡结晶相。但是,液态及高温相往往需靠很大的冷却速度才能冻结下来,这在当时对绝大多数合金,是不可能的。近些年,随着超急冷等技术的进步,关于非晶等亚稳相得研究十分活跃。当超过一定临界冷却速度时,液态合金可固化为非晶态。虽然,亚稳结晶相较非晶应更容易冻结,但是,由于产生各种亚稳相所需的过冷条件各不相同,以及对冷却速度的选择不能是任意的,因此有时它们较非晶还难于形成。与液相凝固过程相似,非晶合金的晶化也服从构型最小重排原理,即在晶化完成之前,存在某些亚稳相变态阶段。但是,限于热力学上的不稳定性及动力学因素,在常压下这些亚稳相同样是难以发现的。作者根据对多种合金系的研究,提出高压暴露亚稳相的设想,并利用非晶等亚稳相的高压变态过程,将进行液态急冷时的速度控制方式,改为便于掌握的高压退火方式,来获得新亚稳相。本文对压力暴露亚稳相的原理和实践,加以论述。     

Diffraction of fast metastable atoms by micrometric reflection gratings

Diffraction of thermal velocity metastable atoms by non-magnetic and magnetic reflection gratings of micrometric period has been observed. This observation is made possible by the use of an ultra narrow beam generated by metastability exchange. Grazing incidence angles are exploited to minimise the quenching of metastable atoms on the grating surface. Potential applications are beam splitting, atom holography and probing of micro-sized solid surfaces.     

Observation of a registered phase in Cs/W(110)

RHEED and AES studies at room temperature have revealed a new metastable state of Cs ad-atoms on W(110) which are in registry at least along [1̄10] W. The ad-atom density in this state is 0.81 ± 0.03 ML, where 1 ML corresponds to the final density of Cs atoms in the saturated close packed hexagonal structure. This new structure has been observed as the final structure in dynamic deposition conditions, i.e. under the constant pressure of the Cs beam. The previously observed 1 ML structure arises when deposition and AES observations are alternated. The possibility that impurities provide the means of overcoming a nucleation barrier to this final structure is discussed.     

Resonant nucleation

We investigate the role played by fast quenching on the decay of metastable (or false vacuum) states. Instead of the exponentially slow decay rate per unit volume, Gamma(HN) approximately exp([-E(b)/k(B)T] (E(b) is the free energy of the critical bubble), predicted by homogeneous nucleation theory, we show that under fast enough quenching the decay rate is a power law Gamma(RN) approximately [E(b)/k(B)T](-B), where B is weakly sensitive to the temperature. For a range of parameters, large-amplitude oscillations about the metastable state trigger the resonant emergence of coherent subcritical configurations. Decay mechanisms for different E(b) are proposed and illustrated in a (2+1)-dimensional scalar field model.     

快速降压下Tween20 液滴真空闪蒸特性

为探究闪蒸喷雾冷却的微观机理, 设计并搭建了液滴悬挂式真空闪蒸实验装置, 利用可视化窗口探究Tween20 液滴闪蒸过程中的闪蒸特性及气泡生长机理. 液滴在快速降压过程中形态会经历气泡成核、气泡生长、伴随气泡生长、爆裂这四个阶段的变化, 并反复循环这一过程直至液滴稳定蒸发. 对于液滴温度的变化, 闪蒸室的终态压力起到了决定性的作用, 并且其终态温度随压力的升高明显上升. 同时通过液滴闪蒸过程形态图分析发现, 液滴在剧烈爆炸阶段其温度也发生明显下降; 在稳定蒸发阶段, 其温度也将开始稳定不变. 因此可知液滴的剧烈爆炸会带走其自身的大量热量. 而 Tween20 浓度对液滴温度的影响微乎其微, 但其会使液滴内气泡的初始成核时间发生明显滞后, 并抑制液滴内的气泡发生破裂.     

Phase transitions in condensed media at a finite rate of formation of a metastable state

The influence of the finite rate of formation of a metastable state on the kinetics of the first-order phase transition is analyzed. The conditions determined by the thermodynamic parameters and the cooling rate of the system under consideration are derived. Under these conditions, the formation of the metastable state can be treated either as an instantaneous process, when nucleation occurs at the end of the cooling stage, or as a slow process, when intensive nucleation of a new phase proceeds within the cooling stage. An equation describing the time and temperature that correspond to intensive nucleation of new-phase particles is obtained. The nucleation stage of the new phase takes place in the immediate vicinity of the temperature determined from this equation. All the other parameters, which determine the kinetics of the initial and transient stages of the phase transition, are calculated with respect to this temperature. As an example, all the relationships for a weak solid solution are presented.     

Predicting initial nucleation events occurred in a metastable nanodroplet during acoustic droplet vaporization

Acoustic droplet vaporization (ADV) capable of converting liquid perfluorocarbon (PFC) micro/nanodroplets into gaseous microbubbles has gained much attention due to its medical potentials. However, its physical mechanisms for nanodroplets have not been well understood due to the disappeared superharmonic focusing effect and the prominent Laplace pressure compared to microdroplets, especially for the initial ADV nucleation occurring in a metastable PFC nanodroplet. The classical nucleation theory (CNT) was modified to describe the ADV nucleation via combining the phase-change thermodynamics of perfluoropentane (PFP) and the Laplace pressure effect on PFP nanodroplets. The thermodynamics was exactly predicted by the Redlich–Kwong equation of state (EoS) rather than the van der Waals EoS, based on which the surface tension of the vapor nucleus as a crucial parameter in the CNT was successfully obtained to modify the CNT. Compared to the CNT, the modified CNT eliminated the intrinsic limitations of the CNT, and it predicted a larger nucleation rate and a lower ADV nucleation threshold, which agree much better with experimental results. Furthermore, it indicated that the nanodroplet properties exert very strong influences on the nucleation threshold instead of the acoustic parameters, providing a potential strategy with an appropriate droplet design to reduce the ADV nucleation threshold. This study may contribute to further understanding the ADV mechanism for PFC nanodroplets and promoting its potential theranostic applications in clinical practice.     

Enhancement of stability in randomly switching potential with metastable state

The overdamped motion of a Brownian particle in randomly switching piece-wise metastable linear potential shows noise enhanced stability (NES): the noise stabilizes the metastable system and the system remains in this state for a longer time than in the absence of white noise. The mean first passage time (MFPT) has a maximum at a finite value of white noise intensity. The analytical expression of MFPT in terms of the white noise intensity, the parameters of the potential barrier, and of the dichotomous noise is derived. The conditions for the NES phenomenon and the parameter region where the effect can be observed are obtained. The mean first passage time behaviors as a function of the mean flipping rate of the potential for unstable and metastable initial configurations are also analyzed. We observe the resonant activation phenomenon for initial metastable configuration of the potential profile.Received: 16 June 2004, Published online: 31 August 2004PACS: 05.40.-a Fluctuation phenomena, random processes, noise, and Brownian motion - 02.50.-r Probability theory, stochastic processes, and statistics - 05.10.Gg Stochastic analysis methods (Fokker-Planck, Langevin, etc.)     

Enhancement of lysozyme crystallization under ultrasound field

With the increasing demand for biopharmaceuticals, a method to crystallize biomolecule products with high quality, high yield and uniform size distribution as well as regular crystal habit is needed. In this work, ultrasound was used as a nucleation accelerator to decrease the energy barrier for lysozyme crystal formation. Crystallization experiments on egg-white lysozyme were carried out with and without ultrasound. The effect of ultrasound on induction time, metastable zone width, crystal size and morphology and process yield was investigated in detail. The nucleation-promoting effect produced by ultrasound is illustrated by the reduction of metastable zone width and induction time. By inducing faster nucleation, ultrasound leads to protein crystals grow at lower supersaturation levels with shorter induction time. It was found that ultrasound could result in uniform size distribution of the product due to the preventing of aggregation. However, long time continuous application of ultrasound could result in smaller particle size. Hence, ultrasonic-stop method was found to be a more appropriate strategy to enhance the crystallization process of proteins such as lysozyme.     

Curvature-dependent surface tension of a growing droplet

A ghost interface simulation technique is developed and applied to supersaturated Lennard-Jones liquid-vapor interfaces. It is shown that the surface tension decreases approximately linearly with the supersaturation ratio and that it vanishes at the spinodal. The effect leads to a curvature-dependent surface tension since, it is argued, the local supersaturation of the vapor above a droplet is greater than in the bulk due to slow diffusion in the vapor phase. An analytic approximation is given for the local supersaturation ratio, and an analytic expression for this contribution to Tolman's length is derived. The theory gives a smaller critical radius and reduces the free energy barrier to nucleation compared to classical homogeneous nucleation theory, which have important implications for the kinetics of droplet and bubble formation.     

Evidence for spinodal singularities in high-dimensional nearest-neighbor ising models

Conventional theories of nucleation predict that the metastable state has an average lifetime which monotonically decreases as the system is quenched further from the condensation point. However, theories based on the coarsegrained Ginzburg-Landau free energy functional seem to indicate that for systems above six dimensions there is a sharp spinodal dividing the metastable and unstable regimes where the lifetime of the metastable state diverges. Monte Carlo simulations are used to investigate this discrepency. Both nucleation rates and bulk susceptibility measurements seem to support the prediction of the Ginzburg-Landau theories.     

Formation of NI80P20 solid solution phase under pressure

A Ni-P solid solution phase was obtained by quenching of melts under a pressure of 4.5 GPa. This was considered as a metastable high pressure phase. Despite the lack of thermodynamic parameters for Ni₈₀, P₂₀ alloy under pressure, the degree of undercooling, nucleation frequency and crystal growth velocity were calculated. We conclude that metastable phases with the same composition as the melting phase, such as supersaturated solid solution phase and amorphous phase, are easily prepared by high-pressure quenching.     

Quenching dynamics of a quantum XY spin-1/2 chain in the presence of transverse field by the application of a generalized Landau-Zener formula

In this paper we review the quenching dynamics of a quantum XY spin-1/2 chain in the presence of a transverse field, when the transverse field or the anisotropic interaction is quenched at a slow but uniform rate. We also extend the results to the cases in which the system starts with any arbitrary initial condition as opposed to the initial fully magnetically aligned state which has been extensively studied earlier. The evolution is non-adiabatic in the time interval when the parameters are close to their critical values, and is adiabatic otherwise. The density of defects produced due to nonadiabatic transitions is calculated by mapping the many-particle system to an equivalent Landau-Zener problem. We show that in one dimension the density of defects in the final state scales as 1/√τ irrespective of the initial condition, where τ is the quenching time-scale. However, the magnitude of density of defects is found to depend on the initial condition.      

纳米结构超疏水表面冷凝现象的三维格子玻尔兹曼方法模拟

采用三维多相流格子玻尔兹曼方法 (lattice Boltzmann method, LBM),对纳米结构超疏水表面液滴的冷凝行为进行模拟研究.通过Laplace定律和光滑表面的本征接触角理论对三维LBM模型进行定量验证.模拟分析了超疏水表面纳米阵列的几何尺寸和润湿性的局部不均匀性对冷凝液滴形核位置和最终润湿状态的影响规律.结果表明,较高的纳米阵列使液滴在纳米结构间隙的上部侧面和底部优先形核长大,通过采用上下不均匀的间隙可避免液滴在底部形核长大,而在上部侧面形核的冷凝液滴在生长过程中向上运动,其润湿状态由Wenzel态转变为Cassie态;较低的纳米阵列使液滴在纳米结构底部优先形核长大,液滴的最终润湿状态为Wenzel态;润湿性不均匀的纳米结构表面使液滴在阵列顶端亲水位置处优先形核长大,成为Cassie态.冷凝液滴在不同几何尺寸的纳米结构表面上的最终润湿状态的模拟结果与文献报道的实验结果符合良好.通过模拟还发现,冷凝液滴在生长过程中的运动行为与液滴统计平均作用力的变化有关.本文的LBM模拟再现了三维空间中液滴的形核、长大和润湿状态转变等物理现象.     

Critical droplets near coexistence of wet and nonwet surface states

In first-order wetting transitions the decay of metastable states starts with a nucleation process on the wall of the system. For a planar wall the critical droplet has cylindrical symmetry and therefore should be described by two different critical lengths. We discuss these quantities and also the excess free energy of the critical droplet as functions of the spreading coefficient near coexistence of the wet and the nonwet state of the wall.     

Nucleation kinetics,growth and hardness parameters of l-alanine alaninium picrate (LAAP) single crystals

Amino acids are considered to be the building blocks of proteins and are gaining importance due to their interesting optical behavior. l-alanine is an amino acid which dissolves in water and it can react with other acids to form new compounds. In this work, l-alanine is mixed with picric acid to prepare l-alanine alaninium picrate (LAAP) salt. Solubility and metastable zone width were measured for LAAP salt and induction period was measured at different supersaturation ratios. The critical nucleation parameters were evaluated based on the classical theory of homogeneous nucleation. Using the optimized nucleation parameters, single crystals of LAAP salt were grown by slow evaporation technique. XRD and FTIR studies were carried out to understand structural and molecular formation of the crystal. Microhardness measurements were performed on the grown LAAP crystal and various parameters such as work hardening constant, stiffness constant, yield strength, resistance pressure and corrected hardness were evaluated. Nonlinear optical behavior of the sample was analyzed.