Kinetics of nucleation of the solid phase in supercooled solutions or liquids under heat-insulating conditions: Intensive nucleation stage

The kinetics of decomposition of a supercooled melt or a viscous fluid under heat-insulating conditions during intensive nucleation has been investigated. Particles of a new phase have been studied, whose size is larger than the critical value, and for which the times are longer than the settling time of the classical quasi-steady state, which is characteristic of subcritical nuclei. The heat removal from the phase boundary is assumed to be the key process in the vicinity of a growing particle. The estimates of the duration of the stage of intensive nucleation, the maximum number of nucleated particles, and their average “size” have been obtained. Numerical simulations have been performed for nickel.     

Two-dimensional nucleation of ice from supercooled water

We report the temperature dependent nucleation rates of ice from single water drops supporting aliphatic alcohol Langmuir films. Analysis in the context of a classical theory of heterogeneous nucleation suggests that the critical nucleus is essentially a monolayer, and that the rate-limiting steps in these nucleation processes are therefore not merely influenced by, but instead dictated by, the physics of the water-alcohol interface. Consequently, reduced dimensionality may be much more important in heterogeneous nucleation than has previously been believed.     

深过冷Ni-15％Sn合金熔体表面张力研究

在电磁悬浮下实现了Ni-15％Sn合金的深过冷，最大过冷度为265K(0.16T_L)，结合悬浮液滴振荡法实验测定了Ni-15％Sn合金在1368—1915K范围内的表面张力.实验表明，在所测量温度范围内，表面张力随温度增加，连续线性递减，函数关系式为σ_Ni-15%Sn=1316.7—1.01(T-T_L)mN／m.根据表面张力的实验数据，理论计算了该合金的黏度系数和扩散系数，并在此基础上研究了合金的扩散激活能E_D和黏液活 关键词： 深过冷 电磁悬浮 表面张力 黏度系数 扩散系数     

Suppression of ice nucleation in supercooled water under temperature gradients

Understanding the behaviours of ice nucleation in non-isothermal conditions is of great importance for the preparation and retention of supercooled water. Here ice nucleation in supercooled water under temperature gradients is analyzed thermodynamically based on classical nucleation theory (CNT). Given that the free energy barrier for nucleation is dependent on temperature, different from a uniform temperature usually used in CNT, an assumption of linear temperature distribution in the ice nucleus was made and taken into consideration in analysis. The critical radius of the ice nucleus for nucleation and the corresponding nucleation model in the presence of a temperature gradient were obtained. It is observed that the critical radius is determined not only by the degree of supercooling, the only dependence in CNT, but also by the temperature gradient and even the Young's contact angle. Effects of temperature gradient on the change in free energy, critical radius, nucleation barrier and nucleation rate with different contact angles and degrees of supercooling are illustrated successively. The results show that a temperature gradient will increase the nucleation barrier and decrease the nucleation rate, particularly in the cases of large contact angle and low degree of supercooling. In addition, there is a critical temperature gradient for a given degree of supercooling and contact angle, at the higher of which the nucleation can be suppressed completely.     

Kinetics of isothermal homogeneous-condensation processes

Isothermal condensation of supersaturated vapors of various substances and formation of lampblack particles by isothermal decomposition of hydrocarbon (acetylene) molecules is investigated by analytic methods. Expressions that differ generally from the classical ones are obtained, on the basis of the quasichemical model of cluster particles, for the quasi-equilibrium and stationary distribution functions of the cluster sizes, as well as for the rates of formation of clusters having critical dimensions. Analytic expressions describing the time evolution of the degree of supersaturation and of the size distribution function of condensed cluster particles are obtained for the case when the system goes over from the supersaturated state to thermodynamic equilibrium. Equations for the principal characteristics of lampblack formation, viz., the characteristic time and the average size and density of the lampblack particles, are obtained with allowance for the properties of the formation and dissociation (evaporation) of small lampblack cluster particles.Translated from Trudy Ordena Lenina Fizicheskogo Instituta im. P. N. Lebedeva AN SSSR, Vol. 145, pp. 189–219, 1984.     

Kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation

The kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation process have been investigated by molecular dynamics simulations, and the microstructure evolution analyzed by the cluster-type index method (CTIM) and the tracing method. It has been found that, the dynamic features are consistently correlated with the microstructure evolution and the crystallization characteristics in the mean square displacement (MSD) and the non-Gaussian parameter (NGP): the β relaxation regime corresponds to the minor structural rearrangement because of the “cage effect”, and the atoms attempt to escape from the “cages”; the α relaxation regime is related to a more diffusive movement of atoms, and the appearance of the second plateau in MSD and the non-zero plateau in NGP corresponds to the completion of crystallization. In addition, three distinct stages of nucleation, growth of nuclei and coarsening of crystallites in the crystallization process have been clearly revealed.     

The effect of two-dimensional of a crystal interface in shear flow on the stability a supercooled melt

A model is developed based on the time-related thermal diffusion equations to investigate the effects of twodimensional shear flow on the stability of a crystal interface in the supercooled melt of a pure substance. Similar to the three-dimensional shear flow as described in our previous paper, the two-dimensional shear flow can also be found to reduce the growth rate of perturbation amplitude. However, compared with the case of the Laplace equation for a steady-state thermal diffusion field, due to the existence of time partial derivatives of the temperature fields in the diffusion equation the absolute value of the gradients of the temperature fields increases, therefore destabilizing the interface. The circular interface is more unstable than in the case of Laplace equation without time partial derivatives. The critical stability radius of the crystal interface increases with shearing rate increasing. The stability effect of shear flow decreases remarkably with the increase of melt undercooling.     

The effect of two-dimensional shear flow on the stability of a crystal interface in a supercooled melt

A model is developed based on the time-related thermal diffusion equations to investigate the effects of twodimensional shear flow on the stability of a crystal interface in the supercooled melt of a pure substance.Similar to the three-dimensional shear flow as described in our previous paper,the two-dimensional shear flow can also be found to reduce the growth rate of perturbation amplitude.However,compared with the case of the Laplace equation for a steady-state thermal diffusion field,due to the existence of time partial derivatives of the temperature fields in the diffusion equation the absolute value of the gradients of the temperature fields increases,therefore destabilizing the interface.The circular interface is more unstable than in the case of Laplace equation without time partial derivatives.The critical stability radius of the crystal interface increases with shearing rate increasing.The stability effect of shear flow decreases remarkably with the increase of melt undercooling.     

The effect of two-dimensional shear flow on the stability of a crystal interface in the supercooled melt

A model is developed based on the time-related thermal diffusion equations to investigate the effects of two-dimensional shear flow on the stability of a crystal interface in the supercooled melt of pure substance. Similar to the three-dimensional shear flow as described in our previous paper, the two-dimensional shear flow can also be found to reduce the growth rate of perturbation amplitude. However, compared with the case of Laplace equation for steady state thermal diffusion field, due to the existence of time partial derivatives of the temperature fields in diffusion equation the absolute value of the gradients of the temperature fields increases, therefore destabilizing the interface. The circular interface is more unstable than in the case of Laplace equation without time partial derivatives. The critical stability radius of the crystal interface increases with shearing rate increasing. The stability effect of shear flow decreases remarkably with the increase of melt undercooling.     

The influence of high pressure on the solidification of supercooled Se melt

Abstract

Under pressures between 1.75 and 8 GPa a supercooling of Se melt and an average grain size of the samples quenched under pressure with constant cooling rate 100 K/s were measured. In framework of the classic theory of nucleation and grain growth the numerical evaluation of surface tension and activation energy of crystal growth was performed. The comparison of properties of supercooled Se melt to that of Pb and In reveals anomalies on the pressure dependences of Se melt properties.

This circumstance is discussed in connection with the semiconductor-metal transition discovered earlier in Se melt.     

Influence of isothermal approximation on the phase-field simulation of directional growth in undercooled melt

By using the phase-field approach,we have simulated the directional growth of alloys in undercooled moten states under the isothermal and nonisothermal conditions.The influences of the isothermal approximation on simulation results are discussed.We found that for undercooling greater than 25K,the isothermal approximation overestimates the interface growth velocity and reduces a critical velocity for an absolute stable planar interface,thus in this simulation,the uinterface morphology shows the plane-cell-plane transition with increasing initial undercooling of the mele,and the planar interface obtained under a large undercooling is absolutely stable.Whereas in the nonisothermal simulation,only plane-cell transition occures in the same range of the initial undercoolings of the melt,and the planar interface tends to be destabilized and evolve into cells.     

过冷液体钾形核初期微观动力学机理的模拟研究

采用分子动力学方法对液态金属钾凝固过程进行了模拟,根据凝固过程体系平均原子能量、原子成键类型和成团类型,以及均方位移和非Gauss参数等动力学参数的演化特征,对过冷熔体形核初期微观动力学机理进行了研究.结果表明:根据过冷液体钾结晶形核过程热力学、动力学和结构特性的演化规律, 其过冷温度区间可以分为两个明显不同的阶段,潜在结晶核心出现在过冷液体较低温区.过冷熔体钾在形核初期,二十面体团簇结构在α-弛豫阶段逐渐解体,同时具有体心立方(bcc)结构的潜在结晶核心逐步形成,其临界晶核包含约300个原子.     

Confinement effects on the slow dynamics of a supercooled polymer melt: Rouse modes and the incoherent scattering function

Results of large-scale molecular-dynamics simulations of a supercooled polymer film are presented (F. Varnik, J. Baschnagel, K. Binder, J. Phys. IV 10, 239 (2000)). The dynamic and static properties of the system are studied for a wide range of film thicknesses (from 3 to about 55 times the bulk radius of gyration) and temperatures (from the normal liquid state to the supercooled region). The system is confined between two completely smooth and purely repulsive walls. Motivated by the previous results on the enhancement of the local relaxation dynamics due to the confinement (F. Varnik, J. Baschnagel, K. Binder, Eur. Phys. J. E 8, 175 (2002); Phys. Rev. E. 65, 021507 (2002)), we now study the effect of the walls on the dynamics of the Rouse modes. It has been reported from Monte Carlo studies of the Bond Fluctuation Model (BFM) that, contrary to the enhancement of the cage dynamics (exemplified by a faster relaxation of the incoherent scattering function in the film), Rouse modes exhibit a slower relaxation in the confined system (C. Mischler, J. Baschnagel, K. Binder, Adv. Colloid Interface Sci. 94, 197 (2001)). However, we do not observe such a discrepancy for our continuum model: At a given temperature, the relaxation of a given Rouse mode is faster in the film than in the bulk in accordance with the acceleration of the dynamics around the cage.Received: 1 January 2003, Published online: 21 October 2003PACS: 61.20.Ja Computer simulation of liquid structure - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 64.70.Pf Glass transitions