Computer simulation of heterogeneous nucleation on curved surfaces using a simplified string method combined with phase-field simulations

We show how the combination of string method with the phase-field approach can be extended from simulations of homogeneous nucleation to heterogeneous nucleation. From these simulations, it is possible to directly obtain nucleation barriers for heterogeneous nucleation on arbitrary surfaces as well as information about the size and shape of the critical nucleus. We test the method by comparing the dependence of the nucleation barrier for heterogeneous nucleation on concave and convex surfaces on the surface curvature obtained from three-dimensional phase-field simulations with predictions from classical nucleation theory and find good agreement between them.     

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.     

Computer simulation of physisorption on a heterogeneous surface

The technique of molecular dynamics was used to determine the structures of krypton physisorbed on a simple heterogeneous surface. The solid was modelled as an infinite set of straight square-walled grooves cut into an otherwise flat surface. The computed local densities show that the atoms adsorb as one-dimensionally ordered rows near the walls of the grooves. This order decays with increasing distance from the walls. Also, the atoms adsorbed on the steps exhibit little order at the simulation temperature of 110 K.     

Coexistence of two colloidal crystals at the nematic-liquid-crystal-air interface

Glycerol droplets at a nematic-liquid-crystal-air interface form two different lattices--hexagonal and dense quasihexagonal--which are separated by the energy barrier and can coexist. Director distortions around each droplet form an elastic dipole. The first order transition between the two lattices is driven by a reduction of the dipole-dipole repulsion through reorientation of these dipoles. The elastic-capillary attraction is essential for the both lattices. The effect has a many-body origin.     

Dynamics of colloidal crystals

We study the lattice dynamics of colloidal crystals on the assumption that the potential interactions are limited to nearest neighbors and next nearest neighbors and that the long range hydrodynamic interactions may be treated in point approximation. We show that this does not lead to satisfactory agreement with existing experimental data.     

Computer simulation of the deformation and fracture of crystals

Methods for computer simulation of strength testing of crystals are proposed. The methods employed are similar to usual static methods, and they are used to investigate deformation and fracture of perfect fcc crystals having different orientations with respect to the tensile force. A strain-induced phase transition from the fcc to the hcp structure is detected, and the formation and displacement of crystal twins are observed. Plastoelastic deformation and fracture of crystals are investigated.     

Crystal nucleation of colloidal suspensions under shear

We use Brownian dynamics simulations in combination with the umbrella sampling technique to study the effect of shear flow on homogeneous crystal nucleation. We find that a homogeneous shear rate leads to a significant suppression of the crystal nucleation rate and to an increase of the size of the critical nucleus. A simple, phenomenological extension of classical nucleation theory accounts for these observations. The orientation of the crystal nucleus is tilted with respect to the shear direction.     

异质原子对液体气泡成核影响的分子动力学模拟

采用分子动力学方法模拟了池沸腾中液体层加入异质原子对气泡成核的影响.分析了异质原子能量参数对液体起始气泡成核时间和温度的影响及其机理.结果表明,当异质原子能量参数小于液氩能量参数时,液体起始气泡成核时间缩短,起始温度降低.当异质原子剂能量参数大于液氩能量参数时,液体起始气泡成核时间增加,起始温度升高.异质原子在壁面上的吸附及在液体中的扩散行为影响固液界面性质,较大能量参数的异质原子扩散系数较小,更多能量参数较大的原子吸附在固体表面上使得壁面势能壁垒增加,导致沸腾时间延迟,液体需要吸收更多的热量克服势能壁垒,进而提高沸腾起始温度.能量参数较小的异质原子扩散系数较大,异质原子更容易分散到液体中,使得壁面附近液体层势能减小,液体层更容易气泡成核行为.     

Computer simulation study of a flexible-rigid-flexible model for liquid crystals

Small molecules that form liquid crystals typically consist of a rigid core with flexible tails on one end or on both ends. To date, most computer simulation studies have used completely rigid models such as hard spherocylinders: cylinders, characterized by their length/diameter ratio L/D, with hemispherical end caps. We have studied a model consisting of spherocylinders with L/D = 4, with a flexible tail attached to each end. The tails are ‘ideal’ in the sense that they have no volume. Using Monte Carlo simulations the phase behaviour of this model was studied and, for comparison, the behaviour of hard spherocylinders with L/D = 4 without tails was studied as well. The addition of the tails is found to stabilize the smectic-A phase at a lower pressure, and the nematic phase disappears. In the smectic-A and crystal phases, the smectic layers are further apart when tails are added. The structure of the layers and the smectic-A–crystal transition pressure change only a little. For both models close to melting the crystal consists of ordered layers, but there is almost no correlation between particle positions in neighbouring layers. In fact, the layer coupling is so weak that in a long simulation the layers are found to glide over each other. As the pressure is increased the crystal gradually becomes more ordered and the crystalline layers ultimately ‘lock’ into place.     

Determination of the colloidal crystal nucleation rate density

Colloidal suspensions of charged latex microspheres in water exhibit liquid-like or crystalline ordering depending on particle interaction and concentration. By virtue of large particle spacing and slow dynamics, colloidal systems offer a unique opportunity to study interfacial structure and dynamics. This paper presents the first reported experimental study of the nucleation rate density, c, of an nonequilibrium (supercooled) colloidal liquid to colloidal crystal first order phase transition. Local and global observations of colloidal crystals growing from a metastable colloidal liquid were used to determine c. Microscopic local observations revealed homogeneous nucleation and constant interface velocity growth of quasispherical crystallites in the bulk and heterogeneous nucleation of a crystalline sheet with lower growth velocity at the cell wall. Complementary global observations of the recrystallization transition made by measuring the time dependence of the suspension transparency (the fraction of transmitted laser light) determined c by fitting this curve to a model based on an extension of Avrami's theory of crystallization.     

Computer simulation of structure and mechanical properties of polymer liquid crystals

In this contribution, we report on a study of the self-organization and mechanical properties of polymer liquid crystals (PLCs). Both processes are computer simulated by the method of molecular dynamics. We investigated two real longitudinal PLCs (thermotropic polyesters) with macromolecules that consist of rigid and flexible parts arranged in a regular way. One rigid and one flexible part form a monomer containing 45 or 47 atoms. The total number of atoms in the macromolecules studied was 4700 (100 monomers) and 5400 (75 monomers). The self-organization was similar to that obtained earlier for a beads-on-a-string model, so compression calculations were done using this simpler model containing 1200 beads (100 monomers). Macroscopic characteristics such as the stress-strain relation, temperature change during deformation, as well as microscopic changes in structure, were investigated.     

Phase field theory of heterogeneous crystal nucleation

The phase field approach is used to model heterogeneous crystal nucleation in an undercooled pure liquid in contact with a foreign wall. We discuss various choices for the boundary condition at the wall and determine the properties of critical nuclei, including their free energy of formation and the contact angle as a function of undercooling. For particular choices of boundary conditions, we may realize either an analog of the classical spherical cap model or decidedly nonclassical behavior, where the contact angle decreases from its value taken at the melting point towards complete wetting at a critical undercooling, an analogue of the surface spinodal of liquid-wall interfaces.     

SiO_2胶体晶体自组装技术

介绍了垂直沉降法和旋涂法制备SiO2胶体晶体,并对两种方法制备的胶体晶体在宏观形貌、微观结构及光子带隙性质进行了比较。采用改进的Stober法在乙醇介质中合成粒径不同、单分散性较好的SiO2微球,用垂直沉积法和旋涂法制备出有序性较好的密排结构的SiO2胶体晶体。宏观照片表明,用旋涂法制备的SiO2胶体晶体经白光照射出现的光柱呈6次对称,而垂直沉降法制备的胶体晶体表面出现条纹。SEM分析表明,选用不同溶剂在同等旋涂工艺下制备SiO2胶体晶体,用乙醇和乙二醇混合溶液作溶剂制备出的SiO2胶体晶体质量最好。透射光谱表明,垂直沉降法所制备的胶体晶体在(111)方向具有明显的光子带隙性质,而旋涂法制备的胶体晶体则不明显。     

Structure transitions of polymer-mediated colloidal crystals

The self-assembled colloidal crystals with structure transitions were realized experimentally on substrates with polymer brushes. Such polymer-mediated colloidal crystals were found to experience a series of in-layer structure transitions including stable columnar, polycrystalline, mixed square-hexagonal, square, hexagonal structures when the mass ratio of colloidal particles to free polymers was adjusted from 0.125 to 10. Among these structures, a large area interfacial square structure was proved to be a body-centered tetragonal (BCT) structure in three dimensions in the polymer-mediated colloidal crystals.