有限尺寸胶体体系的二维结晶

从工业上的大尺寸晶体生长到实验室中受限小体系的结晶,结晶是普遍存在的物理现象,也一直是物理学中的重要研究课题.与大尺度结晶相变的研究相比,对于有限小尺度体系结晶过程的研究相对较少.本文通过设计具有吸引相互作用的胶体体系,在实验上研究了有限小尺寸胶体体系的二维结晶相变.通过计算和分析径向分布函数、泰森多边形以及取向序参量,发现有限小尺寸体系的结晶过程是从中央高密度区域开始,随着结晶的进行,周围液相减小而晶相增加,最后完全转变为晶态的过程.体系结晶速率呈现两个阶段:在结晶初期中央区域是高密度的亚稳态液体,会降低结晶自由能能垒,使得体系快速结晶;随后晶相长大,亚稳态液体消失,体系结晶速率变慢.此外,通过统计有序度参量的分布发现:在结晶过程中,序参量出现双峰分布,分别对应液相和晶相,与大尺度胶体体系的二维结晶行为一致,说明序参量分布的变化规律是二维结晶相变的重要特征.     

Aggregation kinetics in a model colloidal suspension

We present molecular dynamics simulations of aggregation kinetics in a colloidal suspension modeled as a highly asymmetric binary mixture. Starting from a configuration with largely uncorrelated colloidal particles the system relaxes by coagulation-fragmentation dynamics to a structured state of low-dimensionality clusters with an exponential size distribution. The results show that short-range repulsive interactions alone can give rise to so-called cluster phases. For the present model and probably other, more common colloids, the observed clusters appear to be equilibrium phase fluctuations induced by the entropic intercolloidal attractions.     

Microscopic structure and elasticity of weakly aggregated colloidal gels

We directly probe the microscopic structure, connectivity, and elasticity of colloidal gels using confocal microscopy. We show that the gel is a random network of one-dimensional chains of particles. By measuring thermal fluctuations, we determine the effective spring constant between pairs of particles as a function of separation; this is in agreement with the theory for fractal chains. Long-range attractions between particles lead to freely rotating bonds, and the gel is stabilized by multiple connections among the chains. By contrast, short-range attractions lead to bonds that resist bending, with dramatically suppressed formation of loops of particles.     

Colloidal aggregation in a nematic liquid crystal: topological arrest of particles by a single-stroke disclination line

We numerically study many-body interactions among colloidal particles suspended in a nematic liquid crystal, using a fluid particle dynamics method, which properly incorporates dynamical coupling among particles, nematic orientation, and flow field. Based on simulation results, we propose a new type of interparticle interaction in addition to well-known quadrupolar interaction for particles accompanying Saturn-ring defects. This interaction is mediated by the defect of the nematic phase: upon nematic ordering, a closed disclination loop binds more than two particles to form a sheetlike dynamically arrested structure. The interaction depends upon the topology of a disclination loop binding particles, which is determined by aggregation history.     

Noncentral forces in crystals of charged colloids

The elastic properties of fcc crystals consisting of charge stabilized colloidal particles are determined from real space imaging experiments using confocal microscopy. The normal modes and the force constants of the crystal are obtained from the fluctuations of the particles around their lattice sites using the equipartition theorem. We show that the Cauchy relation is not fulfilled and that only noncentral many-body forces can account for the elastic properties.     

Slow dynamics of self-diffusion in metastable colloidal fluids

A simple theory for nonequilibrium density fluctuations in concentrated hard-sphere suspensions of interacting Brownian particles with both hydrodynamic and direct interactions is proposed. The correlation effects due to the many-body hydrodynamic interactions among particles are shown to cause a structural arrest in the relaxation of nonequilibrium density fluctuations. A volume fraction dependence of slow relaxation process in concentrated colloidal suspensions is thus explored from a new unifying point of view.     

Confinement-induced colloidal attractions in equilibrium

The Poisson-Boltzmann theory for colloidal electrostatic interactions predicts that charged colloidal spheres dispersed in water should repel each other, even when confined by charged surfaces. Direct measurements on highly charged polystyrene spheres, however, reveal strong, long-ranged confinement-induced attractions that have yet to be explained. We demonstrate that anomalous attractions also characterize the equilibrium pair potential for more weakly charged colloidal silica spheres sedimented into a monolayer above a glass surface. This observation substantially expands the range of conditions for which mean-field theory incorrectly predicts the sign of macroions' interactions, and provides new insights into how confinement induces long-ranged like-charge attractions.     

实践十号卫星开展空间固液界面胶体自组装动力学行为研究

微流动驱动的胶体自组装是一种非平衡的过程。在定向微流动(如热毛细流)驱动下,胶体体系内的粒子自身的热运动受到抑制,胶体体系中的微粒常常出现宏观有序的结构。但这种粒径的球在重力作用下会显著沉降,造成胶体体系的浓度不均,而胶体体系的相行为与浓度密切相关。因此在重力作用下难以准确地描述相变与局域结构的关联。在微重力条件下,大尺度的胶体球没有重力沉降作用,可提供准确的局域结构信息,而且浮力对流受到较大抑制,没有流体静压力,不产生沉降作用,这为研究界面上的胶体自组装动力学行为提供了有利条件。“胶体有序排列及新型材料研究”是“实践十号卫星”19项科学实验载荷之一,其科学实验将在载荷“胶体材料箱”中完成,将是空间中进行的首次胶体自组装动力学行为的实验研究。     

Nonlinear screening and gas-liquid separation in suspensions of charged colloids

We calculate phase diagrams of charged colloidal spheres (valency Z and radius a) in a 1:1 electrolyte from multicentered nonlinear Poisson-Boltzmann theory. Our theory takes into account charge renormalization of the colloidal interactions and volume terms due to many-body effects. For valencies as small as Z = 1 and as large as 10(4) we find a gas-liquid spinodal instability in the colloid-salt phase diagram provided Z lambdaB/a > or similar 24+/-1, where lambdaB is the Bjerrum length.     

Order-to-disorder transition in ring-shaped colloidal stains

A colloidal dispersion droplet evaporating from a surface, such as a drying coffee drop, leaves a distinct ring-shaped stain. Although this mechanism is frequently used for particle self-assembly, the conditions for crystallization have remained unclear. Our experiments with monodisperse colloidal particles reveal a structural transition in the stain, from ordered crystals to disordered packings. We show that this sharp transition originates from a temporal singularity of the flow velocity inside the evaporating droplet at the end of its life. When the deposition speed is low, particles have time to arrange by Brownian motion, while at the end, high-speed particles are jammed into a disordered phase.     

Attractive colloidal rods in shear flow

The effect of shear flow on the isotropic-nematic phase transition of attractive colloidal rods is investigated by a combination of simulations and experiments. The isotropic phase aligns with the flow, while the nematic phase undergoes a collective rotational motion which frustrates the merging of the coexisting regions. The location of binodals, spinodals, and the tumbling-to-aligning transition line in the shear-rate versus concentration plane are investigated. The phase diagrams in the shear-concentration plane for the various strengths of attractions can be mapped onto a master curve by appropriate scaling.     

Entropic wetting and many-body induced layering in a model colloid-polymer mixture

We develop an efficient simulation scheme to study a model suspension of equally sized colloidal hard spheres and nonadsorbing ideal polymer coils, both in bulk and adsorbed against a planar hard wall. The many-body character of the polymer-mediated effective interactions between the colloids yields a bulk phase diagram and adsorption phenomena that differ substantially from those found for pairwise simple fluids; e.g., we find an anomalously large bulk liquid regime and, far from the bulk triple point, three layering transitions in the partial wetting regime prior to a transition to complete wetting by colloidal liquid.     

在单粒子尺度下用胶体研究相变

悬浮于溶液中的微米胶体粒子可以自组装成多种结构,与原子一样具有丰富的相行为,通过调节粒子的大小、形状、相互作用或密度可以驱动相变。由于胶体粒子可以在光学显微镜下直接成像并测量其热运动轨迹,因此是研究相变微观过程的一种有力的模型系统。近十几年来,作用力可调粒子、非球形粒子和活性粒子的制备有了突破性进展,并在自组装技术和相应的计算机模拟中有很大进步,因此为相变研究开辟了许多可能性。文章总结了利用胶体研究相变过程的最新进展,重点关注结晶、熔化和固—固相变,并简述胶体相变研究中存在的挑战和未来前景。     

Heterogeneous crystallization in colloids and complex plasmas: the role of binary mobilities

Both charged colloidal suspensions and complex (dusty) plasmas represent classical many-body strongly coupled Coulomb systems. Here we discuss their basic properties and focus on their heterogeneous crystallization from an undercooled melt. In particular, a model with different mobilities is proposed which is realizable in binary mixtures of charged particles. Within this binary-mobility model, the crystallization behaviour near a structured wall is explored by Brownian dynamics computer simulations. As a result, the propagation velocity of the crystal-fluid interface is a nonmonotonic function of the mobility ratio (if expressed in terms of an averaged mobility).     

Nematic-wetted colloids in the isotropic phase: pairwise interaction, biaxiality, and defects

We calculate the interaction between two spherical colloidal particles embedded in the isotropic phase of a nematogenic liquid. The surface of the particles induces wetting nematic coronas that mediate an elastic interaction. In the weak wetting regime, we obtain exact results for the interaction energy and the texture, showing that defects and biaxiality arise, although they are not topologically required. We evidence rich behaviors, including the possibility of reversible colloidal aggregation and dispersion. Complex anisotropic self-assembled phases might be formed in dense suspensions.     

Effective interactions of colloids on nematic films

The elastic and capillary interactions between a pair of colloidal particles trapped on top of a nematic film are studied theoretically for large separations d. The elastic interaction is repulsive and of quadrupolar type, varying as d^-5. For macroscopically thick films, the capillary interaction is likewise repulsive and proportional to d^-5 as a consequence of mechanical isolation of the system comprised of the colloids and the interface. A finite film thickness introduces a nonvanishing force on the system (exerted by the substrate supporting the film) leading to logarithmically varying capillary attractions. However, their strength turns out to be too small to be of importance for the recently observed pattern formation of colloidal droplets on nematic films.     

Equilibrium cluster phases and low-density arrested disordered states: the role of short-range attraction and long-range repulsion

We study a model in which particles interact with short-ranged attractive and long-ranged repulsive interactions, in an attempt to model the equilibrium cluster phase recently discovered in sterically stabilized colloidal systems in the presence of depletion interactions. At low packing fractions, particles form stable equilibrium clusters which act as building blocks of a cluster fluid. We study the possibility that cluster fluids generate a low-density disordered arrested phase, a gel, via a glass transition driven by the repulsive interaction. In this model the gel formation is formally described with the same physics of the glass formation.     

冷却速率对温敏聚N-异丙基丙烯酰胺胶体结晶过程的影响

冷却速率对结晶过程具有重要的影响. 本文采用温敏poly-N-isopropylacrylamide (PNIPAM) 胶体晶体体系实时观察了冷却速率对结晶晶粒尺寸的影响. 通过高倍透射明场观察和Bragg衍射观察研究连续冷却下的晶粒形核和生长实时演化过程, 发现随着冷却速率的增加, PNIPAM胶体晶体晶粒尺寸不断减少. 晶粒尺寸与冷却速率符合幂指数关系, 与金属体系具有相似的演化规律.     

Diffusion of colloidal particles in swimming suspensions

Previously, we have proposed to analyse the hydrodynamic interactions in a suspension of swimmers with respect to an effective hydrodynamic diffusion coefficient, which only considers the fluctuating motion caused by the stirring of the fluid. In this work, we study the diffusion of colloidal particles immersed in a bath of swimmers. To accurately resolve the many-body hydrodynamic interactions responsible for this diffusion, we use a direct numerical simulation scheme based on the smooth profile method. We consider a squirmer model for the self-propelled swimmers, as it accurately reproduces the flow field generated by real microorganisms, such as bacteria or spermatozoa. We show that the diffusion coefficients of the colloids are comparable with the effective diffusion coefficients of the swimmers, provided that the concentration of swimmers is high enough. At low concentrations, the difference in the way colloids and swimmers react to the flow leads to a reduction in the diffusion coefficient of the colloids. This is clearly seen in the appearance of a negative-correlation region for the velocity-correlation function of the colloids, which does not exist for the swimmers.     

Phase separation and structure in a concentrated colloidal dispersion of uniform plates

The structure and phase behaviour of a colloidal dispersion of plate-like particles are described. The plates are nickel (II) hydroxide and have short-range, repulsive interactions and a low polydispersity. As the concentration of the plates is increased, an equilibrium phase separation between a columnar phase and a less ordered phase is observed. Complementary measurements using small-angle neutron and small-angle X-ray scattering have been used to distinguish the columnar phase from other possible ordered structures. Previously isotropic-nematic phase transitions have been observed [#!ref1!#], however this dispersion forms the more highly ordered columnar phase, due to the aspect ratio and the low polydispersity of the plate-like particles. The concentration at which phase separation occurs, increases as the range of the particle interactions is reduced. This system provides an interesting model for comparison with theory and calculations of structures in liquid crystal and mesophase in which the particle interactions can be altered. Received 24 February 1999