A statistical-mechanical theory of self-diffusion in glass-forming liquids

A statistical-mechanical theory of self-diffusion in glass-forming liquids is presented. A non-Markov linear Langevin equation is derived from a Newton equation by employing the Tokuyama-Mori projection operator method. The memory function is explicitly written in terms of the force-force correlation functions. The equations for the mean-square displacement, the mean-fourth displacement, and the non-Gaussian parameter are then formally derived. The present theory is applied to the glass transitions in the glass-forming liquids to discuss the crossover phenomena in the dynamics of a single particle from a short-time ballistic motion to a long-time self-diffusion process via a β (caging) stage. The effects of the renormalized friction coefficient on self-diffusion are thus explored with the aid of analyses of the simulation results by the mean-field theory proposed recently by the present author. It is thus shown that the relaxation time of the renormalized memory function is given by the β-relaxation time. It is also shown that for times longer than the β-relaxation time the dynamics of a single particle is identical to that discussed in the suspensions.     

Dynamic properties,scaling and related freezing criteria of two- and three-dimensional colloidal dispersions

The static and dynamic properties of 2- and 3-dimensional dispersions of strongly interacting colloidal spheres are examined. Quasi-2-dimensional dispersions of particles interacting by long range electrostatic and dipolar magnetic forces, respectively, are investigated using Brownian dynamics computer simulations with hydrodynamic interactions included. The dynamics of 3-dimensional bulk dispersions of charge-stabilized and neutral colloidal spheres is determined from a fully self-consistent mode-coupling scheme. For systems with long range repulsive interactions the dynamic correlation functions are shown to obey dynamic scaling in terms of a characteristic relaxation time related to the mean particle distance. Hydrodynamic interactions introduce a second characteristic length scale, and they lead to more restricted scaling behaviour with an enhancement of self-diffusion and, for 2-dimensional systems, to the divergence of the short-time collective diffusion coefficient. As a consequence of dynamic scaling, a dynamic criterion for the onset of colloidal freezing related to long-time self-diffusion is shown to be equivalent to a static freezing criterion related to the 2- and 3-dimensional static structure factors. Alternative freezing criteria are given in terms of the long-time and the mean collective diffusion coefficients.     

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.     

Dynamics in dense suspensions of charge-stabilized colloidal particles

The dynamic behavior of charge-stabilized colloidal particles in suspension was studied by photon correlation spectroscopy with coherent X-rays (XPCS). The short-time diffusion coefficient, D(Q) , was measured for volume concentrations φ ⩽ 0.18 and compared to the free particle diffusion constant D₀ and the static structure factor S(Q) . The data show that indirect, hydrodynamic interactions are relevant for the system and hydrodynamic functions were derived. The results are in striking contrast to the predictions of the PA (pairwise-additive approximation) model, but show features typical for a hard-sphere system. The observed mobility is however considerably smaller than the one of a respective hard-sphere system. The hydrodynamic functions can be modelled quantitatively if one allows for an increased effective viscosity relative to the hard-sphere case.     

Anomalous diffusion of a polymer chain in an unentangled melt

Contrary to common belief, hydrodynamic interactions in polymer melts are not screened beyond the monomer length and are important in transient regimes. We show that viscoelastic hydrodynamic interactions (VHIs) lead to anomalous dynamics of a tagged chain in an unentangled melt at t相似文献   

Short-time dynamics in quasi-two-dimensional colloidal suspensions

The short-time dynamic properties of colloidal particles in quasi-two-dimensional geometries are studied by digital video microscopy. We demonstrate experimentally that the effective-two-dimensional physical quantities such as the dynamic structure factor, the hydrodynamic function, and the hydrodynamic diffusion coefficients are related in exactly the same manner as their three-dimensional counterparts.     

二分量胶体悬浮系统的短时间动力学

研究了二分量带电粒子悬浮系统的短时间平动和转动自扩散系数.由于存在静电相互作用和流体力学作用,扩散系数与两种粒子的尺寸比,它们的体积分数,以及所带的有效电荷都有关.计入了流体力学相互作用对扩散张量的二体贡献和首项三体贡献.计算结果表明,流体力学作用对于带电粒子系统的影响要小于它对硬球粒子系统的影响.扩散系数随两种粒子的尺寸比和它们的体积分数变化的关系可以用有效硬球模型来解释,而其定性结果与实验相符合.     

Dynamic heterogeneity of a colloidal solution near the sol-gel transition

The results of the simulation of the dynamics of particles in a colloidal solution in the vicinity of the sol-gel transition are presented. The Van Hove correlation function, incoherent scattering function, and mean-square displacement of particles at different temperatures and volume densities have been calculated from the simulation data. The effects of dynamic heterogeneity have been evaluated numerically and the gelation temperature at different volume densities has been determined using the non-Gaussian parameter. It has been shown that the specific features observed in the dynamics of particles in the colloidal solution near the sol-gel transition are explained by the conventional separation of the particles in the system into fast particles, which contribute to translational diffusion, and slow particles, which participate predominantly in vibrational processes.     

椭球与圆球混合胶体体系的玻璃化转变

以椭球与圆球混合的胶体体系为研究对象,通过增加体系的面积分数,从实验上研究了混合体系发生玻璃化转变过程中结构和动力学行为的演变规律.在结构方面,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,发现椭球可以有效地抑制圆球结晶,整个体系在结构上始终保持无序.在动力学方面,通过计算体系的均方位移和自散射函数,发现随着面积分数的增加,体系的动力学明显变慢,弛豫时间在接近模耦合理论预测的玻璃化转变点快速增大并发散.通过考察快速粒子参与的协同重排行为,发现协同重排区域形状、大小和位置都与椭球的存在密切关联.     

Dramatic change of the self-diffusions of colloidal ellipsoids by hydrodynamic interactions in narrow channels

The self-diffusion problem of Brownian particles under the constraint of quasi-one-dimensional(q1 D) channel has raised wide concern.The hydrodynamic interaction(HI) plays an important role in many practical problems and two-body interactions remain dominant under q1D constraint.We measure the diffusion coefficient of individual ellipsoid when two ellipsoidal particles are close to each other by video-microscopy measurement.Meanwhile, we obtain the numerical simulation results of diffusion coefficient using finite element software.We find that the self-diffusion coefficient of the ellipsoid decreases exponentially with the decrease of their mutual distance X when X X_0, where X_0 is the maximum distance of the ellipsoids to maintain their mutual influence, X_0 and the variation rate are related to the aspect ratio p = a/b.The mean squared displacement(MSD) of the ellipsoids indicates that the self-diffusion appears as a crossover region, in which the diffusion coefficient increases as the time increases in the intermediate time regime, which is proven to be caused by the spatial variations affected by the hydrodynamic interactions.These findings indicate that hydrodynamic interaction can significantly affect the self-diffusion behavior of adjacent particles and has important implications to the research of microfluidic problems in blood vessels and bones, drug delivery, and lab-on-chip.     

Dynamics and sedimentation velocity in charge-stabilized colloidal suspensions

Summary Charge-stabilized suspensions are characterized by the strong electrostatic interactions between the particles so that rather dilute systems may exhibit strong correlation resulting in a well-developed short-range order. This microstructure, quantitatively described by the pair distribution functiong(r), is rather different from that of (uncharged) hard spheres. It is shown how this difference affects the ?hydrodynamic function?H(k), which appears in the expression for the first cumulant Γ(k)=k ² D _eff(k)=k ² H(k)/S(k) of the dynamic autocorrelation function. Without hydrodynamic interaction,H(k)=D ⁰, which is the free-diffusion coefficient. Using pairwise additive hydrodynamic interaction and the lowest-order many-body theory of hydrodynamic interaction, it is found thatH(k) can deviate considerably fromD ⁰ even for systems of volume fractions ϕ as low as 10⁻³. These effects are more pronounced for collective diffusion than for self-diffusion. SinceH(k=0) is closely related to the sedimentation velocity, we have studied this quantity as a function of volume fraction. It is found that (H(0)/D ⁰) −1 scales asφ ^1/3 at low ϕ in salt-free suspensions. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

GPU-accelerated simulation of colloidal suspensions with direct hydrodynamic interactions

Solvent-mediated hydrodynamic interactions between colloidal particles can significantly alter their dynamics. We discuss the implementation of Stokesian dynamics in leading approximation for streaming processors as provided by the compute unified device architecture (CUDA) of recent graphics processors (GPUs). Thereby, the simulation of explicit solvent particles is avoided and hydrodynamic interactions can easily be accounted for in already available, highly accelerated molecular dynamics simulations. Special emphasis is put on efficient memory access and numerical stability. The algorithm is applied to the periodic sedimentation of a cluster of four suspended particles. Finally, we investigate the runtime performance of generic memory access patterns of complexity O(N ²) for various GPU algorithms relying on either hardware cache or shared memory.     

Self-diffusion of spheres in a concentrated suspension

We calculate the concentration-dependence of the short-time self-diffusion coefficient D_s for spherical particles in suspension. Our analysis is valid up to high densities and fully takes into account the many-body hydrodynamic interactions between an arbitrary number of spheres. The importance of these many-body interactions can be inferred from our calculation of the second virial coefficient of D_s.     

Simulation method of colloidal suspensions with hydrodynamic interactions: fluid particle dynamics

We develop a new simulation method of colloidal suspensions, which we call a "fluid particle dynamics" (FPD) method. This FPD method, which treats a colloid as a fluid particle, removes the difficulties stemming from a solid-fluid boundary condition in the treatment of hydrodynamic interactions between the particles. The importance of interparticle hydrodynamic interactions in the aggregation process of colloidal particles is demonstrated as an example. This method can be applied to a wide range of problems in colloidal science.     

A statistical-mechanical theory of slow dynamics near the glass transition

A statistical-mechanical theory of slow dynamics near the glass transition in two kinds of glass-forming systems, (M) molecular systems and (S) suspensions of colloids, is presented from a unified point of view based on the Tokuyama-Mori projection operator method. The exact diffusion equations for the coherent- and the incoherent-intermediate scattering functions are first derived, whose memory functions are convolutionless in time and contain the correlation effects due to the hydrodynamic interactions in (S). The analytic expressions of the memory functions are then calculated within the mode-coupling theory (MCT) approximation and are shown to coincide with the conventional ones obtained by MCT. Alternative mode-coupling equations are thus obtained in (M) and (S) separately. Self-diffusion is also discussed. Alternative equations for the mean-square displacement and the non-Gaussian parameter are also derived within MCT approximation. All results in both the systems are compared with those obtained by MCT.     

Light-driven oscillations of entangled nematic colloidal chains

Laser tweezers have been used to drive the oscillations of a chain of entangled colloidal particles in the nematic liquid crystal 5CB. The amplitude and phase of light-driven oscillations have been determined for the motion of individual colloidal particles. The collective motion of 4.8μm silica particles is highly damped for a driving frequency above 0.5Hz. The results were compared to an effective bead-spring model, where the motion of elastically coupled particles is hindered by viscous damping and hydrodynamic coupling. Qualitative agreement between theory and experiment was obtained.     

Dynamical density functional theory with hydrodynamic interactions and colloids in unstable traps

A density functional theory for colloidal dynamics is presented which includes hydrodynamic interactions between the colloidal particles. The theory is applied to the dynamics of colloidal particles in an optical trap which switches periodically in time from a stable to an unstable confining potential. In the absence of hydrodynamic interactions, the resulting density breathing mode exhibits huge single peaked oscillations in the trap center which become double peaked and damped by hydrodynamic interactions. The predicted dynamical density fields are in good agreement with Brownian dynamics computer simulations.     

Effects of the rate of evaporation and film thickness on nonuniform drying of film-forming concentrated colloidal suspensions

In this paper, we report on nonuniform distribution of film-forming waterborne colloidal suspensions above the critical concentration _c of the colloidal glass transition during drying. We found that colloidal suspension films dry nonuniformly when the initial rate of evaporation E and/or the initial thickness l₀ are high. We found that a Peclet number Pe, defined as Pe = El₀/D, where D is the diffusion coefficient of the colloids in the diluted suspensions, does not predict uniformity of drying of the concentrated suspensions, contrary to the reported work on drying of diluted suspensions. Since the colloidal particles are crowded and their diffusive motion is restricted in concentrated suspensions, we assumed that above _c water is transported to the drying surface by hydrodynamic flow along the osmotic pressure gradient. The permeability of water through channels between deforming particles is estimated by adapting the theory of foam drainage. We defined a new Peclet number Pe by substituting the transport coefficient of flow (defined as the permeability divided by the viscosity, multiplied by the osmotic pressure gradient) for the diffusion coefficient. This extended Peclet number predicted the nonuniform drying with a criterion of Pe > 1. These results indicate that the mechanism of water transport to the drying surface in concentrated suspensions is water permeation by osmotic pressure, which is faster than mutual diffusion between water and particles --that has been observed in diluted suspensions and discussed by Routh and Russel. The theory fits well the experimental drying curves for various thicknesses and rates of evaporation. The particle distribution in the drying films is also estimated and it is indicated that the latex distribution is nonuniform when Pe > 1.