Patchy粒子聚集的统计力学研究

应用统计力学原理对A_aB_b型Patchy粒子的聚集过程进行研究, 考察了典型平均物理量在聚集过程中的变化情况. 首先基于配分函数导出体系的平衡自由能及描述Patchy粒子之间联接作用的质量作用定律, 进而获得团簇的数量分布函数. 进一步给出Patchy团簇的数均和重均聚合度以及物理凝胶化条件, 探讨了凝胶化区域与Patchy粒子数之间的依赖关系. 同时给出Patchy团簇生长的微分动力学方程, 并进行了相应的Monte Carlo模拟. 本文旨在揭示Patchy粒子的内在和外在因素对体系聚集态结构的影响, 为实现对Patchy粒子体系的有效调控提供理论依据.     

Method to predict and compare the influence of the particle size on the isocratic peak capacity of high-performance liquid chromatography columns

A kinetic plot based method has been used to experimentally predict the optimal particle size yielding the maximal isocratic peak capacity in a given analysis time. Applying the method to columns of three different manufacturers and characterizing them by separating a 4-component paraben mixture at 30 degrees C, it was consistently found that the classical 3 and 3.5 microm particles provide the highest peak capacity for typical isocratic separation run times between 30 and 60 min when operating the columns at a conventional pressure of 400 bar. Even at 1000 bar, the sub-2 microm particles only have a distinct advantage for runs lasting 30 min or less, while for runs lasting 45 min or longer the 3 and 3.5 microm again are to be preferred. This finding points at the advantage for high-resolution separations that could be obtained by producing 3 and 3.5 microm particle columns that can be operated at elevated pressures.     

碘离子催化的H2O2-BAT反应的Monte Carlo模拟

催化动力学分析是痕量分析中检测下限低、选择性较好的一种方法,但目前分析工作者对所用的反应机理常不明瞭,仅能作为“黑箱”应用之。模拟技术可为探讨这类分析反应机理提供有用的信息。前文^[1]报道用溴胺T(BAT)离子电极、跟踪碘离子催化的BAT-H₂O₂反应测定痕量碘效果甚佳。     

Effects of ball-to-powder diameter ratio and powder particle shape on EDEM simulation in a planetary ball mill

The effects of the ball-to-powder diameter ratio (BPDR) and the shape of the powder particles on EDEM simulation results and time in the planetary ball mill was investigated. BPDR was varied from 1 to 40/3 by changing the powder particle diameter from 8 to 0.6 ?mm. The size and shape of the powder particles do not give a significant change in both the ball motion pattern and simulation results when BPDR is over 20/3. It can be assumed that the kinetic energy of the ball has nothing to do with the size and shape of the powder particle. The simulation time and data size increase exponentially as BPDR increases. The effect of change of the powder particle shape on the calculated data size is not significant, but the more complicated its shape, the longer the simulation time, which is linearly related to the number of spheres composing a particle.     

用直接数值模拟对移动颗粒层除尘的研究及实验对比

利用气固两相流数值模拟计算模型，分别采用不同粒径的移动颗粒层过滤除尘器，对不同粒径粉尘颗粒的碰撞次数进行统计，并对移动床除尘中过滤介质尺寸与粉尘粒径尺寸之间的相互选择性进行了初步研究。模拟计算了在同一风速下碰撞次数与粉尘粒径以及移动层颗粒径之间的关系。计算统计的结果与实验结果对比发现，二者存在定性上的一致。结果表明，在移动床过滤除尘器中不同粒径的过滤层对不同粒径尘粒具有明显的选择性。     

Diffusiophoresis in a concentrated suspension of colloidal spheres in nonelectrolyte gradients

The diffusiophoretic motion of a homogeneous suspension of identical spherical particles is considered under conditions of small Reynolds and Peclet numbers. The effects of interaction of the individual particles are taken into explicit account by employing a unit cell model which is known to provide good predictions for the sedimentation of monodisperse suspensions of spherical particles. The appropriate equations of conservation of mass and momentum are solved for each cell, in which a spherical particle is envisaged to be surrounded by a concentric shell of suspending fluid, and the diffusiophoretic velocity of the particle is calculated for various cases. Analytical expressions of this mean particle velocity are obtained in closed form as functions of the volume fraction of the particles. Comparisons between the ensemble-averaged diffusiophoretic velocity of a test particle in a dilute suspension and our cell-model results are made. Received: 30 June 1999 Accepted: 8 December 1999     

A contribution to non-equilibrium chemical kinetics. II. Strongly non-equilibrium “hot” reactions in liquids and solids

The method proposed in part I for non-equilibrium chemical kinetics is applied to processes provoked by non-equilibrium assemblies of energetic particles in liquids and solids. The movement of such an energetic particle belonging to a certain energy group is considered as a stochastic process when the direction of the velocity is changed stochastically at each step. On the ground of this consideration a simplified model of such a process is introduced: the stochastic movement of a particle is replaced by the deterministic movement of the corresponding quasi-particle having parameters determined through corresponding averages of the stochastic process. By use of this model, group constants of kinetic equations of our abovementioned work were expressed through parameters of microscopic processes in solids and liquids, and systems of non-equilibrium chemical kinetics' equations were written for different case. The proposed approach also permits us to consider the non-equilibrium of the crystalline lattice created by energetic particles. “Hot spot” reactions were considered as an example and a method to distinguish between direct and “hot spot” reactions was indicated. The proposed approach and obtained kinetic equations can be applied to recoil atoms (ions), fission products, hot particles produced in radiation chemistry, photochemistry, by laser beams, flash-photolysis etc. The destruction of the crystalline lattice by laser beams can also be considered by use of these equations.     

On the calculation of velocity-dependent properties in molecular dynamics simulations using the leapfrog integration algorithm

Widely used programs for molecular dynamics simulation of (bio)molecular systems are the Verlet and leapfrog algorithms. In these algorithms, the particle velocities are less accurately propagated than the positions. Important quantities for the simulation such as the temperature and the pressure involve the squared velocities at full time steps. Here, we derive an expression for the squared particle velocity at full time step in the leapfrog scheme, which is more accurate than the standardly used one. In particular, this allows us to show that the full time step kinetic energy of a particle is more accurately computed as the average of the kinetic energies at previous and following half steps than as the square of the average velocity as implemented in various molecular dynamics codes. Use of the square of the average velocity introduces a systematic bias in the calculation of the instantaneous temperature and pressure of a molecular dynamics system. We show the consequences when the system is coupled to a thermostat and a barostat.     

Simulation of the latex particle morphology

A model is presented for the simulation of the structuration of polymer particles under conditions in which the new polymer chains are compatible with the polymer previously formed. The model involves the calculation of the monomer concentration gradients within the particles due to discrepancies in thermodynamic interactions between the monomer and the different polymers present in each part of the polymer particle. In addition, the distribution of free radicals in the latex particle is taken into account. This distribution results from the anchoring of the hydrophilic end-group of the growing polymer chain on the surface of the particle. The model was applied to the simulation of the polymerization of vinyl acetate on a butyl acrylate–vinyl acetate copolymer seed. It was found that the development of the particle morphology was mainly due to the profile of concentration of radicals in the particle. On the other hand, the effect of the monomer–polymer thermodynamic interactions on the particle morphology was found to be negligible. However, it has to be pointed out that this is because, for the system studied, the interaction parameters of vinyl acetate with polyvinyl acetate and polybutyl acrylate are nearly identical.     

DSC examination of alloys

The formation and thermal dissolution of dispersed particles was studied in aluminium alloys. It was found that only high heating rates (80°C min⁻¹) could provide DSC curves characteristic of the phase structure of the samples. The kinetic evaluation of the DSC curves was carried out by least squares curve fitting. In this way reasonable kinetic parameters and reliable peak resolution could be obtained for the overlapping peaks.     

Numerical simulation of film coating process in a novel rotating fluidized bed

In this study, numerical simulation of film coating process in a novel rotating fluidized bed (RFB) was conducted by using a Discrete Element Method (DEM)-Computational Fluid Dynamics (CFD) coupling model. Particle movements and fluid motions in a centrifugal force field were simulated at three-dimensional cylindrical coordinate, and this model was applied to film coating process. Film coating process in a RFB was numerically analyzed by using a simplified assumption that a particle was coated only when a particle existed within a spray zone. The experiments were also conducted and uniformity of sprayed material was evaluated by investigating color difference of the coated particles. As a result of the numerical simulation, three-dimensional bubble movements and particle circulation could be well simulated. In addition, mass of the sprayed material on a single particle in a RFB could be visualized by using our proposed model. The relationship between distribution of the sprayed material and the coating time was also analyzed. Calculated mass distributions of the sprayed material could be expressed by a normal distribution function, showing qualitative good agreement with the previous studies. Effect of the operating parameters, such as gas velocity and centrifugal acceleration, on the uniformity of the sprayed material was also investigated by both numerical and experimental approaches. Comparison of the coating process in a RFB with that in a conventional fluidized bed was also conducted by the numerical simulation. The result showed that uniformity of the sprayed material was greatly improved in a RFB due to the much smaller circulation time.     

AC dielectrophoretic deformable particle-particle interactions and their relative motions

This paper develops a numerical simulation model to research the deformable particle-particle interactions caused by dielectrophoresis (DEP) under AC electric fields. The DEP force is calculated by using Maxwell stress tensor method, and the hydrodynamic force is obtained by calculating the hydrodynamic stress tensor. Simulation results show that the DEP interactive motion will facilitate the particles forming particle chains that are parallel to the electric field, and the particles with low shear modulus present a lower x-component velocity. Also, the electric field intensity and particles radius have some effects on the DEP motions, and for different particles, smaller particles with larger electric field intensity easily reach a larger velocity. The numerical research may provide universal guidance for biological cells manipulation and assembly.     

Nano-Impact Electrochemistry Reveals Kinetics Information of Metal-Ion Battery Materials with Multiple Redox Centers

Prussian blue (PB) has emerged as a promising cathode material in aqueous batteries. It possesses two distinct redox centers, and the potassium ions (K⁺) are unevenly distributed throughout the compound, adding complexity to the interpretation of the K⁺ insertion/de-insertion kinetic mechanism. Traditional ensemble-averaged measurements are limited in uncovering the precise kinetic information of the PB particles, as the results are influenced by the construction of the porous composite electrode and the redox behavior from different particles. In this study, the electrochemical processes of individual PB particles were investigated using nano-impact electrochemistry. By varying the potentials, different types of transient current signals were obtained that revealed the kinetic mechanism of each oxidation/reduction reaction in combination with theoretical simulation. Additionally, a partially contradictory conclusion between single-particle analysis and the ensemble-averaged measurement was discussed. These findings contribute to a better understanding of the electrochemical processes of cathode materials with multiple redox centers, which facilitates the development of effective strategies to optimize these materials.     

Relationships between the particle velocity and introduction of drug-loaded microparticles into the skin in a microparticulate bombardment system

Recently, it has been suggested that a microparticulate bombardment system would be a very useful tool for the delivery of a variety of powdered drugs as an alternative to parenteral injection via a needle. However the relationship between the particle dynamics and introduction into the skin has not been researched using this system. In the present study, we analyzed the velocity of microparticles bombarded by the Helios(TM) gun system under various conditions using particle image velocimetry (PIV). The particle kinetic energy, which depended on the particle velocity and particle mass, was increased with increasing helium pressure and particle size, decreasing bombardment dose, resulting in the increased percentage introduction and relative bioavailability (F(0-24 h)). The particle velocity had a greater influence than the particle mass. Therefore, in order to be the most effective system for introduction into the skin, it is necessary to use a high helium pressure and microparticles of high density. However, it is also necessary to consider the skin damage after bombardment.     

Calculation of the number of atoms displaced during the irradiation of monolayer graphene

The irradiation of monolayer graphene, combined with chemical functionalization, could be an effective method for modifying its electronic structure and for achieving specific physical properties adjusted to different applications. A difficulty arising during planning and studying the irradiation in this system is that many of the models of interaction of the radiation with the substance cannot be applied to the two-dimensional structure of graphene. In particular, the mathematical expressions available to calculate the number of atoms displaced during the bombardment with particles can be applied only to 3D isotropic solids. In the present work, an alternative analytic expression is presented for the irradiation of graphene with heavy ions or with protons and other light charged particles. The expression was obtained on the basis of the classic theory of dispersion, using a Coulomb potential for the light charged particles and one of Inverse Square for heavy ions. For medium values of the energy of the incident particle a decreasing dependence of the number of displaced atoms with energy is obtained. This behavior, related with the two-dimensional structure of the target, had been observed in other authors’ works using computational simulation.     

基于布朗棘轮的单通道分离体系的模拟研究

分子在微尺度受限空间内的扩散行为是微观化学的重要研究领域. 本文利用布朗棘轮效应构建了一种微型单通道分离器件模型, 并基于随机行走理论对其中分子的扩散分离运动进行了模拟研究, 阐明了该体系的分离机理并考察了不同条件对分子扩散分离运动的影响. 模拟结果表明, 通过调节驱动力对各组分粒子的作用周期, 可以控制粒子与分离通道两端势垒发生不同程度的相互作用, 从而在单分离通道内实现粒子向不同方向的有效分离. 同时, 也给出了利用该分离体系进行分离的组分粒子本身的扩散运动与受外力驱动运动的相对大小需满足的条件. 通过调整分离器件的结构参数, 可在实现最佳分离效果的同时节约时间成本. 本文提出的模拟方法对开发微型分离器件及优化操作参数等具有参考意义.     

动态光散射法测量颗粒粒径的溯源性

分别对动态光散射粒径测量仪的入射波长、散射角度、测量池温度进行校准,并对影响测量结果准确性各因素的不确定度分量进行了评价,校准后动态光散射仪的测量结果可溯源至国家计量标准。为消除多重散射、颗粒间相互作用、颗粒粒径分布对动态光散射测量结果的影响,建立了动态光散射测量结果修正方法。其中为消除多重散射及颗粒间相互作用的影响,需采用多浓度测量或线性回归的方法得到特定浓度下的颗粒粒径;为修正颗粒粒径分布对动态光散射测量结果的影响,需先采用SEM方法准确测量颗粒粒径分布,然后根据光强加权动力学平均粒径和数量平均粒径的理论公式,得到二者之间的差异。     

Conversion of surface energy and manipulation of a single droplet across micropatterned surfaces

To clarify a driving mechanism for the self-movement of a droplet across hydrophobic textured surfaces in series and to develop applications for a microfluidic device, we report a theoretical model, a microfabrication technique, and experimental measurements. The contact angle of a droplet on a composite surface, the stable surface energy level, and the energy barrier caused by hysteresis were investigated. With increasing patterned density of the microstructure, the contact angle and stable surface energy decreased gradually, but the energy barrier increased. Both the analytical results and the experimental measurements show that the surface energy for a suspended status is greater than that for a collapsed status, which produces increased energy to generate the movement of a droplet. An analysis of interactions between actuation force, resistive force, and viscous force during the motion of a droplet is based on the equilibrium between forces. From the perspective of energy conversion, the difference in surface energy between a higher state and a lower state would drive a single droplet and make it move spontaneously if it could overcome the static friction force resulting from hysteresis and the kinetic friction force under droplet movement. The mean velocity in the present device, measured to be 62.5 mm s (-1), agrees satisfactorily with the theoretical prediction. The model developed for the energy levels enables us to assess the contact mode of a droplet placed on the patterned surface. For a prediction of the transport capability of the designed devices, a theoretical interpretation of the conversion between the surface energy and the kinetic energy of the droplet establishes a criterion that the pattern density of a textured surface should be less than 0.76. The effective rate of energy conversion is estimated to be 20.6%.     

Molecular dynamics simulation of the structural configuration of binary colloidal monolayers

Molecular dynamics simulations of binary colloidal monolayers, i.e., monolayers consisting of mixtures of two different particle sizes, are presented. In the simulations, the colloid particles are located at an oil-water interface and interact via an effective dipole-dipole potential. In particular, the influence of the particle ratio on the configurations of the binary monolayers is investigated for two different relative interaction strengths between the particles, and the pair correlation functions corresponding to the binary monolayers are calculated. The simulations show that the binary monolayers can only form two-dimensional crystals for certain particle ratios, for example, 2:1, 6:1, etc., while, for example, for a particle ratio of 7:1 the monolayers are found to be in a disordered, glassy state. The calculations also reveal that in analogy to the Wigner lattice the configurations are very sensitive to the relative interaction strength between the particles but not to the absolute magnitude of the interaction strength, even when particle size effects are taken into account. Consequently, it is argued that a comparison between the calculated configurations and actual binary particle monolayer systems could provide useful information on the relative interaction strength between large and small particles. Possible mechanisms giving rise to disparities in the interaction strength between large and small particles are described briefly.     

Particle adsorption and deposition: role of electrostatic interactions

This work demonstrates how electrostatic interactions, described in terms of the classical DLVO theory, influence colloid particle deposition phenomena at solid/liquid interfaces. Electrostatic interactions governing particle adsorption in both non-polar and polar media (screened interactions) are discussed. Exact and approximate methods for calculating the interaction energy of spherical and non-spherical (anisotropic) particles are presented, including the Derjaguin method. Phenomenological transport equations governing particle deposition under the linear regime are discussed with the limiting analytical expressions for calculating initial flux. Non-linear adsorption regimes appearing for higher coverage of adsorbed particles are analysed. Various theoretical approaches are exposed, aimed at calculating blocking effects appearing due to the presence of adsorbed particles. The significant role of coupling between bulk transport and surface blocking is demonstrated. Experimental data obtained under well-defined transport conditions, such as diffusion and forced convection (impinging-jet cells), are reviewed. Various experimental techniques for detecting particles at interfaces are discussed, such as reflectometry, ellipsometry, streaming potential, atomic force microscopy, electron and optical microscopy, etc. The influence of ionic strength and flow rate on the initial particle deposition rate (limiting flux) is presented. The essential role of electrostatic interactions in particle deposition on heterogeneous surfaces is demonstrated. Experimental data pertinent to the high-coverage adsorption regime are also presented, especially the dependence of the maximum coverage of particles and proteins on the ionic strength. The influence of lateral electrostatic interactions on the structure of particle monolayers is elucidated, and the links between colloid and molecular systems are pointed out.