Colloidal aggregation with sedimentation: concentration effects

The results of computer models for colloidal aggregation, that consider both Brownian motion and gravitational drift experienced by the colloidal particles and clusters, are extended to include concentrations spanning three orders of magnitude. In previous publications and for a high colloidal concentration, it was obtained that the aggregation crosses over from diffusion-limited colloidal aggregation (DLCA) to another regime with a higher cluster fractal dimension and a speeding up followed by a slowing down of the aggregation rate. In the present work we show, as the concentration is decreased, that we can still cross over to a similar regime during the course of the aggregation, as long as the height of the sample is increased accordingly. Among the differences between the mentioned new regimes for a high and a low colloidal concentration, the cluster fractal dimension is higher for the high concentration case and lowers its value as the concentration is decreased, presumably reaching for low enough concentrations a fixed value above the DLCA value. It is also obtained the fractal dimension of the sediments, arising from the settling clusters that reach the bottom and continue a 2D-like diffusive motion and aggregation, on the floor of the container. For these clusters we now see two and sometimes three regimes, depending on concentration and sedimentation strength, with their corresponding fractal dimensions. The first two coming from the crossover already mentioned, that took place in the bulk of the sample before the cluster deposition, while the third arises from the two-dimensional aggregation on the floor of the container. For these bottom clusters we also obtain their dynamical behavior and aggregation rate.Received: 7 January 2004, Published online: 25 March 2004PACS: 61.43.Hv Fractals; macroscopic aggregates (including diffusion-limited aggregates) - 82.70.Dd Colloids - 05.10.Ln Monte Carlo methods     

Elasticity and critical bending moment of model colloidal aggregates

The bending mechanics of singly bonded colloidal aggregates are measured using laser tweezers. We find that the colloidal bonds are capable of supporting significant torques, providing a direct measurement of the tangential interactions between particles. A critical bending moment marks the limit of linear bending elasticity, past which small-scale rearrangements occur. These mechanical properties underlie the rheology and dynamics of colloidal gels formed by diffusion-limited cluster aggregation, and give critical insight into the contact interactions between Brownian particles.     

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.     

Self-organization in aggregating colloids

Summary The interceluster organization of a two-dimensional colloidal system undergoing diffusion-limited cluster-cluster aggregation is considered. During this process the system evolves into a stationary, scaling state. In this state the organization arises from effective intercluster repulsion due to the mutually exclusive depletion zones surrounding each cluster. It is shown that in the scaling regime the relevant size of the depletion zones is determined by the separation between clusters, rather than the cluster size. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Kinetic arrest in polyion-induced inhomogeneously charged colloidal particle aggregation

Polymer chains adsorbed onto oppositely charged colloidal particles can significantly modify the particle-particle interactions. For sufficient amounts of added polymers, the original electrostatic repulsion can even turn into an effective attraction and relatively large aggregates can form. The attractive interaction contribution between two particles arises from the correlated adsorption of polyions at the oppositely charged particle surfaces, resulting in a non-homogeneous surface charge distribution. Here, we investigate the aggregation kinetics of polyion-induced colloidal complexes through Monte Carlo simulation, in which the effect of charge anisotropy is taken into account by a DLVO-like inter-particle potential, as recentely proposed by Velegol and Thwar (Langmuir 17, 7687 (2001)). The results reveal that the aggregation process slows down due to the progressive increase of the potential barrier height upon clustering. Within this framework, the experimentally observed cluster phases in polyelectrolyte-liposome solutions can be interpreted as a kinetic arrested state.     

Theory of Electrorotation of Clustered Colloidal Particles

When a colloidal suspension is exposed to a strong rotating electric field, an aggregation of the suspended particles is induced to appear. In such clusters, the separation between the suspended particles is so close that one could not neglect the multiple image effect on the electrorotation (ER) spectrum. Since so far the exact multiple image method exists in two dimensions only, rather than in three dimensions, we investigate the ER spectrum of the clustered colloidal particles in two dimensions, in which many cylindrical particles are randomly distributed in a sheet cluster. We report the dependence of the ER spectrum on the material parameters. It is shown that the multiple image method predicts two characteristic frequencies, at which the rotation speed reaches maximum. To this end, the multiple image method is numerically demonstrated to be in good agreement with the known Maxwell-Garnett approximation.     

Kinetics of colloidal fractal aggregation by differential dynamic microscopy

We study the kinetics of an aggregation process induced by adding salt to a stable colloidal suspension of 73 nm (diameter) particles. Despite the subdiffraction size of the colloidal particles, the process is monitored via optical microscopy, which is used here to obtain time-resolved scattering information about the colloidal aggregates. The radius of the aggregates is determined as a function of time and their fractal dimension is extracted. Our results are compatible with a diffusion limited aggregation process, as independently confirmed by spectral turbidimetry measurements on the same sample.     

胶体晶体结晶过程与人造三维周期性集团点阵材料

胶体晶体结晶的物理过程和以胶体晶体为基的三维周期性集团点阵材料的制备是目前实验凝聚态物理的一个热点领域,文章对胶体粒在悬浮液中自组织有序化的物理机制、结构相变与形态的形成和以胶体晶体为基的人造三维周期性点材料作了介绍,无论是从实验上还是理论上看,对胶体体系中发生的自组织有序化的物理机制还有没有给出令人信服的证据和解释。而胶体晶体的制备为具有新异功能的三维周期性集团国材料设计开辟了一条新途径,因而在     

Inter-cluster scaling in two-dimensional colloidal aggregation

Cluster-cluster aggregation has been studied experimentally in two-dimensional colloidal systems of moderately high area fraction. In the diffusion limited regime the system spontaneously exhibits ordering beyond the scale of the fractal aggregates, which persists into the gelled state. This ordering arises from an effective inter-cluster repulsion due to the mutually exclusive depletion zones surrounding each cluster. Various metrical and topological properties of the system indicate that this long-range order is stationary, apart from the inherent change of scale as the clusters grow. Topological correlations show that the inter-cluster self-organization is compatible with maximum entropy: the non-equilibrium system behaves as if it were in statistical equilibrium, and no physical forces are involved in the long-range order. For the reaction-limited case no such inter-cluster ordering is evident at any stage, the system is nonstationary, and the aggregation is governed by specific physical forces.     

有限步扩散反应置限分形聚集

综合考虑扩散粒子浓度n、粒子扩散限制范围Δ、扩散粒子与种粒子或团簇相遇时，反应概率P及粒子扩散步数W的影响，提出了有限步扩散反应置限聚集的分形生长模型，模拟得到一系列典型的聚集生长图形，计算了相应的分形维数.结果表明，在粒子浓度n较小时，呈离散团簇状生长；而在粒子浓度较大时，则随反应概率P或粒子扩散步数W的增大，从离散团簇状生长转变为连续枝叉状生长. 关键词：     

Electric field induced pattern formation in interfacial metal colloid films

First results on electric field induced aggregation in a novel colloidal film are presented. The aggregate appears as a dark structure on the shiny background of the metallic colloidal film that forms at the interface between two immiscible liquids. A variety of shapes are observed, ranging from compact circular, to highly ramified dendritic ones, depending on control parameters such as voltage and chemical composition. The aggregation process was investigated for a wide range of parameters by video photography and subsequent pattern analysis, as well as by Auger spectroscopic measurements of dried samples. A new type of mechanism—a combination of electroaggregation of the colloid particles and electrodeposition of metal ions—is proposed to account for the observations.     

Colloidal crystal growth at externally imposed nucleation clusters

We study the conditions under which and how an imposed cluster of fixed colloidal particles at prescribed positions triggers crystal nucleation from a metastable colloidal fluid. Dynamical density functional theory of freezing and Brownian dynamics simulations are applied to a two-dimensional colloidal system with dipolar interactions. The externally imposed nucleation clusters involve colloidal particles either on a rhombic lattice or along two linear arrays separated by a gap. Crystal growth occurs after the peaks of the nucleation cluster have first relaxed to a cutout of the stable bulk crystal.     

Monte Carlo simulation of Hamaker nanospheres coated with dipolar particles

Parallel tempering Monte Carlo simulation is carried out in systems of N attractive Hamaker spheres dressed with n dipolar particles, able to move on the surface of the spheres. Different cluster configurations emerge for given values of the control parameters. Energy per sphere, pair distribution functions of spheres and dipoles as function of temperature, density, external electric field, and/or the angular orientation of dipoles are used to analyse the state of aggregation of the system. As a consequence of the non-central interaction, the model predicts complex structures like self-assembly of spheres by a double crown of dipoles. This interesting result could be of help in understanding some recent experiments in colloidal science and biology.     

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.     

Fractal aggregates induced by liposome-liposome interaction in the presence of Ca2+

We present a study of the fractal dimension of clusters of large unilamellar vesicles (LUVs) formed by egg yolk phosphatidylcholine (EYPC), dimyristoylphosphocholine (DMPC) and dipalmitoylphosphocholine (DPPC) induced by Ca²⁺ . Fractal dimensions were calculated by application of two methods, measuring the angular dependency of the light scattered by the clusters and following the evolution of the cluster size. In all cases, the fractal dimensions fell in the range from 2.1 to 1.8, corresponding to two regimes: diffusion-limited cluster aggregation (DLCA) and reaction-limited cluster aggregation (RLCA). Whereas DMPC clusters showed a typical transition from the RLCA to the DLCA aggregation, EYPC exhibited an unusual behaviour, since the aggregation was limited for a higher concentration than the critical aggregation concentration. The behaviour of DPPC was intermediate, with a transition from the RLCA to the DLCA regimes with cluster sizes depending on Ca²⁺ concentration. Studies on the reversibility of the aggregates show that EYPC and DPPC clusters can be re-dispersed by dilution with water. DMPC does not present reversibility. Reversibility is evidence of the existence of secondary minima in the DLVO potential between two liposomes. To predict these secondary minima, a correction of the DLVO model was necessary taking into account a repulsive force of hydration.     

Evolution of an ensemble of fractal aggregates in a colloidal system

A theoretical study is presented of primary-minimum aggregation of colloidal particles, which generally leads to the formation of ramified fractal clusters. The focus is placed on the cooperative effects due to competition between aggregates for particles moving freely in the colloidal suspension. An analysis shows that the competition leads to aggregate density distributions and aggregation kinetics governed by more complicated laws as compared to those established in previous numerical and analytical studies of single-cluster growth.     

Quantum mechanics simulation and experimental study of adhesive interaction and aggregation of carbon-silicate nanoparticles—reinforcing fillers of polymer composites

Nanoparticles are widely used as polymer composite-reinforcing additives—fillers. Understanding the interaction mechanisms and regularities responsible for nanoparticle aggregation is of great significance for elucidating the nature of reinforcing of polymer composites. The paper reports on quantum mechanics calculations and full-scale experimental study of adhesive interaction of carbon and silicate adsorption complexes (nanomodels of active filler particles of polymer composites). The quantum mechanics approach allowed describing the adhesive properties of particle aggregates reasoning from nanoscopic structure of their surface. The quantum mechanics data were checked for adequacy on schungite—a natural mineral containing carbon and silicate. Schungite microparticles were milled to nanosizes by colloidal grinding in various disperse liquid media (alcohol, acetone, water) and the structure and properties of aggregated schungite micro- and nanoparticles were studied; fractal analysis of their surface was performed. It is found that smaller aggregates of silicate and carbon particles with higher surface fractal dimension are formed in colloidal grinding with small molecular sizes of disperse media (in our case, ethanol or methanol) and this agrees with the data predicted by quantum mechanics calculations.     

Self-assembly of CuSO4 nanoparticles and bending multi-wall carbon nanotubes on few-layer graphene surfaces

When a colloidal suspension is allowed to wet a suitable substrate, various patterns emerge that can be varied from isolated island-like structures to fractal patterns. In this work we investigate the patterns arising from the interplay of colloidal copper sulfate suspensions containing carbon nanotubes with few-layer graphene substrates. The compositions of the thin film samples were investigated using X-ray photoelectron spectroscopy, surface topography and the nanostructure of the thin films were probed with atomic force microscope and transmission electron microscope respectively. The colloidal suspensions were characterized using contact angle and viscosity measurements. The colloidal suspensions when dip coated on few-layer graphene substrates exhibited fractal like morphology with the aggregation of copper sulfate crystallites to hexagonal platelets. This aggregation is explained invoking the depletion attraction theory. The various patterns observed experimentally were reproduced using a Monte Carlo simulation.     

Two-Photon Fluorescence Tracking of Colloidal Clusters

In situ dynamics of colloidal cluster formation from nanoparticles is yet to be addressed. Using two-photon fluorescence (TPF) that has been amply used for single particle tracking, we demonstrate in situ measurement of effective three-dimensional optical trap stiffness of nanoparticles and their aggregates without using any position sensitive detector. Optical trap stiffness is an essential measure of the strength of an optical trap. TPF is a zero-background detection scheme and has excellent signal-to-noise-ratio, which can be easily extended to study the formation of colloidal cluster of nanospheres in the optical trapping regime. TPF tracking can successfully distinguish colloidal cluster from its monomer.     

杂质对硬球系统团簇成核临界条件的影响

通过CS状态方程及熵极大原理在多元胶体系统研究了杂质对硬球系统团簇成核临界条件的影响. 极少量元素或杂质的小胶球对系统成核的临界条件的影响也是不可忽略的: 成核的临界体积分量显著地降低;此外,研究还发现杂质对成核的临界尺寸影响较少.