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.     

Electron microscopy study of aggregation of microclusters of sulphur

A study of aggregation of sulphur particles in colloidal suspension of sulphur in water-methanol mixture using TEM and electron diffraction is reported. From the micrographs the aggregates formed have been found to be random and tenuous indicating a fractal structure. The electron diffraction patterns of the aggregates are used to study the mechanism of diffusion and reaction limited aggregation.     

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.     

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.     

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     

Self-Assembled Structures of Colloidal Dimers and Disks on a Spherical Surface

We study self-assembly on a spherical surface of a model for a binary mixture of amphiphilic dimers in the presence of guest particles via Monte Carlo (MC) computer simulation. All particles had a hard core, but one monomer of the dimer also interacted with the guest particle by means of a short-range attractive potential. We observed the formation of aggregates of various shapes as a function of the composition of the mixture and of the size of guest particles. Our MC simulations are a further step towards a microscopic understanding of experiments on colloidal aggregation over curved surfaces, such as oil droplets.     

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.     

Quasi-2D Monte Carlo simulations of a colloidal dispersion composed of magnetic plate-like particles with magnetic moment normal to the particle axis

We have investigated aggregation phenomena of a colloidal dispersion composed of magnetic plate-like particles by means of Monte Carlo simulations. Such plate-like particles have been modelled as disk-like particles with magnetic moment normal to the particle axis at the particle centre, with the section shape of a spherocylinder. The main objective of the present study is to clarify the influences of the magnetic field strength and magnetic interactions between particles on particle aggregation phenomena. We have concentrated our attention on a quasi-2D system from an application point of view such as the development of surface quality changing technology using such magnetic plate-like particles. A magnetic field is applied along the direction perpendicular to the plane of the monolayer. Internal structures of particle aggregates are discussed quantitatively in terms of radial distribution and orientational pair correlation functions. For the case of strong magnetic interactions between particles, particles form long column-like clusters with their magnetic moments alternating in direction between the neighbouring particles. These tendencies appear under circumstances of a weak applied magnetic field. However, as the magnetic field strength increases, particles incline towards the magnetic field direction, so that particles do not form such clusters.     

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.     

Inelastic collisions and anisotropic aggregation of particles in a nematic collider driven by backflow

We design a nematic collider for controlled out-of-equilibrium anisotropic aggregation of spherical colloidal particles. The nematic surrounding imparts dipolar interactions among the spheres. A bidirectional backflow of the nematic liquid crystal in a periodic electric field forces the spheres to collide with each other. The inelastic collisions are of two types, head to tail and head to head. Head-to-tail collisions of dipoles result in longitudinal aggregation while head-to-head collisions promote aggregation in the transversal direction. The frequency of head-to-head collisions is set by the impact parameter that controls the resulting shape of aggregates, their anisotropy, and fractal dimension.     

On the influence of the hydrodynamic interactions on the aggregation rate of magnetic spheres in a dilute suspension

Magnetostatic attraction may lead to formation of aggregates in stable colloidal magnetic suspensions and magneto-rheological suspensions. The aggregation problem of magnetic composites under differential sedimentation is a key problem in the control of the instability of non-Brownian suspensions. Against these attractive forces are the electrostatic repulsion and the hydrodynamic interactions acting as stabilizing effects to the suspension. This work concerns an investigation of the pairwise interaction of magnetic particles in a dilute sedimenting suspension. We focus attention on suspensions where the Péclet number is large (negligible Brownian motion) and where the Reynolds number (negligible inertia) is small. The suspension is composed of magnetic micro-spheres of different radius and density immersed in a Newtonian fluid moving under the action of gravity. The theoretical calculations are based on direct computations of the hydrodynamic and the magnetic interactions among the rigid spheres in the regime of low particle Reynolds number. From the limiting trajectory in which aggregation occurs, we calculate the collision efficiency, representing the dimensionless rate at which aggregates are formed. The numerical results show clear evidence that the hydrodynamic interactions are of fundamental relevance in the process of magnetic particle aggregation. We compare the stabilizing effects between electrostatic repulsion and hydrodynamic interactions.     

Aggregation of colloidal particles with a finite interparticle attraction energy

Aggregation of colloidal particles with a finite attraction energy was investigated with computer simulations and with gold particles coated with a surfactant. Computer simulations were carried out with the Shih-Aksay-Kikuchi (SAK) model, which incorporates a finite nearest-neighbor attraction energy-E into the diffusion-limited-cluster-aggregation (DLCA) model. Both the computer simulations and the experiments showed that (i) with a finite interparticle attraction energy, aggregates can still remain fractal, and (ii) the fractal dimension remains unchanged at large interparticle attraction energies and increases when the interparticle attraction energy is smaller than 4k _B T whereT is the temperature andK _B is the Boltzmann constant. The agreement between the simulations and the experimental results suggests that the reversible aggregation process in a colloidal system can be represented by the SAK model.     

具有幂次相互作用的磁性粒子凝聚过程的数值研究

在扩散限制凝聚模型的基础上引入粒子的自旋自由度(包括自旋向上和向下),并假设粒子间存在幂次Ising磁相互作用,采用Monte Carlo方法研究了在不同相互作用力程情况下磁性粒子的分形生长规律.模拟结果表明,当粒子间以反铁磁方式耦合时,凝聚体中的粒子自旋交替凝聚.当粒子间以铁磁方式耦合时,凝聚体中粒子的自旋分布与相互作用力程有关:对于短程作用系统,凝聚体中存在大小不同的自旋畴块,即为铁磁生长;而对于长程相互作用系统,凝聚体中的自旋出现反常分布,即中心区域是近似反铁磁生长的结构,其外围后续生长的粒子却保持 关键词： 幂次相互作用 扩散限制凝聚模型 自旋     

紫外光引发还原制备金溶胶及其SERS活性的研究

文章报道了一种用紫外光引发还原制备金溶胶的新方法,其还原过程经历了自由基机理。用紫外可见光谱观察了不同反应时间溶胶状态的变化。结果表明,光照反应2h时明显出现金溶胶粒子,7h后氯金酸基本转化完毕。同时,研究了稳定剂聚乙烯吡咯烷酮(PVP)的加入对还原过程的影响,结果表明,PVP的加入不仅稳定了溶胶,而且降低了反应速率。用SEM观察了溶胶粒子聚集体的形貌。最后以1,4-bis(4-vinylpyridyl)phenylene为探针分子研究了这种溶胶的SERS活性。     

Plasma resonance — enhanced raman scattering by absorbates on gold colloids: The effects of aggregation

The excitation profile of the 1014 cm^?1 Raman band of pyridine adsorbed on colloidal gold particles, and the extinction and elastic scattering spectra of the colloids, are measured as the colloids slowly aggregate in the presence of pyridine. Transmission electron microscopy shows that the aggregates formed are predominantly strings of particles rather than compact clusters, and the dipolar plasma modes of the aggregates are therefore split into longitudinal and transverse components. It is shown that only for excitation under the longitudinal resonance extinction band is there a large Raman intensity enhancement. The Raman excitation profile maximum corresponding to excitation under this resonance moves progressively to longer wavelengths, increasing substantially in height, as the aggregation proceeds. Thus aggregation is most advantageous for the realization of large Raman signals from these colloids, the Raman intensity at a given excitation wavelength increasing approximately as the square of the absorbance at that wavelength as the aggregation proceeds. These observations are discussed in relation to the electromagnetic field enhancement contribution to the surface Raman effect, with which they are in general agreement, and the large increase in ¦?¦² for gold and silver with increase in wavelength is shown to be a significant factor in accounting for some of these effects of aggregation.     

Measurement of Aggregate Fractal Dimensions Using Static Light Scattering

Aggregates formed from colloidal particles will vary in shape according to the aggregation regime prevalent. Compact structures are formed when the aggregation is slow, whilst loose tenuous structures are formed when rapid (or diffusion limited) aggregation prevails. These structures can be fractal in nature, that is, there is a relationship between porosity and the number of primary particles making up the aggregate, and is described by the fractal dimension, d_F. Fractal dimensions of hematite aggregates have been measured experimentally using the static light scattering technique. Fractal dimensions varied with aggregation regimes; for the rapid aggregation regime, d_F was found to be 2.8, whilst for conditions in which aggregation was slow (retardation forces prevail), d_F's of 2.3 were measured. For conditions which lead to aggregation in which both diffusion and retardation forces play a part, structures with fractal dimensions such that 2.3 < d_F < 2.8 were found. The effects of adsorbed fulvic acid, a naturally occuring organic acid, on the kinetics of hematite aggregation and on the resulting structure of hematite aggregates were also investigated. The study of aggregate structure shows that the fractal dimensions of hematite aggregates which are partially coated with fulvic acid molecules are higher than those obtained with no adsorbed fulvic acid. The scattering exponents obtained from static light scattering experiments of these aggregates range from 2.83 ± 0.08 to 3.42 ± 0.1. The scattering exponents of greater than 3 indicate that the scattering is the result of objects that contains pores which are bounded by surfaces with a fractal structure, and can be related only to surface fractal dimension. The high fractal dimensions are due to restructuring within the aggregates, which only occured at low coverage by the organic acid.     

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.     

One‐pot synthesis of silver particle aggregation as highly active SERS substrate

Silver particles with different degrees of aggregation were synthesized through a sodium dodecyl sulfate‐assisted one‐pot reaction in an aqueous medium. The products were characterized by transmission electron microscopy, scanning electron microscopy and UV‐visible spectroscopy. The results showed that the degree of aggregation of the Ag nanoparticles could be tuned by changing the reaction parameters, such as the reaction temperature and time. A possible formation process of the Ag aggregate is proposed on the basis of a series of experimental results. Moreover, the surface‐enhanced Raman scattering (SERS) effect of the Ag aggregates was evaluated by using rhodamine 6G as a Raman probe molecule. It was demonstrated that the SERS enhancement ability is related to the degree of aggregation of Ag particles, and a high SERS signal can be observed by selecting Ag nanoparticles with the proper degree of aggregation as substrates. Moreover, the aggregates showed good reproducibility and stability to SERS from organic molecules. Copyright © 2010 John Wiley & Sons, Ltd.     

Light scattering from colloids

This paper presents a review of light scattering results on static and dynamic properties of ordered colloidal suspensions of charged polystyrene particles and fractal colloidal aggregates. Our studies on static structure factor,S(Q), of ordered monodisperse colloidal suspensions and binary mixtures of particles with different particle diameters, measured by angle-resolved Rayleigh scattering will be discussed. This will include determination of bulk modulus using gravitational compression and observation of colloidal glass (inferred from splitting of the second peak inS(Q)). Dynamic light scattering, with real time analysis of scattered intensity fluctuations, is used to get information about Brownian dynamics of the particles. Recent advances in the field of light scattering from colloidal aggregates which show fractal geometry will also be discussed.     

Organization of Functionalized Gold Nanoparticles by Controlled Protein Interactions

Gold colloidal particles were synthesized and modified by molecular self‐assembly. In addition, the reaction of biotinylated colloids with a tetrameric protein, avidin, was studied by optical absorption spectroscopy and dynamic light scattering. The modification involves the chemisorption of octadecanethiol on the gold, with the further attachment of alkyl biotin and cross‐linking with avidin molecules. The specific interaction of avidin with biotin leads to the controlled cross‐linking of particles. The degree of flocculation was quantified using a semi‐empirical flocculation parameter and its dependence on the biotinylation system was studied. The measured data were in good agreement, showing the possibility of regulating the aggregation rate and size of the aggregates using the experimental time, degree of biotinylation, and avidin concentration. The morphology of the self‐assembled gold monolayers, from the aggregated particles, was imaged by high‐resolution scanning electron microscopy. The structure of the thin particulate film depends on the bulk aggregate size and aggregation rate.