Formation and Aggregation Kinetics of Mixed Metal Hydroxides Agglomerates

The aggregation and fractal structure of mixed metal hydroxides ( MMH ) agglomerates with increasing ionic strength have been studied by dynamic light scattering ( DLS ) and SEM techniques. The experiments indicate that the MMH agglomerates have two different structures in RLA regime and DLA regime, and also give the proof that the transition region between RLA and DLA may occur.     

Cluster-cluster aggregation controlled by the number of intercluster connections: kinetics of aggregation and cluster mass frequency

The aggregation of colloids in the presence of hydrodynamic forces was investigated, employing a numerical model that took into account the masses of the individual clusters and the number of intercluster connections established when two clusters stuck together. The number of possible connections was determined by analyzing all the possible nonoverlapping configurations of stuck clusters. This operation was done for a couple of clusters of various masses, taking into account the assembly of clusters of even and uneven masses. The formulation of the constraints established a certain hierarchy in the sticking on a basis compatible with the irregular fracture model of Horwatt and co-workers. As a result, the permanent sticking of large clusters required the formation of a large number of connections, whereas that of small clusters might be realized even with a small number of connections. Thus, the aggregation started with the features of the standard reaction-limited process and this cluster growth became progressively inhibited as a result of the prevailing effects of the connection constraints. The cluster-mass frequency showed the emergence at least of a second population whose bell-shaped mass distribution was superimposed on the monotonically decreasing distribution resulting from the reaction-limited aggregation process. The results of the numerical study were confronted with those previously obtained in the aggregation of hydrated polystyrene latex particles dispersed in 1 M sodium chloride solution. The two striking features--the aggregate growth kinetics and the mass distribution function--were common to the computer-generated clusters and the latex aggregates.     

煤的缔合结构研究Ⅱ溶液黏度变化

采用Pal-Rhodes方程描述了一种煤可溶组分PI-1溶液黏度随时间的变化关系,并计算得到了缔合物的缔合维数。25 ℃下PI-1在NMP和CS2/NMP混合溶剂中缔合物的缔合维数分别为2.08和2.19,表明其在低温下缔合属于反应控制机理。随着温度的提高,缔合维数趋于减小,表明在较高温度下,PI-1具有较快的缔合动力学过程,在50 ℃时PI-1在NMP中的缔合维数大于在CS2/NMP混合溶剂中的缔合维数,表明PI-1在NMP的缔合速率相对低于CS2/NMP混合溶剂。     

Phase-field modeling of two-dimensional solute precipitation∕dissolution: solid fingers and diffusion-limited precipitation

Two-dimensional dendritic growth due to solute precipitation was simulated using a phase-field model reported earlier [Z. Xu and P. Meakin, J. Chem. Phys. 129, 014705 (2008)]. It was shown that diffusion-limited precipitation due to the chemical reaction at the solid-liquid interface has similarities with diffusion-limited aggregation (DLA). The diffusion-limited precipitation is attained by setting the chemical reaction rate much larger compared to the solute diffusion to eliminate the effect of the interface growth kinetics. The phase-field simulation results were in reasonable agreement with the analytical solutions. The fractal solid fingers can be formed in the diffusion-limited precipitation and have a fractal dimension measured d(f)=1.68, close to 1.64, the fractal dimensionality of large square lattice DLA clusters.     

Study of thermodynamic parameters in amphiphilic systems by lattice Monte Carlo: effect of tails and heads

Results from three-dimensional lattice Monte Carlo simulations of amphiphile–solvent mixtures are presented. The chemical potential is derived from the monomer distribution in different clusters rather than using a Widom particle insertion approach. The effect of tail and head characteristics on the non-ideality of these systems, aggregation number, and premicellar phenomena is considered. The aggregation number and CMC behavior of the simulated amphiphilic systems are compared with existing experimental results for non-ionic amphiphiles. Two kinds of polydispersity changing with total concentration of surfactants are observed which are related to phase transition phenomena. Shape variations in clusters are studied by calculating the eigenvalues of the gyration matrix; it is shown that large clusters are non-spherical. With the Maclaurin’s expansion of activity coefficient into volume fraction, the distribution of excess chemical potential with changing aggregation number is considered. Study of the degree of non-ideality of these amphiphiles reveals that asymmetric amphiphiles are characterized by greater non-ideality than symmetric amphiphiles. Goldstein’s parameters are calculated taking non-ideality into consideration. The difference between the phenomenological model and the simulation data is investigated.     

Pore curvature effect on the stability of Co-MCM-41 and the formation of size-controllable subnanometer Co clusters

Samples of Co-MCM-41 with different pore diameters have been synthesized using organic templates with different alkyl chain lengths. The reducibility of cobalt in these highly stable samples was investigated by TPR and X-ray absorption spectroscopy. We have found that the reducibility correlates strongly with the pore diameter of the MCM-41, with the cobalt incorporated in the smaller pore MCM-41 being more resistant to complete reduction. It is proposed that the distribution of cobalt ions in the pore wall is affected by both the preparation procedure and the pore diameter. The size of the metallic Co clusters formed after different reducing treatments correlates linearly with the pore size, giving direct evidence for the effect of the radius of curvature on reducibility. Complete cobalt reduction after TPR causes an inverse variation of the cluster size with the pore size, resulting from differences in the density of Co clusters and from differences in the rate of Co migration and aggregation outside the pores of MCM-41 with different pore sizes.     

Colloidal aggregation induced by long range attractions

The structure of colloidal clusters formed by long-range attractive interactions under diluted conditions is studied by means of Monte Carlo simulations. For a not-too-long attraction range, clusters show self-similar internal structure with lower density than that typical for diffusive aggregation. For long-range interactions, low kappa, nonfractal clusters are formed (dense at short scales but open at long ones). The dependence on the volume fraction shows that more-compact clusters are grown the higher the colloidal density for diffusive aggregation and attraction-driven aggregation in the fractal regime. The whole trend is explained in terms of the interpenetration among aggregates. In attraction-driven aggregations, the interpenetration of clusters competes with aggregation in the tips of the clusters, causing low-density clusters.     

Experimental analysis of the reaction layer structure in a gas diffusion electrode

The micro-structure of the reaction layer and the performance of a PTFE-bonded gas diffusion electrode having different PTFE contents have been studied experimentally using electrochemical techniques and a mercury pore sizer. A more practical image of the structure has resulted in comparison with any of the models postulated previously. Maximum performance was obtained at 30% PTFE content for oxygen reduction with ca. 75% utilization of platinum clusters, where an activation process is controlling the performance. The reaction layer consists of two distinctive pore distributions with a boundary of ca. 0.1 μm. The smaller pore (primary pore) was assigned to the space in-between the primary particles in their agglomerate and the larger one (secondary pore) to that in-between the agglomerates. Platinum clusters of ca. 80% were located in the primary pores and most of the PTFE was in the secondary pores. On the basis of the experimental results, a schematic micro-structure for the reaction layer is proposed. It was possible to determine the degree of occupation of each pore by the electrolyte or gas from the experimental results. It was revealed that the primary pore works as a reaction volume while the secondary pore works as main gas channels, e.g. 80% of the former is occupied by electrolyte and 30% of the latter contains gas at the composition of maximum performance. Increased gas channels and high utilization of platinum clusters are essential for a high-performance gas diffusion electrode. They were achieved by dispersing efficiently both the catalysed carbon black and the PTFE.     

Computer simulation of selective aggregation in binary colloids

The morphology of clusters formed by selective aggregation of binary colloids is studied in a two-dimensional Monte Carlo simulation for a large range of number fractions (200:1, 100:1, 10:1, 2:1). We find remarkable similarity in morphology to those observed in experiments, from the formation of closed "micelles" to large branched clusters. Quantitative studies of the fractal dimension, kinetics, and cluster size distribution are also carried out and compared with diffusion-limited cluster aggregation and reaction-limited cluster aggregation models.     

Cell-cell contact and membrane spreading in an ultrasound trap

An ultrasonic standing wave trap [Langmuir 19 (2003) 3635] in which the morphologies of 2-D latex–microparticle aggregates, forming a pressure node plane, were characterised has been applied here to different cell suspensions with increasing order of specificity of cross-linking molecule, i.e. polylysine with chondrocytes; wheat germ agglutinin (WGA) with erythrocytes and surface receptors on neural cells. The outcome of initial cell–cell contact, i.e. whether the cells stuck at the point of contact (collision efficiency=1) or rolled around each other (collision efficiency=0), was monitored in situ by video-microscopy. The perimeter fractal dimensions (FD) of 2-D hexagonally symmetric, closely packed aggregates of control erythrocytes and chondrocytes were 1.16 and 1.18, respectively while those for the dendrititc aggregates formed initially by erythrocytes in 0.5 μg/ml WGA and chondrocytes in 20 μg/ml polylysine were 1.49 and 1.66. The FDs for control and molecularly cross-linked cells were typical of reaction-limited aggregation (RLA) and transport diffusion-limited aggregation (DLA), respectively. The FDs of the aggregates of cross-linked cells decreased with time to give more closely packed aggregates without clear hexagonal symmetry. Suspensions of neural cells formed dendritic aggregates. Spreading of inter-cellular membrane contact area occurred over 15 min for both erythrocyte and neural cell dendritic aggregates. The potential of the technique to characterise and control the progression of cell adhesion in suspension away from solid substrata is discussed.     

Detailed model of the aggregation event between two fractal clusters

A model has been developed for describing the aggregation process of two fractal clusters under quiescent conditions. The model uses the approach originally proposed by Smoluchowski for the diffusion-limited aggregation of two spherical particles but accounts for the possibility of interpenetration between the fractal clusters. It is assumed that when a cluster diffuses toward a reference cluster their center-to-center distance can be smaller than the sum of their radii, and their aggregation process is modeled using a diffusion-reaction equation. The reactivity of the clusters is assumed to depend on the reactivity and number of their particles involved in the aggregation event. The model can be applied to evaluate the aggregation rate constant as a function of the prevailing operating conditions by simply changing the value of the particle stability ratio, without any a priori specification of a diffusion-limited cluster aggregation, reaction-limited cluster aggregation, or transition regime. Furthermore, the model allows one to estimate the structure properties of the formed cluster after the aggregation, based on the computed distance between the aggregating clusters in the final cluster.     

Fractal growth of rotating DLA‐clusters

A theoretical model for fractal growth of DLA‐clusters in two‐ and three‐dimensional Euclidean space is proposed. This model allows to study some statistical properties of growing clusters in two different situations: in the static case (the cluster is fixed), and in the case when the growing structure has a nonzero rotation around its germ. By the direct computer simulation the growth of rotating clusters is investigated. The fractal dimension of such clusters as a function of the rotation velocity is found. It is shown that for small enough velocities the fractal dimension is growing, but then, with increasing rotation velocity, it tends to the unity.     

Orthokinetic Aggregation in Two Dimensions of Monodisperse and Bidisperse Colloidal Systems

Orthokinetic aggregation of colloids trapped at the air–liquid interface was studied by direct imaging in a couette cell. This method allowed us to follow the temporal evolution of both the cluster-mass distribution and the cluster structure at a shear rate where Brownian aggregation is suppressed. The interactions between the monodisperse latex particles floating at the air–liquid interface were controlled either by varying the electrolyte concentration or by creating a bidisperse system through the addition of small particles. The results show that the clusters in all of the systems are characterized by a high fractal dimension, indicating that the clusters are rearranged and densified by the shear. Kinetic analysis suggests that aggregation of monodisperse systems mainly proceeds through homogeneous aggregation, i.e., large clusters sticking to other large clusters. The bidisperse system, finally, with a size ratio around 10, favored a more heterogeneous aggregation among small and large clusters throughout the aggregation process; a slightly lower fractal dimension was observed compared to the strongly aggregated monodisperse system.     

Particle design of tolbutamide by the spherical crystallization technique. III. Micromeritic properties and dissolution rate of tolbutamide spherical agglomerates prepared by the quasi-emulsion solvent diffusion method and the solvent change method

With the objective of modifying the micromeritic properties of tolbutamide (i.e., to manufacture a highly functional powder form), particle design was attempted using a quasi-emulsion solvent diffusion (QESD) method, and the micromeritic properties and dissolution rate of the obtained spherical agglomerates were evaluated by comparison with agglomerates prepared by the solvent change (SC) method. For the production of tolbutamide agglomerates by the QESD method, a necessary condition was the addition of a sucrose fatty acid ester to the system as an emulsifying agent. The particle diameter of the agglomerates obtained by the QESD method depended on the size of the initially formed quasi-emulsion droplets, which in turn depended on the viscosity of the solution. In addition, the agglomerates were nearly perfectly spherical in shape. In the QESD method, the quasi-emulsion droplets crystallized instantaneously from the droplet surface inward. The resultant agglomerates were dense, had great mechanical strength and showed excellent flowability due to their perfect spherical shape. On the other hand, the agglomerates produced by the SC method were conglomerates of primary crystals, and fine, needle-like crystals formed on their surface. As a result, these agglomerates had a large specific surface area, and they therefore showed greater solubility than the agglomerates prepared by the QESD method.     

胜利超稠油的乳化降黏机理研究

研究了胜利油田滨南超稠油单56-4X4高黏的内在原因。油品性质分析结果表明,影响其高黏度的主要因素有两个:胶质、沥青质的总含量超过30%;有机杂原子O、N、S及过渡金属Ni等形成的配位络合物增加了沥青质分子的内聚力。实验筛选出的降黏剂OP-10对该超稠油降黏率高达99.59%。通过FT-IR、SEM、分子量和偶极矩等分析对比了降黏剂作用前后胶质、沥青质的结构性质变化,结果表明,OP-10使胶质、沥青质的氢键缔合作用减弱,部分拆散沥青质的堆积结构,从而使胶质、沥青质的分子量和偶极矩减小,分析得到降黏剂分子能渗透及分散胶质、沥青质的堆砌聚集体。偏光显微镜对乳状液及蜡晶微观形态的分析表明,降黏剂OP-10使超稠油乳状液由W/O型反相为O/W型而起到降黏作用;使蜡晶的聚集形态由细小均匀转变为尺寸较大的絮凝体,破坏蜡晶的三维网络结构,促进稠油黏度的下降。     

Aggregation Behavior of Polyether Block Copolymers with Dendritic Structure in Aqueous Solutions

Two dendritic block copolymers with the same contents of PPO and PEO but different branches and blocks were synthesized by anion polymerization. Their aggregation behavior and aggregation morphology were investigated by steady-state fluorescence and transmission electron microscopy. For SD64 copolymer with PPO-PEO diblock branch, it can be proved that only intermolecular aggregates are formed, the aggregation number and aggregation diameter are increased with concentration. Whereas for SD343 dendritic copolymer with PPO-PEO-PPO triblock branch, hydrophobic PPO chains located on the edge of SD343 copolymers can associate within the same polymer chain and also between different polymer chains, so the aggregates were inclined to change from intramolecular micelles to intermolecular clusters with concentration increasing.     

Simulation of diffusion-limited aggregation and reactions over its surfaces

Modifications of Witten–Sander diffusion-limited aggregation (DLA ) were proposed. Effects caused by releasing boundary shape, nonfixed seed, and rotating biased drift on the morphology of the resulting DLA were examined. The diffusion-limited reaction on surfaces of DLA were also studied by performing a multifractal scaling analysis. © 1994 John Wiley & Sons, Inc.     

Aggregation behavior of single-walled carbon nanotubes in dilute aqueous suspension

The aggregation behavior of colloidal single-walled carbon nanotubes (SWNT) in dilute aqueous suspensions was investigated using a novel light scattering measurement technique. The aggregation of SWNT in three suspensions was examined: (1) nanotubes after acid treatment; (2) as-received nanotubes stabilized by a nonionic surfactant; and (3) acid-treated nanotubes with nonionic surfactant. Continuous light scattering measurements of the SWNT suspensions (probing the 38-436 nm length scale) made over two weeks showed that the nanotubes in each sample formed networks with fractal-like structures. The as-received nanotubes were stable over the measurement period, while the acid-treated nanotube suspension showed greater dispersion variability over time, yielding looser structures at large length scales and more compact structures at smaller length scales. The addition of surfactant to the acid-treated suspension significantly enhanced nanotube dispersion.     

Control of particle cluster dispersion using responsive polymeric additives

The dispersion behavior of clusters of hydrophilic and hydrophobic silica treated with a thermoresponsive polymer has been investigated. The influence of the thermoresponsive interfacial chemistry was assessed by performing dispersion studies in poly(dimethylsiloxane) (PDMS) at 25 and 68 degrees C for agglomerates of powders incorporating poly(N-isopropyl acrylamide) (PNIPAM), a thermoresponsive polymer, and water. While the dispersion of clusters of hydrophilic silica was found to be temperature independent, dispersion of hydrophobic silica exhibited a temperature dependency. The response of the polymer upon temperature variation brings about modifications in the interparticle interactions of the PNIPAM-treated powders thus leading to changes in the cluster cohesivity. The dependence of the cluster cohesivity on temperature was evidenced through changes in the dispersion mechanism and kinetics of the treated silica clusters at both tested temperatures. In addition, optical microscopy of silica suspensions with and without PNIPAM at 25 and 60 degrees C, illustrated the effect of the polymer presence and configuration on the particle-particle interaction forces. While micrographs of the particles at 25 degrees C show less evidence of particle aggregation, the micrographs at 60 degrees C illustrate an increase in aggregation suggesting an enhancement in the attractive forces between particles.     

Aluminium ions at polyelectrolyte interfaces. III. Role in polyacrylic acid/aluminium oxide and humic acid/kaolinite aggregate cohesion

Understanding the formation and breakup of humic acids and clays agglomerates is a difficult challenge owing to their complex nature. Thus, to progress in the study of the stability of such systems, attempts were made to replace the humic acid/kaolinite natural system by the polyacrylic acid/aluminium oxide synthetic system. Since the present investigation was dedicated to determine some characteristics of acidic soils which contain traces of aluminium ions, these ions were added to the adsorbent/polyacid systems as trace constituents. Initial and short-term phenomena related to the adsorption of humic and polyacrylic acids on aluminium oxide and kaolinite clay have been presented elsewhere. Here we present long-term phenomena regarding the formation and cohesion of oxide and clay aggregates formed in the presence of polyacrylic and humic acids, respectively. The results of electrophoretic mobility measurements demonstrated the amphipathic character of polymeric layers adsorbed on aluminium oxide and the amphoteric character of humic acid layers adsorbed on kaolinite. The long-term stability of the two colloidal systems was determined to evolve similarly despite the existence of the these typical characteristics. Received: 24 July 2000 Accepted: 20 December 2000