A comparative study on the effect of hydrodynamic interactions in the non-sequential deposition of concentrated colloidal dispersions: stochastic rotation dynamics and Brownian dynamics simulations

Irreversible adsorption of particles onto a flat surface as a consequence of sedimentation colloidal suspension has been studied by two simulation techniques: Brownian dynamics (BD) and stochastic rotation dynamics (SRD). The purpose of using both methods is to investigate the effect of hydrodynamic interactions on adsorption kinetics and structure of the first monolayer of sediment obtained from the sedimentation of a concentrated and monodisperse colloidal suspension. Three systems were studied, characterised by the Péclet numbers: 0.1, 1.0 and 10. To physically understand the kinetic behaviour, simulation results were analysed using a kinetic model based on chemical reactions. High values of jamming limit (θ_∞ > 0.61) were obtained for both simulation techniques, with the SRD showing the highest figures (0.631) due to the hydrodynamics effect that takes into account the fluid backflow produced on particle sedimentation. A two-step adsorption mechanism was proposed based on the observed kinetic behaviour.     

Irreversible adsorption of diffusing hard disks: an effective medium approach

We propose an effective medium theory to analyze the kinetics of nonsequential adsorption of colloidal particles, including transport and blocking effects, valid at all values of surface coverage. The theory is applied to the irreversible adsorption of diffusing hard disks obtaining a kinetic law, which is in excellent agreement with nonsequential computer simulations at all densities of adsorbed particles.     

Adsorption thermodynamics of interacting particles on diffusion-limited aggregates

Grand canonical Monte Carlo simulations have been performed in order to study adsorption thermodynamics of pairwise interacting particles on fractal surfaces. Diffusion-limited aggregates (DLA) have been used as a substrate where interacting particles are adsorbed. In order to obtain aggregates with different morphologies, DLA clusters are generated on different strongly correlated surfaces. Adsorption isotherm, adsorption energy and differential heat of adsorption were calculated for attractive and repulsive nearest-neighbor (NN) lateral interactions. For the case of repulsive couplings and low temperatures, four novel ordered phases has been found in the adsorbate, each one corresponding to the formation of a chessboard-like structure on sites with one, two, three and four NN sites, respectively. The values of coverage at which these ordered phases emerge are not symmetrical around θ=0.5. This is a consequence of the non-equivalence between vacancy and particle in the case of adsorption on fractal structures. The influence of ordered structures on thermodynamic quantities associated to the adsorbed monolayer has been analyzed and discussed in the context of the Lattice-Gas model.     

Aerosol Catalysis on Nickel Nanoparticles

Nickel nanoparticles produced by spark discharges were used as aerosol catalyst for the formation of methane. The available surface area of the particles was determined using different methods. It was found that the surface area available for nitrogen adsorption and, therefore, for the methanation reaction remained virtually constant during restructuring of the agglomerates while the surface area based on the mobility was significantly reduced. In general, the reaction parameters such as activation energy and reaction rates agree well with the values for single nickel crystals and foils. At temperatures above 350°C the activation energy and the photoelectric activity of the particles decrease indicating the formation of graphite on the particle surface. Also the change of the work function points to the build up of multiple layers of graphite on the particle surface. The surprisingly low temperature for the surface deactivation may indicate an enhanced formation of carbon atoms at the surface.     

Diffusion of a chemically active colloidal particle in composite channels

Diffusion of colloidal particles in microchannels has been extensively investigated, where the channel wall is either a no-slip or a slip-passive boundary. However, in the context of active fluids, driving boundary walls are ubiquitous and are expected to have a substantial effect on the particle dynamics. By mesoscale simulations, we study the diffusion of a chemically active colloidal particle in composite channels, which are constructed by alternately arranging the no-slip and diffusio-osmotic boundary walls. In this case, the chemical reaction catalyzed by the active colloidal particle creates a local chemical gradient along the channel wall, which drives a diffusio-osmotic flow parallel to the wall. We show that the diffusio-osmotic flow can significantly change the spatial distribution and diffusion dynamics of the colloidal particle in the composite channels. By modulating the surface properties of the channel wall, we can achieve different patterns of colloidal position distribution. The findings thus propose a novel possibility to manipulate colloidal diffusion in microfluidics, and highlight the importance of driving boundary walls in dynamics of colloidal particles in microchannels.     

Osmotic propulsion: the osmotic motor

A model for self-propulsion of a colloidal particle--the osmotic motor--immersed in a dispersion of "bath" particles is presented. The nonequilibrium concentration of bath particles induced by a surface chemical reaction creates an osmotic pressure imbalance on the motor causing it to move. The ratio of the speed of reaction to that of diffusion governs the bath particle distribution which is employed to calculate the driving force on the motor, and from which the self-induced osmotic velocity is determined. For slow reactions, the self-propulsion is proportional to the reaction velocity. When surface reaction dominates over diffusion the osmotic velocity cannot exceed the diffusive speed of the bath particles. Implications of these features for different bath particle volume fractions and motor sizes are discussed. Theoretical predictions are compared with Brownian dynamics simulations.     

Formation of square-order areas on the colloidosome surface

The self-assembly of the colloidosome, i.e., the system of rather densely packed colloidal particles arranged at the spherical interface of two phases, has been simulated. Particles are retained on the sphere surface by surface tension and are ordered due to the interaction described by the Lennard-Jones potential. The particle coordinates are obtained by conditional minimization of the free energy of the system. The violations of the average hexagonal order of colloidosome surface particles, not reduced to the topologically caused formation of pentagonal point defects, are studied. It is shown that the average area excess per colloidal particle can cause the formation of square-order areas observed in colloidosomes.     

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.     

DNA‐Mediated Stabilization of Self‐Assembling Bead Monolayers for Microfluidic Applications

Forming ordered 2D or 3D arrays of colloidal particles on the micro‐ or nanometer scale in a bottom‐up process is a challenging task. In previous works by various groups, hybridization between DNA strands localized on the particle surface is used to create crystalline arrays. However, this method requires an annealing process with a duration of one day or more and usually yields agglomerates of only a few dozen particles. In this work, a method for the rapid formation of highly‐ordered 2D agglomerates of superparamagnetic microparticles (beads) is presented. Dipolar coupling between the beads under the influence of a rotating magnetic field leads to the formation of a dense monolayer. The monolayer is then stabilized through DNA hybridization between DNA strands immobilized on the bead surface and a linker strand in solution. The whole self‐assembly process requires less than an hour and is therefore significantly faster than comparable methods.     

Dispersion of nano-silicon carbide (SiC) powder in aqueous suspensions

The dispersion characteristics of nanosize silicon carbide (SiC) suspension were investigated in terms of surface charge, particle size, rheological measurement and adsorption study. Ammonium polycarboxylate has been used as dispersant to stabilize the suspension. It was found that the isoelectric point (iep) of SiC powder was pH_iep (4.9). The surface charge of powder changed significantly in presence of the ammonium polycarboxylate dispersant and iep shifted significantly towards lower acidic pH (3.6). The shift in iep has been quantified in terms of ΔG ⁰ _SP, the specific free energy of adsorption between the surface sites and the adsorbing polyelectrolyte (APC). The values of ΔG ⁰ _SP (−10.85 RT unit) estimated by the electro kinetic data compare well with those obtained from adsorption isotherms (−9.521 RT unit). The experimentally determined optimum concentration of dispersant required for maximizing the dispersion was found to be 2.4 mg/g of SiC (corresponding to an adsorbed amount of 1.10 mg/g), at pH 7.5. This is much below the full monolayer coverage (corresponding to adsorbed amount of 1.75 mg/g) of the particles surface by the dispersant. The surface charge quantity, rheological, pH, electro kinetic and adsorption isotherm results were used to explain and correlate the stability of the nanosize silicon carbide in aqueous media. At pH 7.5, where both SiC surface and APC are negatively charged, the adsorption of APC was low because of limited availability of favourable adsorption sites. In addition, the brush-like configuration of the adsorbed polymer prevented close approach of any additional dispersant; hence stabilization of the slurry happens at a comparatively lower concentration than the monolayer coverage.     

New cooperative effects in ballistic deposition of hard disks

In this Letter, we analyze the problem of monolayer formation onto a flat surface by deposition of hard particles. Our detailed computer simulations of ballistic deposition of hard disks show significant deviations from the classical analytical solution obtained by J. Talbot [Phys. Rev. Lett. 68, 958 (1992)]. These deviations are due to cooperative adsorption induced by particles trapped above the adsorbed layer. We show that not only the adsorption kinetics but also the jamming (saturation) coverage of the surface depends on the volume fraction of the suspension, a prediction which is completely new. These new cooperative effects cannot be neglected even in the case of very diluted suspensions.     

A molecular beam study of the adsorption dynamics of CO on Ru(0001), Cu(111) and a pseudomorphic Cu monolayer on Ru(0001)

We have investigated the sticking coefficient of CO on Ru(0001), a pseudomorphic Cu monolayer on Ru(0001), and a fully relaxed Cu(111) multilayer as function of kinetic energy, surface coverage, and surface temperature. At a low kinetic energy of 0.09 eV, the initial sticking coefficients, S₀, on these surfaces are determined to be 0.92, 0.96 and 0.87, respectively. In all cases, a decrease of S₀ with increasing beam energy was observed, yielding values of 0.58, 0.14 and 0.07, respectively, at a kinetic energy of 2.0 eV. For all three surfaces the coverage dependent sticking coefficients, S(Θ), display very characteristic behavior at low kinetic energies: S(Θ) remains more or less constant up to coverages close to saturation, indicative of precursor adsorption kinetics. However, characteristic minima at intermediate coverages are observed, which are correlated to the formation of well ordered adsorbate phases. For high kinetic energies we observe a transition towards a linear decrease of S(Θ) for Ru(0001). In contrast, for the pseudomorphic Cu monolayer and for Cu(111) we find an increase in the sticking coefficients at low coverages, followed by a decrease close to saturation. This behavior is attributed to adsorbate assisted sticking, that is, to a higher sticking coefficient on adsorbate covered regions than on the bare surface. The comparison between the pseudomorphic monolayer and Cu(111) reveals that the CO bond strength to the former is larger by 40%. The initial sticking coefficients for both surfaces are very similar at low kinetic energies; at high kinetic energies, S₀ for the pseudomorphic Cu monolayer is, however, larger by a factor of two.     

Formation mechanisms of colloidal silica via sodium silicate

Colloidal silica is formed by titrating active silicic acid into a heated KOH with seed solution. The colloidal silica formation mechanisms are investigated by sampling the heated solution during titration. In the initial stage, the added seeds were dissolved. This might due to the dilution of seed concentration, the addition of potassium hydroxide (KOH) and the heating at 100°C. Homogenous nucleation and surface growth occur simultaneously in the second stage of colloidal silica formation. Homogenous nucleation is more important when the seed concentration is relatively low. On the other hand, surface growth plays an important role when the seed concentration is increased. In the middle seed concentration, the seed particles grow up and some new small particles are born by the homogenous nucleation process to form a bimodal size distribution product. As the titrating volume of active silicic acid exceeds a specific value in the last stage the particle size increases rapidly and the particle number decreases, which may be caused by the aggregation of particles. The intervals between each stage were varied with the seed concentration. Increasing the seed concentration led to the formation of uniform particle size colloidal silica.     

溶液液滴蒸发变干的环状沉积

液体蒸发驱动的颗粒自组装现象在许多的工业技术中有重要应用. 本文利用显微镜观测含有颗粒物质的液滴变干后留在固体表面的颗粒形成的环状沉积图案. 采用微米粒径的SiO₂小球水溶液液滴蒸发变干模拟咖啡环的形成过程, 结果发现液滴蒸发过程中接触线的钉扎是环状沉积的必要条件. 在液滴蒸发过程中颗粒随着补偿流不断的向液滴边缘移动, 聚集在接触线处形成环. 液滴蒸发变干后残留在液滴内部的颗粒数随颗粒质量分数的增加而增加, 可以达到单层的颗粒排列. 而玻璃衬底上的颗粒环在颗粒质量分数很小时, 形成单层排列, 且一排一排地生长. 蒸发过程中颗粒环由于液滴边缘的尺寸限制向液滴中心缓慢移动. 这会导致液滴中不同大小颗粒的分离. 关键词： 液滴 接触线 蒸发 颗粒     

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.     

Self-assembly of charged CdTe nanoparticles

We show a method of the organization of charged CdTe nanoparticles which allows the generation of a self-assembled monolayer of above 10.000 μm² in a time of about 90 s. The analysis of adsorption kinetics of particles on a surface shows that it is well described by the Langmuir isotherm. We have found that thermal and electrical conductivity of a substrate play an important role. Nevertheless, deficiency of a substrate does not affect the adsorption kinetic. The structure of a formed monolayer essentially depends on pH and, as a consequence, on the charge of the particles. This method can be effective for the production of a CdTe nanoparticle monolayer with well controlled area and a degree of filling on a surface.     

电解质浓度对胶体粒子表面有效电荷的影响

胶体粒子的表面有效电荷是决定胶体性质的重要物理量,但溶液环境(如电解质溶液浓度)是否影响其数值至今尚无统一认识,近年来的一些研究工作给出了存在争议的不同结果和假设.在直接实验测量方面,由于电解质离子和胶体表面吸附离子的置换,粒子表面基团的不完全电离和胶体粒子对离子吸附的共同作用,使得对这类粒子在不同溶液环境下的表面有效电荷的测量和变化机理的认识极为困难.针对该问题,本文测定了羧基和磺酸基修饰的聚苯乙烯胶体颗粒在不同粒子浓度和HCl浓度下的电导率,由于两种粒子与HCl电离产生的阳离子相同(均为H+),可根据电导率-数密度法(迁移法)得到胶体颗粒表面有效电荷数.通过实验结果分析,明确了HCl浓度以及粒子数密度对胶体粒子表面电荷的影响规律以及表面电荷随HCl浓度增大的原因.除此之外,羧基修饰颗粒比磺酸基修饰颗粒的表面电荷随HCl浓度变化更快;对于同一HCl浓度,磺酸基修饰胶体表面电荷不受粒子数密度影响,而羧基修饰胶体颗粒却与之相关.基于粒子表面电荷的理论模型,对这些问题都给出了相应的解释.     

First nucleation steps during deposition of SiO2 thin films by plasma enhanced chemical vapour deposition

The initial nucleation stages during deposition of SiO₂ by remote plasma enhanced chemical vapour deposition (PECVD) have been monitored by XPS inelastic peak shape analysis. Experiments have been carried out on two substrates, a flat ZrO₂ thin film and a silicon wafer with a native silicon oxide layer on its surface. For the two substrates it is found that PECVD SiO₂ grows in the form of islands. When the SiO₂ particles reach heights close to 10 nm they coalesce and cover completely the substrate surface. The particle formation mechanism has been confirmed by TEM observation of the particles grown on silicon substrates. The kinetic Monte Carlo simulation of the nucleation and growth of the SiO₂ particles has shown that formation of islands is favoured under PECVD conditions because the plasma species may reach the substrate surface according to off-perpendicular directions. The average energy of these species is the main parameter used to describe their angular distribution function, while the reactivity of the surface is another key parameter used in the simulations.     

Localised forced ignition of globally stoichiometric stratified mixtures: A numerical investigation

Localised forced ignition of globally stoichiometric stratified mixtures (i.e. < φ > =1.0) has been analysed here based on direct numerical simulations for different initial values of velocity and equivalence ratio fluctuations (i.e. u′ and φ′), and the Taylor micro-scale l_φ of equivalence ratio φ variation. The localised ignition is accounted for by a source term in the energy transport equation which deposits energy over a stipulated time interval. It has been found that combustion takes place predominantly under premixed mode in the case of successful ignition. The initial values of φ′ and l_φ have been found to have significant effects on the extent of burning of stratified mixtures following localised ignition. It has been found that an increase in u′(φ′) has adverse effects on the burned gas mass, whereas the effects of l_φ on the extent of burning are non-monotonic and dependent on φ′. Detailed physical explanations have been provided for the observed u′, φ′ and l_φ dependences on the extent of burning in stratified mixtures.     

Does thermophoretic mobility depend on particle size?

Thermophoresis is particle drift induced by a temperature gradient. By measuring the full temperature dependence of this effect for polystyrene latex suspensions, we show that the thermophoretic mobility (or "thermal diffusion coefficient") D(T) is basically independent on particle size, in particular, when the interfacial properties of the colloidal particles are carefully standardized by adsorbing a surfactant layer on the particle surface. Even more, all investigated systems show values of D(T) which are very close to those measured for simple micellar solutions of the adsorbed surfactant. Our findings could be of relevance for downsizing microfluidics to the nanometric range.