Simulating (electro)hydrodynamic effects in colloidal dispersions: Smoothed profile method

Previously, we have proposed a direct simulation scheme for colloidal dispersions in a Newtonian solvent (Phys. Rev. E 71, 036707 (2005)). An improved formulation called the “Smoothed Profile (SP) method” is presented here in which simultaneous time-marching is used for the host fluid and colloids. The SP method is a direct numerical simulation of particulate flows and provides a coupling scheme between the continuum fluid dynamics and rigid-body dynamics through utilization of a smoothed profile for the colloidal particles. Moreover, the improved formulation includes an extension to incorporate multi-component fluids, allowing systems such as charged colloids in electrolyte solutions to be studied. The dynamics of the colloidal dispersions are solved with the same computational cost as required for solving non-particulate flows. Numerical results which assess the hydrodynamic interactions of colloidal dispersions are presented to validate the SP method. The SP method is not restricted to particular constitutive models of the host fluids and can hence be applied to colloidal dispersions in complex fluids.     

Electrostatic lattice sums for semi-infinite lattices

The techniques for the rapid computation of energies of three-dimensional neutral periodic assemblies of charged particles are extended to semi-infinite arrays and assemblies of ions in infinite filsm. The results will be useful for simulation of ionic movements in fast-ion conductors and dense colloidal dispersions.     

平板电极间胶体晶体在电场作用下的各向同性压缩

用直径 300 nm的聚苯乙烯微球配制不同浓度的胶体晶体溶液, 将其快速注入内表面镀有导电薄膜的玻璃样品池中, 形成 (111) 晶面平行于玻璃表面的面心立方单晶结构. 通过激光衍射Kossel线方法, 研究了不同体积分数的胶体晶体样品 及它们在均匀电场作用下晶体结构的变化. 实验发现, 随着电场强度的增加, 胶体晶体表现为各向同性的压缩. 胶体晶体在恒定电场下始终保持面心立方结构, 晶格常数随着电场强度的增加逐渐减小. 实验结果可用电场力、电流体力学作用力及颗粒间静电斥力共同解释: 电场力使带电微球克服静电斥力并沿电场反方向运动导致晶体压缩, 而由电场力作用引起的电流体力学液流产生的持续推力使垂直于电场平面上的胶体微球相互靠近. 本实验为天宫一号搭载科学实验的地基实验. 关键词： 胶体晶体 Kossel衍射 结构变化     

Electrohydrodynamic controlled assembly and fracturing of thin colloidal particle films confined at drop interfaces

Particles can adsorb strongly at liquid interfaces due to capillary forces, which in practice can confine the particles to the interface. Here we investigate the electrohydrodynamic flow driven packing and deformation of colloidal particle layers confined at the surface of liquid drops. The electrohydrodynamic flow has a stagnation point at the drop equator, leading to assembly of particles in a ribbon shaped film. The flow is entirely controlled by the electric field, and we demonstrate that AC fields can be used to induce hydrodynamic “shaking” of the colloidal particle film. We find that the mechanical properties of the film is highly dependent on the particles: monodisperse polystyrene beads form packed granular monolayers which “liquefies” upon shaking, whereas clay mineral particles form cohesive films that fracture upon shaking. The results are expected to be relevant for understanding the mechanics and rheology of particle stabilized emulsions.     

Electrokinetic and hydrodynamic properties of charged-particles systems

Dynamic processes in dispersions of charged spherical particles are of importance both in fundamental science, and in technical and bio-medical applications. There exists a large variety of charged-particles systems, ranging from nanometer-sized electrolyte ions to micron-sized charge-stabilized colloids. We review recent advances in theoretical methods for the calculation of linear transport coefficients in concentrated particulate systems, with the focus on hydrodynamic interactions and electrokinetic effects. Considered transport properties are the dispersion viscosity, self- and collective diffusion coefficients, sedimentation coefficients, and electrophoretic mobilities and conductivities of ionic particle species in an external electric field. Advances by our group are also discussed, including a novel mode-coupling-theory method for conduction-diffusion and viscoelastic properties of strong electrolyte solutions. Furthermore, results are presented for dispersions of solvent-permeable particles, and particles with non-zero hydrodynamic surface slip. The concentration-dependent swelling of ionic microgels is discussed, as well as a far-reaching dynamic scaling behavior relating colloidal long- to short-time dynamics.     

Colloidal Crystals of NaYF4 Upconversion Nanocrystals Studied by Small‐Angle X‐Ray Scattering (SAXS)

Spherical NaYF₄ upconversion nanocrystals with mean radii of about 5 and 11 nm are observed to form colloidal crystals, i.e., 3D assemblies of the particles with long‐range order. The colloidal crystals of the larger particles form directly in solution when dispersions of the particles in toluene are stored at room temperature for several weeks. Crystallization of the smaller particles takes place when their dispersions in hexane are slowly dried at elevated temperatures. The formation and the structure of the colloidal crystals are studied by small‐angle X‐ray scattering (SAXS). SAXS measurements show that the smaller as well as the larger particles assemble into a face‐centered cubic lattice with unit cell dimensions of a = 18.7 nm and a = 35.5 nm, respectively. The SAXS data also show that the particles in the colloidal crystals still bear a layer of oleic acid on their surfaces. The thickness of this layer is 1.5–1.8 nm, as determined by comparing the unit cell dimensions of the colloidal crystals with the mean particle sizes. The latter could be very precisely determined from the distinct oscillations observed in the SAXS data of dilute colloidal dispersions of the nanocrystals.     

Direct determination of free energies of colloidal dispersions

Helmholtz free energies of electrostatically-stabilized colloidal dispersions of monodispersed spherical particles have been obtained using computer experiments. Boltzmann sampling has been shown to be sufficient for determining free energy differences between two dispersions whose pair-potentials are close to each other. Non-Boltzmann sampling has been used when the pair-potentials differ substantially. These results have been compared with the results based on perturbation theory. The techniques used, thus, offer a direct method to test the latter.     

On the dynamics of the disorder-order transition

Extant theories for nucleation and growth of crystals in molecular systems are adapted to colloidal dispersions and used to compare observations for charged spheres at low ionic strengths; soft, polymerically stabilized spheres: and hard spheres.     

Formation of structures from amorphous metallic nanoparticles by dispersing metal drops continuously charging in an electron beam

The formation of amorphous metal nanoparticles by the method of electrohydrodynamic dispersion is studied. In this method, fine liquid metal drops are generated, charged in an electron beam to an unstable state, and dispersed into nanometer droplets. Rapid cooling of these nanometer droplets results in the formation of amorphous metal nanoparticles. The chief problem in the formation of such particles is that it is difficult to charge molten metal drops to an unstable state, since the bombardment of the drop by an electron beam may cause intense emission of electrons. To overcome this difficulty, the drops are charged by a beam of slow electrons. Charging proceeds in such a way that the electron energy rises with the drop’s charge. It is shown that this method makes it possible to obtain granulated films made up of amorphous metal particles. Copper films with a nanoparticle mean size of 2 nm and a small dimensional variation are prepared.     

Interpretation of Light Scattering Spectra of Dispersions – A Hybrid Approach to Account for Interparticle Interactions

The problem of extracting quantitative information on individual particle properties from spectroscopic measurements conducted at concentrations where particle interactions become significant is of great industrial and theoretical importance. For dispersions of charged particles, this can happen at fairly low concentrations. The effect of the fluid (slurry) structure has to be taken into account to interpret the light scattering spectra of such dispersions. In this paper, a hybrid method that addresses the effect of the fluid structure is proposed. The hybrid approach describes the fluid structure by relating the “effective” Percus‐Yevick hard‐sphere parameters to the system parameters using empirical models. The feasibility of this approach is examined through a theoretical study with data generated by Monte Carlo simulations of a monodisperse dispersion of charged spherical particles using realistic interaction potentials under single scattering conditions.     

Comparative structural characterization of the water dispersions of detonation nanodiamonds by small-angle neutron scattering

The structure of nanodiamond water dispersions prepared under different conditions was investigated by small-angle neutron scattering at the scale of 1 to 100 nm. The study of diluted dispersions was regarded as of paramount importance. Similarly to previous studies, strong clustering of particles was revealed in the solutions. The typical size of clusters (40 nm and above) depends on the modification of the dispersions. A common property can be distinguished for different systems: the fractal dimension of the clusters is in the range of 2.3?C2.4, which indicates that there is a common clustering mechanism in such systems. Using contrast variation, the existence of a nondiamond component in the colloidal particles of the dispersions was confirmed; it correlates with the presence of a graphene shell on crystallite surfaces.     

Simulation of nonstationary electrohydrodynamic flows in a symmetric system of electrodes of the wire-wire type

Computer simulation is carried out for the process of formation of electrohydrodynamic flows emerging in a system of two parallel wires as a result of symmetric injection from each electrode (2D case). Simulation is performed using the ANSYS system. A simulation algorithm is developed for nonstationary electrohydrodynamic flows. The results of simulation are presented. Analysis of the results shows that the evolution of electrohydrodynamic flows is accompanied by the formation of thin oppositely charged liquid streams moving in opposite direction from near-electrode charged layers.     

模拟研究电荷的大小和温度对带电胶体纳米粒子稳定性的影响

利用蒙特卡罗方法和原始模型对正则系综中的带电胶体悬浮液进行分子模拟研究. 同时利用众所周知的DLVO理论研究颗粒之间的有效相互作用. 另外研究了温度、微离子价态和胶体粒子对溶液相稳定性的影响. 结果表明,在较高的温度下悬浮液更稳定. 另一方面,低价态的微离子更有利于形成稳定的悬浮液. 对于高电荷的微离子,平均每个集合体中的聚集体的数量和颗粒数更高,较大的胶体粒子稳定性差. 理论结果与表面曲率影响的理论公式有很好的一致性.     

Dynamic properties,scaling and related freezing criteria of two- and three-dimensional colloidal dispersions

The static and dynamic properties of 2- and 3-dimensional dispersions of strongly interacting colloidal spheres are examined. Quasi-2-dimensional dispersions of particles interacting by long range electrostatic and dipolar magnetic forces, respectively, are investigated using Brownian dynamics computer simulations with hydrodynamic interactions included. The dynamics of 3-dimensional bulk dispersions of charge-stabilized and neutral colloidal spheres is determined from a fully self-consistent mode-coupling scheme. For systems with long range repulsive interactions the dynamic correlation functions are shown to obey dynamic scaling in terms of a characteristic relaxation time related to the mean particle distance. Hydrodynamic interactions introduce a second characteristic length scale, and they lead to more restricted scaling behaviour with an enhancement of self-diffusion and, for 2-dimensional systems, to the divergence of the short-time collective diffusion coefficient. As a consequence of dynamic scaling, a dynamic criterion for the onset of colloidal freezing related to long-time self-diffusion is shown to be equivalent to a static freezing criterion related to the 2- and 3-dimensional static structure factors. Alternative freezing criteria are given in terms of the long-time and the mean collective diffusion coefficients.     

Structure of the near-electrode dissociation-recombination charged layers at various low-voltage conductivities of a low-conducting liquid

The current passage through a low-conducting liquid is simulated for a system of electrodes with a highly nonuniform electric-field distribution at voltages lower and higher than the threshold of appearance of electrohydrodynamic flows. The structure of the near-electrode dissociation-recombination charged layers is considered in terms of the following two-charge formation models: constant dissociation in the volume but without injection and injection from an electrode and constant dissociation in the volume. The change in the polarity of the near-electrode charged layer caused by an increase in the voltage or a change in the low-voltage conductivity of the liquid is analyzed. Two types of electrohydrodynamic flows, which appear in real electrohydrodynamic devices and have opposite directions, are obtained using one mathematical model.     

Patterned colloidal deposition controlled by electrostatic and capillary forces

We use substrates chemically micropatterned with anionic and cationic regions to govern the deposition of charged colloidal particles. The direct observation of the colloidal assembly suggests that this process includes two steps: an initial patterned attachment of colloids to the substrate and an additional ordering of the structure upon drying. The driving forces of the process, i.e. , screened electrostatic and lateral capillary interactions, are discussed. This approach makes it possible to fabricate complex, high-resolution two-dimensional arrays of colloidal particles.     

Synthesis and characterization of magnetite particles covered with α-trietoxysilil-polydimethylsiloxane

New silicon magnetite ferrofluids were prepared by dispersing siloxane-coated magnetite particles in polydimethylsiloxane with low or high molecular weights. Ferrofluids are stable colloidal dispersions of ultra fine covered magnetite particles, which may be selected for a specific application. We demonstrated new methods of stabilizing the magnetic particles by reacting the hydroxyl groups on the surface of magnetite particles with terminal ethoxy groups of polydimethylsiloxane, followed by their dispersion in silicon fluids. The new silicon ferrofluids were tested from the morphology, magnetic properties/losses, and rheological properties point of view.     

Absence of the liquid phase when the attraction is not pairwise additive

Recent work on charged colloidal suspensions with very low levels of added salt has suggested that although pairs of the colloidal particles repel, clusters of the particles attract. Motivated by this, we study simple model particles which have many-body attractions. These attractions are generic many-body attractions and are not calculated for any specific colloidal suspension. We find that many-body attractions can stabilize solid phases at low pressures but that the liquid phase is either completely absent from the equilibrium phase diagram or present only within a small region of parameter space.     

Ion specificity and the theory of stability of colloidal suspensions

A theory is presented which allows us to accurately calculate the critical coagulation concentration of hydrophobic colloidal suspensions. For positively charged particles, the critical coagulation concentrations follow the Hofmeister (lyotropic) series. For negatively charged particles, the series is reversed. We find that strongly polarizable chaotropic anions are driven towards the colloidal surface by electrostatic and hydrophobic forces. Within approximately one ionic radius from the surface, the chaotropic anions lose part of their hydration sheath and become strongly adsorbed. The kosmotropic anions, on the other hand, are repelled from the hydrophobic surface. The theory is quantitatively accurate without any adjustable parameters. We speculate that the same mechanism is responsible for the Hofmeister series that governs stability of protein solutions.     

Phase behavior of dispersions of hard spherical particles

A series of experiments on concentrated dispersions of hard colloidal spheres is discussed. The observed phase behavior is analogous to that of simple atomic systems: colloidal fluid, crystal and glass phases are found. The structure of the crystals, revealed by light diffraction, is a strongly faulted stacking of hexagonally-packed layers of particles. Dynamic light scattering confirms that the concentration of the metastable fluid phase for which long-ranged particle diffusion ceases coincides with the concentration where the glass transition is observed macroscopically. In studies of a binary mixture of colloidal spheres with a size ratio 0.61 eutectics, glass formation and the AB₁₃ type alloy structure have been identified.