Kinetic analyses of colloidal crystallization in shear flow

Colloidal crystallization kinetics is studied in the shear flow of a suspension of colloidal silica spheres (110 nm in diameter), using a continuously-circulating type of stopped flow cell system. The crystallization rate from a suspension containing a small amount of nuclei and/or single crystals is high compared with that from a suspension containing no nuclei and/or single crystals. Crystal growth takes place at shear rates smaller than 3.4 s^–1 and at sphere concentrations higher than a volume fraction of 0.004.     

Interactions between colloidal particles in simple shear flow

Recent progress in experimental and theoretical developments dealing with colloidal. interactions between two spheres in shear flow is reviewed. A systematic comparison is made between spheres suspended in simple electrolyte and in cationic polyelectrolye solutions. Microrheological observations, performed with the traveling microtube, make an in-depth investigation possible of the colloidal forces and the mechanisms of polymer bridge formation. Reasons are discussed for the often-observed aging of colloidal aggregates. Finally, coagulation rates are presented for systems with weak and strong Brownian motion. It is shown that the often-used assumption of additivity of the ortho- and perikinetic coagulation rates is incorrect.     

Crystallization kinetics of polyethylene under high pressure

The kinetics of isothermal crystallization of polyethylene under high pressures ranging from 840 to 5300 kg/cm² has been studied dilatometrically. The crystallization rate estimated from the half-time of the overall transformation increases markedly with pressure. The Avrami exponent n becomes smaller with increasing pressure. Values of n ≈ 2 for the crystallization at 840 and 1950 kg/cm², and n ≈ 1 at 5100 and 5300 kg/cm² were obtained. Differential scanning calorimetry and electron microscopy data are presented. It is concluded that extended-chain crystals grow rapidly, predominantly in one dimension, at high pressure. Relations between log k and T_m/T(ΔT) and T_m²/T(ΔT)² are nearly linear. Here, k is the crystallization rate constant from an Avrami equation, ΔT = T_m – T, T_m is the melting point, and T is the temperature of crystallization. From the dependence of the slope of the straight line on the crystallization pressure it is concluded that the surface energy of crystal nuclei decreases with increasing pressure.     

Clusters of amphiphilic colloidal spheres

Orientation-dependent interactions can drive unusual self-assembly of colloidal particles. This study, based on combined epifluorescence microscopy and Monte Carlo simulations, shows that amphiphilic colloidal spheres, hydrophobic on one hemisphere and charged on the other, assemble in water into extended structures not formed by spheres of uniform surface chemical makeup. Small, compact clusters each comprised of less than 10 of these Janus spheres link up, as increasing salt concentration enhances electrostatic screening, into wormlike strings.     

Breakage rate of colloidal aggregates in shear flow through stokesian dynamics

We study the first breakage event of colloidal aggregates exposed to shear flow by detailed numerical analysis of the process. We have formulated a model, which uses stokesian dynamics to estimate the hydrodynamic interactions among the particles in a cluster, van der Waals interactions and Born repulsion to describe the normal interparticle interactions, and the tangential interactions through discrete element method to account for contact forces. Fractal clusters composed of monodisperse spherical particles were generated using different Monte Carlo methods, covering a wide range of cluster masses (N(sphere) = 30-215) and fractal dimensions (d(f) = 1.8-3.0). The breakup process of these clusters was quantified for various flow magnitudes (γ), under both simple shear and extensional flow conditions, in terms of breakage rate constant (K(B)), mass distribution of the produced fragments (FMD, f(m,k)), and critical stable aggregate mass (N(c)), defined as the largest cluster mass that does not break under defined flow conditions. The breakage rate K(B) showed a power law dependence on the product of the aggregate size and the applied stress, with values of the corresponding exponents depending only on the aggregate fractal dimension and the type of flow field, whereas the prefactor of the power law relation also depends on the size of the primary particles comprising a cluster. The FMD was fitted by Schultz-Zimm distribution, and the parameter values showed an analogous dependence on the product of the aggregate size and the applied stress similar to the rate constant. Finally, a power law relation between the applied stress and corresponding largest stable aggregate mass was found, with an exponent value depending on the aggregate fractal dimension. This unique and detailed analysis of the breakage process can be directly utilized to formulate a breakage kernel used in solving population balance equations.     

Stacking in sediments of colloidal hard spheres

We use computer simulations to investigate the crystallization dynamics of sedimenting hard spheres in large systems (hundreds of thousands of particles). We show that slow sedimentation results primarily in face-centered cubic (fcc) stacked crystals, instead of random hexagonal close packed or hexagonal close packed (hcp) crystals. We also find slanted stacking faults, in the fcc regions. However, we attribute the formation of fcc to the free energy difference between fcc and hcp and not to the presence of these slanted stacking faults. Although the free energy difference between hcp and fcc per particle is small (only 10(-3) times the thermal energy), it can become considerable, when multiplied by the number of particles in each domain. The ratio of fcc to hcp obtained from dynamic simulations is in excellent agreement with well-equilibrated Monte Carlo simulations, in which no slanted stacking faults were found. Our results explain a range of experiments on colloids, in which the amount of fcc increases upon lowering the sedimentation rate or decreasing the initial volume fraction.     

Copper-mediated synthesis of PdI_2 colloidal spheres

A novel copper-mediated solvothermal method was proposed for synthesizing colloidal spheres of a new composition,palladium iodide(PdI2).Typical procedure was designed to involve the introduction of cupric chloride(CuCl2) as weak oxidant.CuCl2 was found to be essential for preventing the easy formation of palladium deposits as well as facilitating the synthesis and assembly.Under the co-effect of CuCl2 and the surfactant of polyvinylpyrrolidone(PVP),neutral PdI2 colloidal spheres with narrow size distributio...     

Stability of colloidal solutions containing various surface-modified cadmium sulfide particles under stationary illumination

Stability of the various colloidal solutions containing CdS particles with the surface modified by thiols such as thioglycerol (TG-CdS), mercaptophenyltetrazole (MPT-CdS), mercaptobenzimidazole (MBI-CdS), and mercaptoacetate (MA-CdS) (capped CdS particles) under the stationary illumination was studied by monitoring the changes in the absorption spectra to obtain knowledge about the influence of these capping agents on photocatalytic events such as electron and hole transfer processes at the capped semiconductor particle-solution interface. By the stationary illumination of the capped CdS particles, the photo-aggregation of the particles was observed in water and the photo-dissolution in organic solvents. The observed difference may be ascribed to the oxidative elimination of the capping agents from the CdS particles which occurs assisted by proton dissociation from the agents in water but not in organic solvents with aprotic nature. Addition of iodide which is known as a hole scavenger enhanced the photo-dissolution of both the capped and ordinary non-capped CdS particles, contrary to the expected photo-aggregation.     

Crystallization kinetics of amorphous

The active sites of hydrogen-exchanged Y zeolite (HY) and dealuminated (HDY) zeolites are investigated by TPD of carbon monoxide. Only the high temperature TPD spectra of CO (TM»620-690°C) were observed, meaning that CO molecules interact with very strong acid sites. The amounts of CO bonded on these sites are small (less than 1 molecule per unit cell). The strong influence of dealumination on the coverage degree is found. The calculated values for kinetic parameters indicate chemisorption of CO in the investigated systems (Edes»240 kJ mol^-1, A»1011 s^-1).     

Effect of polydispersity on the crystallization kinetics of suspensions of colloidal hard spheres when approaching the glass transition

We present a comprehensive study of the solidification scenario in suspensions of colloidal hard spheres for three polydispersities between 4.8% and 5.8%, over a range of volume fractions from near freezing to near the glass transition. From these results, we identify four stages in the crystallization process: (i) an induction stage where large numbers of precursor structures are observed, (ii) a conversion stage as precursors are converted to close packed structures, (iii) a nucleation stage, and (iv) a ripening stage. It is found that the behavior is qualitatively different for volume fractions below or above the melting volume fraction. The main effect of increasing polydispersity is to increase the duration of the induction stage, due to the requirement for local fractionation of particles of larger or smaller than average size. Near the glass transition, the nucleation process is entirely frustrated, and the sample is locked into a compressed crystal precursor structure. Interestingly, neither polydispersity nor volume fraction significantly influences the precursor stage, suggesting that the crystal precursors are present in all solidifying samples. We speculate that these precursors are related to the dynamical heterogeneities observed in a number of dynamical studies.     

Diffusiophoresis in a suspension of charge-regulating colloidal spheres

An analytical study of diffusiophoresis in a homogeneous suspension of identical spherical charge-regulating particles with an arbitrary thickness of the electric double layers in a solution of a symmetrically charged electrolyte with a uniform prescribed concentration gradient is presented. The charge regulation due to association/dissociation reactions of ionogenic functional groups on the particle surface is approximated by a linearized regulation model, which specifies a linear relationship between the surface charge density and the surface potential. The effects of particle-particle electrohydrodynamic interactions are taken into account by employing a unit cell model, and the overlap of the double layers of adjacent particles is allowed. The electrokinetic equations that govern the electric potential profile, the ionic concentration distributions, and the fluid flow field in the electrolyte solution surrounding the particle in a unit cell are linearized assuming that the system is only slightly distorted from equilibrium. Using a regular perturbation method, these linearized equations are solved with the equilibrium surface charge density (or zeta potential) of the particle as the small perturbation parameter. Closed-form formulas for the diffusiophoretic velocity of the charge-regulating sphere correct to the second order of its surface charge density or zeta potential are derived. Our results indicate that the charge regulation effect on the diffusiophoretic mobility is quite sensitive to the boundary condition for the electric potential specified at the outer surface of the unit cell. For the limiting cases of a very dilute suspension and a very thin or very thick electric double layer, the particle velocity is independent of the charge regulation parameter.     

Mechanical strength of amorphous CaCO3 colloidal spheres

Amorphous glassy CaCO3 colloidal spheres of monomodal size distribution were studied by high-resolution Brillouin light scattering. The Young modulus of 37 GPa and shear modulus of 14 GPa of glassy CaCO3 at a density of 1.9 g/cm3 were extracted from the particle vibration frequencies by employing acoustic wave scattering cross-section calculations. The line shape of the low-frequency modes is a sensitive index of the particle polydispersity.     

Temperature-responsive semipermeable capsules composed of colloidal microgel spheres

We present semipermeable, hollow capsules (colloidosomes) that expand and contract upon heating and cooling. The capsules are composed of micrometer-sized poly(N-isopropylacrylamide)-co-acrylic acid microgel particles, which exhibit a reversible size transition near 34 degrees C. The microgel particles assemble on the surfaces of water droplets in oil. Addition of the diblock copolymer poly(butadiene-b-N-methyl 4-vinyl pyridinium iodide) to the oil results in soft, elastic membranes of microgel particles that remain intact after the droplet interfaces are dissolved. Under heating, the capsules contract reversibly by 13% or irreversibly by 40% in radius. These stimulus-responsive colloidosomes might be useful for controlled release or as microscopic actuators.     

Computational modelling of declination loops under shear flow

Optical observations of sheared lyotropic and thermotropic liquid crystals have shown them to have a rich microstructure dominated by disclination loops and networks. In thermotropic liquid crystalline polymers it has been possible to freeze in the microstructures, which are then sectioned and analysed by optical and electron microscopy, to enable the identification of the predominant types of disclinations. In this work a computational model is presented which simulates the development of texture in liquid crystalline materials. The model has been designed so that it is possible to study large localised distortions which are subjected to a flow field. In the aspect of the work reported here, simulations have been used to study the influence of simple shear on individual disclination loops placed in an otherwise undeformed sample. The subsequent deformation of the loop is shown to be dependent on the angle that the rotation vector of the loop makes with the vorticity direction.     

Photoinduced deformation of amphiphilic azo polymer colloidal spheres

Photoinduced shape deformation of colloidal spheres made of an amphiphilic azo polymer has been demonstrated in this work. The polymer contains the donor-and-acceptor-type azobenzene chromophores and can form uniform colloidal spheres by dropwise adding water into its THF solution. When the colloidal spheres obtained were exposed to the interfering p-polarized Ar+ laser beams (150 mW/cm2), the colloidal spheres changed to prolates (i.e., "rugby-balls"), "spindles", and finally "rods", depending on the irradiation times. The elongated direction of the spheres was observed to be the same as the polarization direction of the laser beam. The average major-to-minor ratio of the ellipsoids could be easily adjusted by controlling the irradiation time. The deformation effect observed in this work can offer a new way to prepare nonspherical colloids from colloidal spheres and will shed new light on the correlation between the photodriven shape deformation and photoinduced surface relief gratings for the same type of polymers.     

Electrically induced colloidal clusters for generating shear mixing and visualizing flow in microchannels

When aqueous suspensions of 1 μm, negatively charged polystyrene particles are subject to a 1 kHz alternating electric field of strength greater than 7 kV(rms) m(-1), dynamic elliptical clusters of particles spontaneously form. With potential applications in microchannel fluidics in mind, we characterize how cluster formation and particle circulation, driven by induced dipole-dipole interactions, is critically dependent on time, field strength, electrolyte concentration, and cell thickness. Logarithmic growth of cluster size is observed, and particle velocity within the clusters is found to be proportional to cluster length. Increasing cell thickness from 10 to 60 μm increases the projected cluster area but decreases cluster aspect ratio as the result of changing particle dispersal rates. Clusters are shown to generate significant fluid shear suitable for microchannel mixing applications. These clusters are observed to distort under transverse fluid flow and, above a critical flow rate, to undergo a transition to form regularly spaced particle streams, which may be suitable for two-dimensional visualization of fluid flow.     

Crystallization of colloidal crystal on hydrogel surface

A dip-coating method to fabricate wet and dry type of colloidal crystal films was developed. The wet type of colloidal crystal film was fabricated by lifting an agarose-hydrogel-coated substrate out of an aqueous suspension containing monodisperse polymer spheres and the dry type of colloidal crystal film was derived by following desiccation of the wet film. Monodisperse spheres formed ordered structures in the both type of the films, which contributed sharp reflection peaks. Brilliant colors were observed when the reflection peaks fell in the visible region. Formation mechanism of the colloidal crystal and their optical properties were discussed.