Short-time rheology and diffusion in suspensions of Yukawa-type colloidal particles

A comprehensive study is presented on the short-time dynamics in suspensions of charged colloidal spheres. The explored parameter space covers the major part of the fluid-state regime, with colloid concentrations extending up to the freezing transition. The particles are assumed to interact directly by a hard-core plus screened Coulomb potential, and indirectly by solvent-mediated hydrodynamic interactions. By comparison with accurate accelerated Stokesian Dynamics (ASD) simulations of the hydrodynamic function H(q), and the high-frequency viscosity η(∞), we investigate the accuracy of two fast and easy-to-implement analytical schemes. The first scheme, referred to as the pairwise additive (PA) scheme, uses exact two-body hydrodynamic mobility tensors. It is in good agreement with the ASD simulations of H(q) and η(∞), for smaller volume fractions up to about 10% and 20%, respectively. The second scheme is a hybrid method combining the virtues of the δγ scheme by Beenakker and Mazur with those of the PA scheme. It leads to predictions in good agreement with the simulation data, for all considered concentrations, combining thus precision with computational efficiency. The hybrid method is used to test the accuracy of a generalized Stokes-Einstein (GSE) relation proposed by Kholodenko and Douglas, showing its severe violation in low salinity systems. For hard spheres, however, this GSE relation applies decently well.     

Collective diffusion in charge-stabilized suspensions: concentration and salt effects

The authors present a joint experimental-theoretical study of collective diffusion properties in aqueous suspensions of charge-stabilized fluorinated latex spheres. Small-angle x-ray scattering and x-ray photon correlation spectroscopy have been used to explore the concentration and ionic-strength dependence of the static and short-time dynamic properties including the hydrodynamic function H(q), the wave-number-dependent collective diffusion coefficient D(q), and the intermediate scattering function over the entire accessible range. They show that all experimental data can be quantitatively described and explained by means of a recently developed accelerated Stokesian dynamics simulation method, in combination with a modified hydrodynamic many-body theory. In particular, the behavior of H(q) for de-ionized and dense suspensions can be attributed to the influence of many-body hydrodynamics, without any need for postulating hydrodynamic screening to be present, as it was done in earlier work. Upper and lower boundaries are provided for the peak height of the hydrodynamic function and for the short-time self-diffusion coefficient over the entire range of added salt concentrations.     

Investigation of structure factors in dense colloidal suspensions using frequency domain photon migration: polydisperse systems

Frequency domain photon migration (FDPM) technique was employed to investigate the structure factors of dense, polydisperse colloidal suspensions. The angle-integrated structure factors, [S(q)], extracted from FDPM measurements of scattering properties at volume fractions ranging from 0.05 to 0.4, were compared with the values predicted from the polydisperse hard sphere Percus-Yevick (HSPY) model, as well as decoupling approximation (DA) and local monodisperse approximation (LMA) models that incorporated independently measured particle size information. Results show that the polydisperse HSPY model is the most suitable for accounting for particle interactions which predominantly arise from volume exclusion effects. Furthermore, the influence of size polydispersity upon [S(q)] is most significant at high volume fractions. The static structure factors at small wave vector q, S(0), were also assessed from dual wavelength FDPM measurements by using the small wave number approximation as well as the local monodisperse approximation. The measured S(0) agrees well with the values predicted by the polydisperse HSPY model.     

Polyion-induced aggregation of lipidic-coated solid polystyrene spheres: the many facets of complex formation in low-density colloidal suspensions

We have investigated the formation of a cluster phase in low-density colloidal systems formed by charged solid charged particles stuck together by an oppositely charged polyion. In analogy with what we have previously observed in the case of soft charged particles, also in this case the same basic phenomenology occurs, consisting of the presence of the two well-known characteristic phenomena of this class of colloids, that is, reentrant condensation and charge inversion. With the aim of comparing the cluster formation in both soft and solid charged particles, we have, in previous works, employed cationic liposomes (soft particles, lipidic vesicles built up by dioleoyltrimethylammonium propane [DOTAP] lipid) and, in the present work, polystyrene particles (solid particles) covered by the same lipidic bilayer as the one of the soft particles, so that the two classes of particles share electrostatic interactions of the same nature. These charged particle clusters, where the single aggregating particles maintain their integrity without undergoing a structural rearrangement, join to a class of different aggregated structures (lamellar or inverse hexagonal phases) observed as well in the polyion-induced aggregation of oppositely charged mesoscopic particles, in particular, lipidic vesicles. Our results show that the formation of relatively large, equilibrium clusters of particles which maintain their integrity, stuck together by a polyion which acts as an electrostatic glue, is one of the many facets of the complex phenomenology underlying the interactions of charged particles with oppositely charged objects.     

Phase diagram of alloy crystal in the exhaustively deionized suspensions of binary mixtures of colloidal spheres

Phase diagrams of liquidlike, alloy crystal-like and amorphous solid-like(AS) structures have been obtained for the exhaustively deionized aqueous suspensions of the binary mixtures of polystyrene or silica spheres. Diameter, polydispersity index (standard deviation of diameter divided by the mean diameter) and size ratio of the binary spheres (diameter of small sphere divided by that of large one) range from 85 to 136 nm, 0.07 to 0.26 and 0.76 to 0.93, respectively. Close-up color photographs of the alloy crystals are taken and the crystal structure has been analysed from reflection spectroscopy. Most of the alloy crystals aresubstitutional solid-solution (sss) type and body-contered cubic lattice structure. Formation of the alloy crystals is attributed to the important role of the expanded electrical double layers in the deionized condition and increase toward unity in the effective size ratio, which is the effective diameter of small sphere including double layer divided by that of large sphere AS structure is formed at the rather high concentrations of two spheres, where the thickness of the electrical double layer is thin and the effective size rado is comparatively small.     

Dynamics of proteins: light scattering study of dilute and dense colloidal suspensions of eye lens homogenates

We report a dynamic light scattering study on protein suspensions of bovine lens homogenates at conditions (pH and ionic strength) similar to the physiological ones. Light scattering data were collected at two temperatures, 20 and 37 degrees C, over a wide range of concentrations from the very dilute limit up to the dense regime approaching the physiological lens concentration. A comparison with experimental data from intact bovine lenses was advanced, revealing differences between dispersions and lenses at similar concentrations. In the dilute regime, two scattering entities were detected and identified with the long-time self-diffusion modes of alpha-crystallins and their aggregates, which naturally exist in lens nucleus. Upon increasing protein concentration, significant changes in time correlation function were observed starting at approximately 75 mg ml(-1), where a new mode originating from collective diffusive motions becomes visible. Self-diffusion coefficients are temperature insensitive, whereas the collective diffusion coefficient depends strongly on temperature revealing a reduction of the net repulsive interparticle forces with decreasing temperature. While there are no rigorous theoretical approaches on particle diffusion properties for multicomponent, nonideal hard sphere polydispersed systems, as the suspensions studied here, a discussion of the volume fraction dependence of the long-time self-diffusion coefficient in the context of existing theoretical approaches was undertaken. This study is purported to provide some insight into the complex light scattering pattern of intact lenses and the interactions between the constituent proteins that are responsible for lens transparency. This would lead to understand basic mechanisms of specific protein interactions that lead to lens opacification (cataract) under pathological conditions.     

Effective interactions in the colloidal suspensions from hypernetted-chain theory

The hypernetted-chain (HNC) Ornstein-Zernike integral equations are used to determine the properties of simple models of colloidal solutions where the colloids and ions are immersed in a solvent considered as a dielectric continuum and have a size ratio equal to 80 and a charge ratio varying between 1 and 4000. At an infinite dilution of colloids, the effective interactions between colloids and ions are determined for ionic concentrations ranging from 0.001 to 0.1 mol/l and compared to those derived from the Poisson-Boltzmann theory. At finite concentrations, we discuss on the basis of the HNC results the possibility of an unambiguous definition of the effective interactions between the colloidal molecules.     

Luminescence properties of polycyclic aromatic hydrocarbons in colloidal or microcrystalline suspensions

The luminescence properties of polycyclic aromatic hydrocarbons in colloidal suspension in water are compared and contrasted to like concentrations dissolved in methanol. Spectral changes noted in the colloidal state involve apparent quantum yield, self-absorption, excimer formation and room temperature phosphorescence that is oxygen insensitive. All of these effects are constant down to the insolubility limit of each compound in water and this feature can be employed to differentiate dissolved or suspended matter without matrix manipulation.     

Sedimentation and drying dissipative patterns of binary suspensions of colloidal silica spheres having different sizes

The sedimentation and drying dissipative structural patterns were formed during the course of drying binary mixtures among colloidal silica spheres of 183 nm, 305 nm, and 1.205 μm in diameter in aqueous suspension on a watch glass, a glass dish, and a cover glass, respectively. The broad ring-like sedimentation patterns were formed within several hours in suspension state for all the substrates used. Colorful macroscopic broad ring-like drying patterns were formed for the three substrates. In a watch glass, macroscopic drying patterns were composed of the outer and inner layers of small and large spheres, respectively. The two colored layers were ascribed to the Bragg diffractions of light by the dried colloidal crystals of the corresponding spheres. The width ratio of the layers changed in proportion to the mixing ratio of each spheres. In a glass dish, wave-like macroscopic drying patterns were observed in the intermediate areas between the outside edges of the broad ring and the inner wall of the cell. On a cover glass, the sphere mixing ratios were analyzed from the widths of the drying broad rings of the small spheres at the outside edge. High and distinct broad rings of small spheres and the low and vague broad one formed at the outer edges and in the inner area, respectively. Drying dissipative pattern was clarified to be one of the novel analysis techniques of colloidal size in binary colloidal mixtures.     

Transparent coatings made from spray deposited colloidal suspensions

The goal of this study is to elaborate few-micrometer thick optically active coatings based on nanoparticles spray-deposited onto a substrate and to control their scattering properties through a progressive suppression of the coffee-ring effect. The modification of the aggregation state of the nanoparticles to be sprayed induces a change of the surface roughness of the films and consequently of their optical transmission. We draw the counterintuitive conclusion that a nonstable colloidal solution gives a smoother coating than a highly stabilized colloidal solution, leading to a more transparent coating. This phenomenon is demonstrated in the case of commercial TiO(2) nanoparticles, as well as of homemade luminescent YVO(4):Eu nanoparticles, and seems to be generalized to a large range of systems.     

Destabilization of colloidal suspensions by multivalent ions and polyelectrolytes: from screening to overcharging

The destabilization of charged colloidal suspensions is studied in the presence of polyelectrolytes and the corresponding oligomers. Two different systems are investigated, namely, negatively charged particles in the presence of polyamines and positively charged ones in the presence of polycarboxylates. Multivalent oligomers of low valence destabilize the particles by screening according to the Schulze-Hardy rule. Polyelectrolytes induce destabilization by overcharging. Both regimes can be observed for oligomers of intermediate valence. The stability data of any valence can be rather well described by the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO), indicating that the interactions are mainly governed by van der Waals and electrostatic double-layer forces.     

Light-regulated electrostatic interactions in colloidal suspensions

The net charge of a colloidal particle was controlled using light and a new photocleavable self-assembled monolayer (SAM). The SAM contained a terminal ammonium group and a centrally located carboxylic acid group that was masked with an ortho-nitrobenzyl functionality. Once exposed to UV light, the 2-nitrobenzyl group was cleaved, therefore transforming the colloidal particle from a net positive (silica-SAM-NH3+) to a net negative (silica-SAM-COO-) charge. By varying the UV exposure time, their zeta potential could be tailored between +26 and -60 mV at neutral pH. To demonstrate a photoinduced gel-to-fluid phase transition, a binary colloidal suspension composed of silica-SAM-NH3+ and negatively charged, rhodamine-labeled silica particles was mixed to form a gel. Exposure to UV light rendered all of the particles negative and therefore converted the system into a colloidal fluid that settles to form a dense sediment.     

Elasticity of the crystal-like,amorphous solid-like,and liquid-like structures in deionized suspensions of colloidal silica spheres

Elastic moduli (G) of deionized suspensions of colloidal silica spheres (diameters=45–192 nm; standard deviations of sphere size divided by the mean diameter=0.05–0.21; surface charge densities=0.33–0.94 C/cm²; volume fractions of sphere ()=0.019–0.21) have been determined by the reflection spectrum measurements in a sedimentation equilibrium and the rotatory viscometry. TheG-values are 56–460 Pa (=0.019–0.051), 330–890 Pa (0.06–0.09), and 100 Pa (0.025) for the crystal-like, amorphous solid-like, and liquid-like structures, respectively. TheG-values seem to be in the order amorphous solid-like > crystal-like > liquid-like at the same sphere concentration. The suspension structures and their elastic moduli are highly influenced by the sizes and their monodispersities of the spheres. These results support that the electrostatic intersphere repulsion and the long Debye-screening length around the spheres are important for the appearance of the suspension structures.     

Understanding interactions in zeolite colloidal suspensions: A review

Over the last five years significant progress has been made in understanding interactions in zeolite colloidal suspensions by elucidating the molecular interactions between zeolite crystal surface and species such as water, cations, and organic templates. This is the outcome of multidisciplinary work involving the generation of experimental data concerning the magnitude of ζ-potential, the theoretical and experimental identification of the zeolite crystal surface structure, combined with theoretical models spanning different length scales.     

Cluster expansion for the transport properties of suspensions

The cluster expansion of the transport coefficients of suspensions is discussed. As an exmaple, the effective dielectic constant of a suspension of polarizable spheres is considered. The absolute convergence of the cluster integrals is studied . We show how to derive the Clausius-Mossotti formula from the cluster expansion and how to obtain corrections to that formula. Analogous conclusions hold for the viscosity of a fluid suspension or the elastic constants of a solid suspension.     

Giant colloidal crystals of fluorine-containing polymer spheres in exhaustively deionized aqueous suspensions and in the presence of sodium chloride

 Gigantic colloidal single crystals (2–6 mm) are formed for fluorine-containing polymer spheres (120–210 nm in diameter) in exhaustively deionized aqueous suspensions. The spheres used are poly(tetrafluoroethylene) (PTFEA and PTFEB), copolymer of tetrafluoroethylene and perfluorovinylether (PFA) and copolymer of tetrafluoroethylene and perfluoropropylene (PTP). The phase diagrams of these spheres are obtained in the deionized suspensions and also in the presence of sodium chloride for PFA. The critical sphere concentrations of crystal melting (φ _c) for these spheres are around 0.0006 in volume fraction, which are close to, but slightly larger than, those of monodispersed polystyrene spheres (φ _c ≈ 0.00015) and colloidal silica spheres(φ _c = 0.0002–0.0004) reported previously. The crystals are largest when the sphere concentrations are a bit higher than the φ _c value and their size decreases as the sphere concentration increases. Reflection spectra are taken in sedimentation equilibrium as a function of the height from the bottom of the suspension. The static elastic modulus is estimated to be 10.8 and 28.7 Pa for PTFEA and PTP spheres at the sphere concentrations 0.00325 and 0.00322 in volume fraction, respectively. Received: 27 October 1999 Accepted in revised form: 16 November 1999     

Ion size effects on the dielectric and electrokinetic properties in aqueous colloidal suspensions

One of the main assumptions of the classical theory most widely used to characterize electrokinetic phenomena is that ions behave as point-like entities. While the realization of the importance of the finite ion size goes back to Stern, 1924, it was Bikerman who presented in 1942 the first expression for the steric interactions among ions. Even now, this is the most often used expression, mainly due to its analytic simplicity. However, once ions are considered to have a finite size, other consequences besides the steric interactions have to be considered. For example, the finite closest approach distance of ions to the interface, the dielectrophoretic force acting on ions in a non-uniform electric field, the variation of the electrolyte solution permittivity with the local ion concentration, and the corresponding Born force acting on the ions, have to be taken into account. In this work, we examine these items in detail and discuss the main contributions made in this field. They show that even for the relatively low surface charge and electrolyte concentration values encountered in colloidal suspension studies, corrections to the classical theory due to ion size effects are far from negligible.     

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.