Aggregation of nanosized colloidal silica in the presence of various alkali cations investigated by the electrospray technique.

The slow aggregation process of a concentrated silica dispersion (Bindzil 40/220) in the presence of alkali chlorides (LiCl, NaCl, KCl, RbCl, and CsCl) was investigated by means of mobility measurements. At intervals during the aggregation, particles and aggregates were transferred from the liquid phase to the gas phase via electrospray (ES) and subsequently size selected and counted using a scanning mobility particle sizer (SMPS). This method enables the acquisition of particle and aggregate size distributions with a time resolution of minutes. To our knowledge, this is the first time that the method has been applied to study the process of colloidal aggregation. The obtained results indicate that, independent of the type of counterion, a sufficient dilution of the formed gel will cause the particles to redisperse. Hence, the silica particles are, at least initially, reversibly aggregated. The reversibility of the aggregation indicates additional non-DLVO repulsive steric interactions that are likely due to the presence of a gel layer at the surface. The size of the disintegrating aggregates was monitored as a function of the time after dilution. It was found that the most stable aggregates were formed by the ions that adsorb most strongly on the particle surface. This attractive effect was ascribed to an ion-ion correlation interaction.

A general gel layer model for the transport of colloids and macroions in dilute solution.

A general boundary element methodology for studying the dilute solution transport of rigid macroions that contain gel layers on their outer surfaces is developed and applied to several model systems. The methodology can be applied to particles of arbitrary size, shape, charge distribution, and gel layer geometry. Account is also taken of the steady state distortion of the ion atmosphere from equilibrium, which makes it applicable to the transport of highly charged structures. The coupled field equations (Poisson, ion-transport, low-Reynolds-number Navier-Stokes, and Brinkman) are solved numerically and from this, transport properties (diffusion constants, electrophoretic mobilities, excess viscosities) can be computed. In the present work, the methodology is first applied to a gel sphere model over a wide range of particle charge and the resulting transport properties are found to be in excellent agreement with independent theory under those conditions where independent theory is available. It is then applied to several prolate spheroidal models of a particular silica sol sample in an attempt to identify possible solution structures. A single model, that is able to account simultaneously for all of the transport behavior, which does not undergo significant conformational change with salt concentration, could not be found. A model with a thin (

The primary electroviscous effect of prolate silica sols.

The intrinsic viscosity and the dynamic mobility of four silica sols have been measured as a function of the ionic strength. It was found that intrinsic viscosity decreased with increasing ionic strength, which we attribute to the primary electroviscous effect. The geometry and the charge of the particles were fitted using experimental viscosity, light scattering, and dynamic mobility data, where the intrinsic viscosity measured at the highest ionic strength for a given sol was used as input data in our analysis. Further, the boundary element (BE) method was used to calculate the primary electroviscous effect and electrophoretic mobility of charged prolate ellipsoids. These calculations were then compared with experimental data, and the primary electroviscous effect was subtracted from the intrinsic viscosity at a given ionic strength, which led to a slightly altered geometry of the particles. This revised geometry was used as input data using the BE method, and the procedure was repeated iteratively until agreement was obtained at high ionic strength. In general, good agreement between theory and experiment was found.

The primary electroviscous effect, free solution electrophoretic mobility, and diffusion of dilute prolate ellipsoid particles (minor axis = 3 nm) in monovalent salt solution.

The principal objective of the present work is the modeling of the primary electroviscous effect of charged prolate ellipsoid models of low axial ratio. Other transport properties examined include (free solution) electrophoretic mobilities and translational diffusion constants. A numerical boundary element method is employed to solve the coupled Poisson, low Reynolds number Navier-Stokes, and ion transport equations. The methodology is first applied to the primary electroviscous effect of spheres with a centrosymmetric charge distribution and excellent agreement with independent theory is obtained. Specific model studies are also carried out for prolate ellipsoid models with axial ratios less than 4 and a minor axis equal to 3 nm. Most studies are carried out in aqueous NaCl solution (2 to 50 mM) at 20 degrees C for a range of different particle charges, although limited results are also presented in LiCl and KCl solution. The primary electroviscous effect for weakly charged prolate ellipsoids is smaller than that of a sphere under similar conditions. These studies are also carried out at high absolute particle charge. A comparison is made between the primary electroviscous effect and electrophoretic mobilities of prolate ellipsoids and corresponding spherical models.

Electroacoustic and Potentiometric Studies of the Hematite/Water Interface.

The basic charging properties of nearly spherical hematite particles were studied by using potentiometric titration and the electroacoustic technique. Both the pH and the ionic strength dependence of the surface charge and the zeta-potential were studied in detail. For calculating the zeta-potential from mobility data a few different theories were used and obtained differences are discussed. At pH values higher than 7 and at high electrolyte concentrations (50 mM and 100 mM NaNO(3)), it was difficult to fit the mobility data by using the full mobility spectra including both magnitude and phase angle at several frequencies. In this regime the best fits were obtained by using a theory for aggregated complexes (porous particles). From potentiometric titrations in 0.01, 0.1, and 1.0 M NaNO(3), parameters for a 1-pK Basic Stern Model were determined. The model was used to examine the possibility of correlating the experimentally determined zeta-potentials to the model-calculated potentials at the Stern plane. Qualitatively, the model predicted the correct ionic strength dependence of the zeta-potentials, and there was also a rather good quantitative agreement at high ionic strengths (50 and 100 mM NaNO(3)). However, at lower ionic strengths the model predicted values up to 40% higher than those found from the electroacoustic study. Surface conduction behind the slip plane was discussed as a possible cause for this discrepancy. Copyright 2001 Academic Press.