Johan Bergenholtz

Nonergodicity transitions in colloidal suspensions with attractive interactions.

Colloidal gel and glass transitions are investigated using the idealized mode coupling theory (MCT) for model systems characterized by short-range attractive interactions. Results are presented for adhesive hard sphere and hard core attractive Yukawa systems. According to MCT, the former system shows a critical glass transition concentration that increases significantly with introduction of a weak attraction. For the latter attractive Yukawa system, MCT predicts low temperature nonergodic states that extend to the critical and subcritical region. Several features of the MCT nonergodicity transition in this system agree qualitatively with experimental observations on the colloidal gel transition, suggesting that the gel transition is caused by a low temperature extension of the glass transition. The range of the attraction is shown to govern the way the glass transition line traverses the phase diagram relative to the critical point, analogous to findings for the fluid-solid freezing transition.

Gel transitions in colloidal suspensions

The idealized mode-coupling theory (MCT) is applied to colloidal systems interacting via short-range attractive interactions of Yukawa form. At low temperatures, MCT predicts a slowing down of the local dynamics and ergodicity-breaking transitions. The non-ergodicity transitions share many features with the colloidal gel transition, and are proposed to be the source of gelation in colloidal systems. Previous calculations of the phase diagram are complemented with additional data for shorter ranges of the attractive interaction, showing that the path of the non- ergodicity transition line is then unimpeded by the gas-liquid critical curve at low temperatures. Particular attention is given to the critical non-ergodicity parameters; this is motivated by recent experimental measurements. An asymptotic model is developed, valid for dilute systems of spheres interacting via strong short-range attractions, and is shown to capture all aspects of the low-temperature MCT non-ergodicity transitions.

Colloidal gelation and non-ergodicity transitions

Within the framework of the mode coupling theory (MCT) of structural relaxation, mechanisms and properties of non-ergodicity transitions in rather dilute suspensions of colloidal particles characterized by strong short-ranged attractions are studied. Results building on the virial expansion for particles with hard cores and interacting via an attractive square-well potential are presented, and their relevance to colloidal gelation is discussed.

Surface charge and interfacial potential of titanium dioxide nanoparticles: Experimental and theoretical investigations

Size dependent surface charging and interfacial potential of titanium dioxide (TiO2) nanoparticles are investigated by experimental and theoretical methods. Commercially available TiO2 (P25) nanoparticles were used for surface charge determinations by potentiometric titrations. Anatase particles, 10 and 22 nm in diameter, were synthesized by controlled hydrolysis of TiCl4, and electrophoretic mobilities were determined at a fixed pH but at increasing salt concentrations. Corrected Debye-Hückel theory of surface complexation (CDH-SC) was modified to model the size dependent surface charging behavior of TiO2 nanoparticles. Experimentally determined surface charge densities of rutile and P25 nanoparticles in different electrolytes were accurately modeled by the CDH-SC theory. Stern layer capacitances calculated by the CDH-SC theory were in good agreement with the values found by the classical surface complexation approach, and the interaction of protons with OH groups is found to be less exothermic than for iron oxide surfaces. Moreover, the CDH-SC theory predicts that the surface charge density of TiO2 nanoparticles of diameter <10nm is considerably higher than for larger particles, and pH at the point of zero charge (pHPZC) shifts to higher pH values as the particle size decreases. The importance of including the particle size in calculating the zeta potentials from mobilities is demonstrated. Smoluchowski theory showed that 10nm particles had lower zeta potential than 22 nm particles, whereas a reverse trend was seen when zeta potentials were calculated by Ohshimas theory in which particle size is included. Electrokinetic charge densities calculated from zeta potentials were found to be only one third of the true surface charge densities.

Theory of rheology of colloidal dispersions

This brief review contains a survey of recent literature on theory of rheology of colloidal dispersions. Areas of active research are highlighted, such as approximations for many body interactions in weakly sheared dispersions and the flow-induced microstructural distortions in more strongly sheared dispersions. The former approach seeks to capture the viscosity increase on increasing particle concentration, whereas the latter explains shear thinning and shear thickening.

Scattering Functions of Core-Shell-Struct ured Hard Spheres with Schulz-Distributed Radii

The scattering intensity of polydisperse systems of core-shell and layered hard spheres is considered. The Percus-Yevick solution for the partial structure factors is cast in a form suitable for numerical and analytical treatment. Closed-form, analytical expressions are given for an effective hard-sphere model of the scattering intensity of particles with an internal layered structure and a size polydispersity governed by a Schulz distribution. A similar model for polydisperse hard spheres of core-shell structure but with a monodisperse shell thickness is also presented. The models are tested against small-angle X-ray scattering experiments on a hard-sphere-like microemulsion system.

Concentration- and pH-dependence of highly alkaline sodium silicate solutions

In this study two routes for the gelation of water glass have been investigated; the destabilization by a change in pH and by an increase in concentration through evaporation. Both methods produce optically transparent, highly viscous, homogeneous solutions. The structure and dynamics of the solutions along the two routes have been investigated with dynamic light scattering, (29)Si-Nuclear Magnetic Resonance spectroscopy, viscosity measurements and infrared spectroscopy. We find that the two routes are fundamentally different. Increasing the concentration of the sodium silicate system leaves the silica speciation apparently unchanged. Lowering the pH leads to condensation reactions, thus a change in the silica speciation.

Variations in Structure Explain the Viscometric Behavior of AOT Microemulsions at Low Water/AOT Molar Ratios

Abstract The viscosity of AOT/water/decane water-in-oil microemulsions exhibits a well-known maximum as a function of water/AOT molar ratio, which is usually attributed to increased attractions among nearly spherical droplets. The maximum can be removed by adding salt or by changing the oil to CCl4. Systematic small-angle X-ray scattering (SAXS) measurements have been used to monitor the structure of the microemulsion droplets in the composition regime where the maximum appears. On increasing the droplet concentration, the scattering intensity is found to scale with the inverse of the wavevector, a behavior which is consistent with cylindrical structures. The inverse wavevector scaling is not observed when the molar ratio is changed, moving the system away from the value corresponding to the viscosity maximum. It is also not present in the scattering from systems containing enough added salt to essentially eliminate the viscosity maximum. An asymptotic analysis of the SA XS data, complemented by some quantitative modeling, is consistent with cylindrical growth of droplets as their concentration is increased. Such elongated structures are familiar from related AOT systems in which the sodium counterion has been exchanged for a divalent one. However, the results of this study suggest that the formation of non-spherical aggregates at low molar ratios is an intrinsic property of AOT.

Intrinsic viscosity of dispersions of core-shell particles

An analytic solution of the Brinkman and Stokes equations for a rigid sphere surrounded by a porous shell in pure straining flow is presented. The solution permits for an analytic determination of the intrinsic viscosity in the dilute-limiting expansion for the steady shear viscosity. The porous layer, characterized by a thickness and a constant permeability, alters the intrinsic viscosity from the Einstein value. A hydrodynamic layer thickness based on the intrinsic viscosity exhibits only a tenuous connection to the actual layer thickness within the present model. Together with the analytical solution for the translational diffusion coefficient, derived previously by Masliyah and co-workers, the present solution allows for a more detailed characterization of polymerically stabilized particles than the commonly used effective hard-sphere model.

Solid lipid nanoparticles from amphiphilic calixpyrroles

HYPOTHESIS Macrocyclic amphiphiles form interesting self-assembling structures, including solid lipid nanoparticles, which have potential applications in drug encapsulation. Aryl-extended calixpyrroles, which act as anion binding hosts, are expected to form solid lipid nanoparticles, even though the alkyl chains have unusual perpendicular geometry with respect to the hydrophilic head group. The preparation conditions and the alkyl chain length should affect the size and stability of the particles. EXPERIMENTS Solid lipid nanoparticles of two aryl-extended calixpyrroles with resorcinol walls and either meso-dodecyl or meso-methyl alkyl chains were compared. Ethanolic solutions of the calixpyrroles were mixed with water and the resulting nanoparticle dispersions were studied with dynamic light scattering and nanoparticle tracking analysis. The effect of different calixpyrrole/ethanol/water ratios on particle size was tested. The surface charge of the particles at different pH and NaCl concentration was determined by zeta potential measurements. FINDINGS The meso-dodecyl calixpyrrole produced small nanoparticles with mean hydrodynamic diameters between 40 and 70nm in 0.86-4.28M ethanol. The particles were stable in solution for several months. Particles prepared from meso-methyl calixpyrrole were larger and less stable. The smallest particles were obtained with low calixpyrrole concentration and calixpyrrole/ethanol ratio. Larger ethanol/water ratio induced broader particle size distributions. Increasing pH aided the stability of the particles due to increased negative surface charge.