Colloid and Interface Chemistry

This study raises doubts about some fundamental ideas of electrostatics, namely the uniqueness theorems. The Poisson-Boltzmann equation (PBE) gives us very simple formula for charge density distribution (ρe) within fluids. Here we show that the old boundary conditions (BC), which are usually used to solve PBE, have serious defects. For example, Dirichlet condition (DC) assigns values to electrostatic potential (ψ) at different boundaries in an absolute sense i.e. without specifying any reference, which is meaningless and leads to violation of charge conservation principle. The Neumann condition (NC) assigns 'independent' values to ψ at different boundaries, whereas they are actually 'related' to each other through Poisson's equation in electrostatics (PES), which makes the solutions non-unique. We use BCs of mixed type to derive correct formula for ρe that addresses the above defects. A remarkable conclusion follows: the present physical interpretation of 'Debye length' (λD) as a screening length is incorrect.

Gold nanoparticles and their arrays are some of the most studied nanomaterials, with promising applications in many fields such as electronics, optoelectronics, catalysis and biology. In order to protect bare gold nanoparticles from aggregation, to manipulate the optical, electronic and catalytic properties of the gold core, as well as to control interfacial properties, the gold nanoparticles are generally capped by an organic layer. Previous studies [C.D. Bain, G.M. Whitesides, J. Am. Chem. Soc. 110 (1988) 3665–3666] have revealed that many phenomena (e.g., wetting, friction and adhesion), are sensitive to the top few angstroms of a surface. The interfacial properties of a gold surface derivatized with a self-assembled monolayer will thus be dictated by the functionalities present on the outer side of the monolayer. The synthesis, functionalization and surface structure of monolayer-protected gold nanoparticles have been intensively studied in recent times [M.-C. Daniel, D. Astruc, Chem. Rev. 104 (2004) 293–346]. In addition, the aggregation and dispersion of colloidal nanoparticles is one of the key issues related to their potential applications. The forces that govern the colloid stability of nanoparticle dispersions, and how to control them, have yet to be fully investigated. Here special attention has been paid to control of colloid stability using external stimuli. In this feature article, the following five areas are reviewed: synthesis and applications of nanostructured particles; formation and structure of self-assembled monolayer protected gold nanoparticles; colloid stability—DLVO and non-DLVO forces; photochemistry, photochromism and pyrimidine; and manipulation of colloid stability with external stimuli.

An experimental study was carried out to investigate aggregation and breakup of particles in a Couette flow system with the inner cylinder rotating at constant speed. Experiments were conducted with monodisperse and polydisperse suspensions at different particle volume concentrations. Depending on both the shear stress and the particle concentration, three different regimes were found. In the first regime, when the concentration is less than a critical value, the final diameter of the aggregate is independent of concentration and depends only on the shear. When the concentration is higher, two new regimes are identified, with the final diameter of the aggregate depending on both shear stress and particle concentration. Also, the transition between these two regimes corresponds to the transition from laminar to turbulent flow. In addition, the final diameter of the aggregates in the turbulent flow regime is independent of the size of the primary particles and results to be is controlled by the Kolmogorov length scale. On the contrary, in the laminar flow regime the final diameter of the aggregates shows a light tendency to decrease as the diameter of the primary particles increases.