Electrostatic Interaction of Colloidal Surfaces with Variable Charge

When two surfaces with ionizable groups interact across an electrolyte solution, both their equilibrium charge density and the corresponding electrostatic surface potential will depend on the surface separation (charge regulation). The corresponding nonlinear boundary conditions are often replaced, for simplicity, by the limiting conditions of constant charge or constant surface potential. A strategy to linearize the boundary conditions, initially devised for the case of low potentials only, has recently been adapted to situations of arbitrary potential. Within a 1-pK Basic Stern Model suitable for a large class of surface materials, we now address the implications of charge regulation on the level of Poisson−Boltzmann theory. The regulation behavior can be characterized in terms of a single parameter taking values between 0 for constant potential and 1 for constant charge conditions. This parameter depends on the capacities associated with the diffuse part and the compact part of the electrical double layer and can be inferred from acid−base titrations. We discuss the effect of regulation on a variety of measurable quantities for exemplary surfaces of carboxyl latex, silica, and iron hydroxide

Image Charge Effects on the Formation of Pickering Emulsions

Vigorous mixing of an aqueous particle dispersion with oil usually produces a particle-stabilized emulsion (a “Pickering emulsion”), the longevity of which depends on the particles’ wetting properties. A known exception occurs when particles fail to adsorb to the oil–water interface created during mixing because of a strong repulsion between charges on the particle surface and similar charges on the oil–water interface; in this case, no Pickering emulsion is formed. Here, we present experimental evidence that the rarely considered electrostatic image force can cause a much bigger hindrance to particle adsorption and prevent the formation of Pickering emulsions even when the particle interaction with the interface charge is attractive. A simple theoretical estimate confirms the observed magnitude of this effect and points at an important limitation of Pickering emulsification, a technology with widespread industrial applications and increasing popularity in materials research and development

Interfaces Charged by a Nonionic Surfactant

Highly hydrophobic, water-insoluble nonionic surfactants are often considered irrelevant to the ionization of interfaces at which they adsorb, despite observations that suggest otherwise. In the present study, we provide unambiguous evidence for the participation of a water-insoluble surfactant in interfacial ionization by conducting electrophoresis experiments for surfactant-stabilized nonpolar oil droplets in aqueous continuous phase. It was found that the surfactant with amine headgroup positively charged the surface of oil suspended in aqueous continuous phase (oil/water interface), which is consistent with its basic nature. In nonpolar oil continuous phase, the same surfactant positively charged the surface of solid silica (solid/oil interface) which is often considered acidic. The latter observation is exactly opposite to what the traditional <i>acid–base mechanism of surface charging</i> would predict, most clearly suggesting the possibility for another charging mechanism

Charging Mechanism for Polymer Particles in Nonpolar Surfactant Solutions: Influence of Polymer Type and Surface Functionality

Surface charging phenomena in nonpolar dispersions are exploited in a wide range of industrial applications, but their mechanistic understanding lags far behind. We investigate the surface charging of a variety of polymer particles with different surface functionality in alkane solutions of a custom-synthesized and purified polyisobutylene succinimide (PIBS) polyamine surfactant and a related commercial surfactant mixture commonly used to control particle charge. We find that the observed electrophoretic particle mobility cannot be explained exclusively by donor–acceptor interactions between surface functional groups and surfactant polar moieties. Our results instead suggest an interplay of multiple charging pathways, which likely include the competitive adsorption of ions generated among inverse micelles in the solution bulk. We discuss possible factors affecting the competitive adsorption of micellar ions, such as the chemical nature of the particle bulk material and the size asymmetry between inverse micelles of opposite charge

Effect of Shear on Pumped Capillary Foams

Foam flow in many applications, like firefighting and oil recovery, requires stable foams that can withstand the stress and aging that result from both shear and thermodynamic instability. Events of drainage and coarsening drive the collapse of foams and greatly affect foam efficacy in processes relying on foam transport. Recently, it was discovered that foams can be stabilized by the synergistic action of colloidal particles and a small amount of a water-immiscible liquid that mediates capillary forces. The so-called capillary foams contain gas bubbles that are coated by a thin oil-particle film and integrated in a network of oil-bridged particles; the present study explores how this unique architecture impacts the foams’ flow dynamics. We pumped capillary foams through millimeter-sized tubing (ID: 790 μm) at different flow rates and analyzed the influence of stress and aging on capillary foam stability. We find that the foams remain stable when pumped at higher flow rates but undergo phase separation when pumped at low flow rates. Our observations further show that the particle network is responsible for the observed stability in capillary foams and that network strength and stability of an existing foam can be increased by shearing

Mechanisms of Particle Charging by Surfactants in Nonpolar Dispersions

Electric charging of colloidal particles in nonpolar solvents plays a crucial role for many industrial applications and products, including rubbers, engine oils, toners, or electronic displays. Although disfavored by the low solvent permittivity, particle charging can be induced by added surfactants, even nonionic ones, but the underlying mechanism is poorly understood, and neither the magnitude nor the sign of charge can generally be predicted from the particle and surfactant properties. The conclusiveness of scientific studies has been limited partly by a traditional focus on few surfactant types with many differences in their chemical structure and often poorly defined composition. Here we investigate the surface charging of poly­(methyl methacrylate) particles dispersed in hexane-based solutions of three purified polyisobutylene succinimide polyamine surfactants with “subtle” structural variations. We precisely vary the surfactant chemistry by replacing only a single electronegative atom located at a fixed position within the polar headgroup. Electrophoresis reveals that these small differences between the surfactants lead to qualitatively different particle charging. In the respective particle-free surfactant solutions we also find potentially telling differences in the size of the surfactant aggregates (inverse micelles), the residual water content, and the electric solution conductivity as well as indications for a significant size difference between oppositely charged inverse micelles of the most hygroscopic surfactant. An analysis that accounts for the acid/base properties of all constituents suggests that the observed particle charging is better described by asymmetric adsorption of charged inverse micelles from the liquid bulk than by charge creation at the particle surface. Intramicellar acid–base interaction and intermicellar surfactant exchange help rationalize the formation of micellar ions pairs with size asymmetry

Janus Particles in a Nonpolar Solvent

Amphiphilic Janus particles are currently receiving great attention as “solid surfactants”. Previous studies have introduced such particles with a variety of shapes and functions, but there has so far been a strong emphasis on water-dispersible particles that mimic the molecular surfactants soluble in polar solvents. Here we present an example of lipophilic Janus particles which are selectively dispersible in very nonpolar solvents such as alkanes. Interfacial tension measurements between the alkane dispersions and pure water indicate that these particles do have interfacial activity, and like typical hydrophobic, nonionic surfactants, they do not partition to the aqueous bulk. We also show that the oil-borne particles, by retaining locally polar domains where charges can reside, generate electric conductivity in nonpolar liquidsanother feature familiar from molecular surfactants and one commonly exploited to mitigate explosion hazards due to flow electrification during petroleum pumping and in the formulation of electronic inks

Programming Semiconductor Nanowire Composition with Sub-100 nm Resolution via the Geode Process

We demonstrate the vapor–liquid–solid growth of single-crystalline i-Si, i-Si/n-Si, and SixGe1–x/SiyGe1–y nanowires via the Geode process. By enabling nanowire growth on the large internal surface area of a microcapsule powder, the Geode process improves the scalability of semiconductor nanowire manufacturing while maintaining nanoscale programmability. Here, we show that heat and mass transport limitations introduced by the microcapsule wall are negligible, enabling the same degree of compositional control for nanowires grown inside microcapsules and on conventional flat substrates. Efficient heat and mass transport also minimize the structural variations of nanowires grown in microcapsules with different diameters and wall thicknesses. Nanowires containing at least 16 segments and segment lengths below 75 nm are demonstrated