Determination of the shell growth direction during the formation of silica microcapsules by confocal fluorescence microscopy.

A novel procedure was developed to determine the direction of silica growth during the formation of a silica shell around aqueous microdroplets in water-in-oil Pickering emulsions. Two fluorescently labeled silica precursors were added consecutively and the resulting microcapsules were visualized via confocal fluorescence microscopy, allowing the conclusion that the locus of reaction moves in the positive radial direction, i.e. from the inside to the outside. A consequence of the growth direction is that water has to diffuse through the shell to participate in the reaction on the outer surface of the shell.

Deformation of the water/oil interface during the adsorption of sterically stabilized particles.

The adsorption of sterically stabilized colloids at water/oil (w/o) interfaces is studied experimentally by the formation of Pickering emulsions. Specifically, the effect of the steric stabilizer with respect to the rate of particle adsorption is investigated. Uniform, micrometer-sized poly(methyl methacrylate) (pMMA) particles, which are sterically stabilized with poly(isobutylene) (pIB), are used. The pIB concentration on the particle surface (ΓPIB) is controlled during the synthesis by adjusting the pIB/monomer ratio. Pickering emulsions are formed directly by the addition of water to the nonaqueous pMMA dispersions and subsequent emulsification. A strong dependence of the rate of particle adsorption on ΓPIB is found. The rate constant k for particle adsorption decays exponentially with ΓPIB, which suggest the use of a Boltzmann factor to model the experimentally found rate constants. The experimental results can be explained when the activation barrier for particle adsorption EA is of the same order as the average kinetic energy EK of a particle colliding with an emulsion droplet, which is equivalent to 10(5) kBT. Interestingly, this makes EA several orders of magnitude greater than the steric interaction with another particle. A possible mechanism that can lead to such a significant repulsive force is the inhibited drainage of solvent between the particle and o/w interface. Deformation of the o/w interface then occurs, when the solvent does not have time to drain, which results in a dramatic increase in the interfacial energy. This study identified the relevance of drainage in the formation of Pickering emulsions.

Poly(methyl methacrylate)-silica microcapsules synthesized by templating Pickering emulsion droplets.

In this contribution, we present the silica microencapsulation of hydrophilic compounds by templating Pickering emulsion droplets without contamination of the dispersed phase by either the catalyst or the silica precursor. This is accomplished by the use of an amphiphilic catalyst, which situates around the Pickering emulsion droplets and directs the reaction to the interface. Both the silica precursor and the amphiphilic catalyst are soluble in the oil phase and therefore initially do not reside in the hydrophilic microcapsule templates. The thickness of the capsules can be tuned by adjusting the amount of precursor. Thus, the permeability of the capsules can in principle be controlled. The possibility of tuning the permeability holds promise for a variety of applications of the microcapsules. Because of the straightforward synthesis method and minimized mixing of the core with contaminants, the technique is potentially suitable for the encapsulation of delicate matter including live organisms, drugs, enzymes or bacteria.

Pickering emulsions: wetting and colloidal stability of hairy particles--a self-consistent field theory.

The assembly of sterically stabilized colloids at liquid-liquid interfaces is studied with the self-consistent field (SCF) theory using the discretization scheme that was developed by Scheutjens, Fleer, and co-workers. The model is based on a poly(methyl methacrylate) (pMMA) particle with poly(isobutylene) (pIB) grafted to the surface. The stabilizing groups on the particle surface have a significant effect on the interfacial assembly and, therefore, also on the formation and properties of Pickering emulsions. The wetting behavior of the particle is altered by the presence of the stabilizing groups, which affects the equilibrium position of the particles at the interface. The stabilizing groups can also lead to an activation barrier before interfacial adsorption, analogous to the steric repulsion between two particles. These effects are numerically solved with the SCF theory. It is commonly known that flocculating conditions enhance the interfacial adsorption and yield stable Pickering emulsions, which is confirmed in this work. Additionally, it is concluded that those conditions are not an absolute requirement. There is a window of stabilizer concentrations Γ(pIB), 2.2-3.3 mg/m(2) pIB, that shows both partial wetting and colloidal stability. The activation barrier for interfacial assembly is 140-550 k(B)T and is an order of magnitude higher than the colloidal stability. The difference can be attributed to the unfavorable interaction of pIB with water and a difference in geometry (plate-sphere vs sphere-sphere). This study demonstrates the interplay and provides a quantitative comparison between the wetting behavior and the colloidal stability, and it gives a better understanding of the colloidal assembly at soft interfaces and formation of Pickering emulsions in general.

Steric stabilization of Pickering emulsions for the efficient synthesis of polymeric microcapsules.

It is commonly known that Pickering emulsions are extremely stable against coalescence and are, therefore, potentially interesting for the synthesis of new materials, such as colloidosomes, microcapsules, composite particles, foams, and so on. However, for the efficient synthesis of such materials, one also has to consider the colloidal stability against aggregation, which is often neglected. In this study, it is demonstrated that steric stabilization is provided to Pickering emulsion droplets by the adsorption of poly(styrene-block-ethylene-co-propylene) (pS-b-EP) and that it is a requirement for the efficient synthesis of polymeric microcapsules. Monodisperse polystyrene particles of 648 nm are synthesized by soap-free emulsion polymerization. A model Pickering emulsion is then formed by the addition of sodium chloride at a critical concentration of 325 mM and mixing it with either heptane or decane. Subsequently, pS-b-EP is added to the Pickering emulsion to provide steric stabilization. Size exclusion chromatography is used to prove and quantify the adsorption of pS-b-EP onto the Pickering emulsion droplets. A maximum surface coverage of 1.3 mg/m(2) is obtained after 2 h, which is approximately one-third of the adsorption on a pure pS surface. We believe that the presence of polar sulfate groups on the particle, which initially stabilized the particle in water, reduces the adsorption of pS-b-EP. Microcapsules are formed by heating the Pickering emulsion above the glass-transition temperature of the particles. Significant aggregation is observed, if no pS-b-EP is used. The adsorption of pS-b-EP provides steric stabilization to the Pickering emulsion droplets, reduces aggregation significantly, and ultimately leads to the successful and efficient synthesis of pS microcapsules.