Joe W. Tavacoli

Inversion of particle-stabilized emulsions of partially miscible liquids by mild drying of modified silica particles

Using a system of modified silica particles and mixtures of water and 2,6-lutidine to form particle-stabilized emulsions, we show that subtle alterations to the hydration of the particle surface can cause major shifts in emulsion structure. We use fluorescence confocal microscopy, solid state nuclear magnetic resonance (NMR) and thermo-gravimetric analysis (TGA) to explore this sensitivity, along with other shifts caused by modifications to the silica surface chemistry. The silica particles are prepared by a variant of the Stöber procedure and are modified by the inclusion of 3-(aminopropyl)triethoxysilane and the dye fluorescein isothiocyanate. Treatment prior to emulsification consists of gently drying the particles under carefully controlled conditions. In mixtures of water and 2,6-lutidine of critical composition, the particles stabilize droplet emulsions and bijels. Decreasing particle hydration yields an inversion of the emulsions from lutidine-in-water (L/W) to water-in-lutidine (W/L), with bijels forming around inversion. So dependent is the emulsion behavior on particle hydration that microscopic differences in drying within a particle sample can cause differences in the wetting behavior of that sample, which helps to stabilize multiple emulsions. The formation of bijels at emulsion inversion is also crucially dependent on the surface modification of the silica.

Size limit for particle-stabilized emulsion droplets under gravity.

We demonstrate that emulsion droplets stabilized by interfacial particles become unstable beyond a size threshold set by gravity. This holds not only for colloids but also for supracolloidal glass beads, using which we directly observe the ejection of particles near the droplet base. The number of particles acting together in these ejection events decreases with time until a stable acornlike configuration is reached. Stability occurs when the weight of all remaining particles is less than the interfacial binding force of one particle. We also show the importance of the curvature of the droplet surface in promoting particle ejection.

The fabrication and directed self-assembly of micron-sized superparamagnetic non-spherical particles

We outline a simple technique to engineer monodisperse, superparamagnetic, micron-sized prisms of arbitrary cross-section and large magnetic susceptibility. The fabrication process allows pre-positioning of the particles that introduces another lever to guide self-assembly. In this method, a dispersion of magnetic colloids in a UV-curable monomer is molded in PDMS wells and subsequently reticulated. High homogeneous magnetic content is achieved by preventing colloidal aggregation through careful choice of the colloid and monomer. Additionally, on their removal from the PDMS molds, the relative position of the magnetic particles is conserved: they are extracted as arrays whose patterns are set by the PDMS mold. This novel method therefore offers unique control of the self-assembly of specific ‘higher order’ structures mediated by dipolar interactions and directed by the geometry and initial positioning of the particles. This is also a promising approach to develop devices with complex responses to external fields.

Particle-stabilized oscillating diver: a self-assembled responsive capsule

We report the experimental discovery of a self-assembled capsule, with density set by interfacial glass beads and an internal bubble, that automatically performs regular oscillations up and down a vial in response to a temperature gradient. Similar composites featuring interfacial particles and multiple internal compartments could be the solution to a variety of application challenges.

One-step production of multiple emulsions

Multiple emulsions have great potential for application in food science as a means to reduce fat content or for controlled encapsulation and release of actives. However, neither production nor stability is straightforward. Typically, multiple emulsions are prepared via two emulsification steps and a variety of approaches have been deployed to give long-term stability. It is well known that multiple emulsions can be prepared in a single step by harnessing emulsion inversion, although the resulting emulsions are usually short lived. Recently, several contrasting methods have been demonstrated which give rise to stable multiple emulsions via one-step production processes. Here we review the current state of microfluidic, polymer-stabilized and particle-stabilized approaches; these rely on phase separation, the role of electrolyte and the trapping of solvent with particles respectively.

Solid microscopic rings formed via wetting and subsequent dewetting

We report the spontaneous formation of rings when a colloidal dispersion, containing silica-coated iron-oxide particles and the liquids ethanol and ethoxylated trimethylolpropane triacrylate, is deposited within micron-sized PDMS wells. Just after filling, the interface between air and the dispersion is a meniscus dictated by the dispersions contact angle on PDMS. Upon evaporation of ethanol the meniscus lowers and, if a critical volume is reached, a rupture process is initiated and the dispersion adopts a ring morphology. The final dispersion consists only of particles and ethoxylated trimethylolpropane triacrylate that can be reticulated to solidify the ring geometry. The colloidal particles within the dispersion are essential for the stability of the rings prior to the reticulation. Here, by using iron-oxide based colloidal particles we fabricated superparamagnetic rings, opening up new avenues for applications. The dimensions of the rings can be tuned by adjusting both the size of the PDMS wells and the amount of ethanol in the dispersion. In this manner it is possible to fabricate rings with annuli smaller than a micron – a scale below the lower limit of standard lithography. Calculations assuming an equilibrium contact angle of ethoxylated trimethylolpropane triacrylate on PDMS reproduce the experimental results strikingly well.

CHAPTER 6:Bicontinuous Emulsions Stabilized by Colloidal Particles

The liquid–liquid phase separation of binary fluids, induced by a temperature quench, can be arrested by colloidal particles trapped at the interface. The arrested structure, a novel soft solid known as a bicontinuous interfacially jammed emulsion gel (bijel), was first predicted by computer simulations and subsequently realized in the lab. Initially the mechanical properties are controlled by the interfacial tension between the two fluid domains (e.g. a deeper quench yields a stronger bijel) and the volume fraction of particles. Reversing the temperature quench results in the two fluids becoming miscible again. Whether or not this leaves a colloidal gel in place which is stable without a liquid–liquid interface (a ‘monogel’) depends on the age of the gel and the choice of liquids. In this chapter we describe the current state of bijel research using experimental, theoretical and computational approaches. We discuss possible areas of application and, finally, we contrast the physical route with which the bijel is prepared with a related material that is prepared via direct particle–particle interactions.

Assembly Modulated by Particle Position and Shape: A New Concept in Self-Assembly

In this communication we outline how the bespoke arrangements and design of micron-sized superparamagnetic shapes provide levers to modulate their assembly under homogeneous magnetic fields. We label this new approach, ‘assembly modulated by particle position and shape’ (APPS). Specifically, using rectangular lattices of superparamagnetic micron-sized cuboids, we construct distinct microstructures by adjusting lattice pitch and angle of array with respect to a magnetic field. Broadly, we find two modes of assembly: (1) immediate 2D jamming of the cuboids as they rotate to align with the applied field (rotation-induced jamming) and (2) aggregation via translation after their full alignment (dipole-dipole assembly). The boundary between these two assembly pathways is independent on field strength being solely a function of the cuboid’s dimensions, lattice pitch, and array angle with respect to field—a relationship which we capture, along with other features of the assembly process, in a ‘phase diagram’. In doing so, we set out initial design rules to build custom made assemblies. Moreover, these assemblies can be made flexible thanks to the hinged contacts of their particle building blocks. This flexibility, combined with the superparamagnetic nature of the architectures, renders our assembly method particularly appropriate for the construction of complex actuators at a scale hitherto not possible.