Dr Peter Ireland

We report an unusually large spacing observed between microparticles after delivery to the surface of a pendent water droplet using a DC nonuniform electrostatic field, primarily via dielectrophoresis. The influence of particle properties was investigated using core particles, which were either coated or surface-modified to alter their wettability and conductivity. Particles that exhibited this spacing were both hydrophobic and possessed some dielectric material exposed to the external field, such as a coating or exposed dielectric core. The origin of this behavior is proposed to be the induced dipole-dipole repulsion between particles, which increases with particle size and decreases when the magnitude of the electric field is reduced. When the particles were no longer subjected to an external field, this large interparticle repulsion ceased and the particles settled to the bottom of the droplet under the force of gravity. We derive a simple model to predict this spacing, with the dipole-dipole repulsion balanced against particle weight. The external electric field was calculated using the existing electric field models. The spacing was found to be dependent on particle density and the induced dipole moment as well as the number of particles present on the droplet interface. As the number of particles increased, a decrease in interparticle spacing was observed.

Liquid marbles may be traditionally formed by rolling a droplet on a bed of non-wetting particles resulting in encapsulation and stabilisation. Particles used in this process may range from nanometre to millimetre if handled with sufficient care. This method, however, runs the risk of droplet coalescence and is limited to non-wetting particles. Currently there exist some alternative methods of formulation including using electrostatics to either deliver a particle bed to the droplet or pull the droplet to the particles. The former has shown some promise in potential batch processes but is hindered by interparticle forces. Additional production methods include a form of blender, but this has shown to be unable to produce marbles of a narrow size distribution. Once formed, liquid marbles have demonstrated value as potential blood typing devices, as micro-reaction vessels due to the inherent barrier between the internal phase and the substrate whilst maintaining gas permeability, and as contaminant sensors. Liquid marbles also demonstrate a remarkable level of elasticity under compressive force and reduced evaporation rates when compared to bare water droplets, a function of the size and composition of the stabilising particles. In addition to this, liquid marbles have been proposed as actuators. Locomotion may easily be induced in these structures, using electrostatics, sound, magnetism or light depending on the particle/liquid combinations used in formation, and the environment of deployment. This review seeks to present and summarise recent advances in the field of liquid marble manufacture and methods for actuation. We also aim to highlight potential future avenues of further study within this arena.

Specific particle material properties such as conductivity, cohesion, and density have been neither directly nor thoroughly studied regarding particle behavior in an electrostatic field and the follow-on impact this has on the electrostatic formation of liquid marbles. In this method, an applied electric field drives the extraction of particles from a bed and their transport to a pendent, earthed water droplet. Herein, prior studies of electrostatic formation of particle-stabilized droplets and liquid marbles have been expanded to compare the impact of density using the spherical polystyrene (PS) latex and glass particles of similar shape and size. The addition of thin polymer shells to both samples, which increases the conductivity and cohesion, allows the interplay of these three properties to be examined systematically. Separation distances between the particle bed and the droplet from which particles can initially be extracted increase as the negative applied potential increases. Initial extraction distances of both core particles were found to be similar, ~1.5 mm at 2.0 kV applied potential, despite the greater density, and thus mass of the glass particles. It is demonstrated that this is a result of competitive interactions between particle density, conductivity, and cohesion; PS is less conductive and more cohesive than glass. Introducing a polypyrrole shell increases the separation distance for extraction to approximately 4 mm for PS core particles but has little impact on glass core particles, demonstrating that for particles with constant conductivity and cohesion reducing the density facilitates extraction. Modeling and quantification of extraction threshold forces for each particle type were undertaken, utilizing the measurement of a radially symmetric area of the particle bed from which particles were observed in the initial extraction stages. This measurement highlighted that it is significantly easier to extract PS compared to glass, with particles extracted from a region in the bed up to 5 times the width in the PS case. Particle density is hypothesized to not be the determining factor in the stabilization of the coated liquid droplets; therefore, the interplay of a multitude of physical properties must be considered when determining the suitability of particulate materials for this electrostatic method.

We report the manufacture of complex structures of silica, coal or sphalerite particles around a water droplet, driven by an electrostatic field. A particle bed was deposited on an electrically biased substrate and an earthed water drop brought close, such that the particles jumped to the drop. These structures' shape and internal composition were determined by a combination of the particles' wettability and electrical properties, and other attributes such as shape, size and density were also thought to play a role. Hydrophilic particles tend to be internalised by the drop, while hydrophobic ones tend to form a layer or shell on the surface. Thus, one example of these structures was a 'complex liquid marble', with a hydrophilic particle suspension core and a stabilising shell of hydrophobic particles.

We report the first study of the influence of drop and particle size on the electrostatic manufacture and subsequent stability of liquid marbles. It is clear from this study that the ¿rules¿ for electrostatic formation of liquid marbles are quite different for those for conventional direct-contact manufacture. Formation of liquid marbles was observed when an earthed water drop of volume 3¿7¿µL was brought into proximity with a bed of highly-charged polystyrene particles of diameter 22¿153¿µm. Under appropriate conditions the particles jumped to and coated the drop, producing a particle-liquid aggregate that dropped to the bed surface in the form of either a stable liquid marble or a particle-stabilised sessile drop. The subsequent evolution of the physical dimensions of the metastable aggregate was measured as the liquid drained into the bed, and its stability assessed. Formation of stable liquid marbles appeared to occur more easily for smaller drops and larger particles, and some of these considerably exceeded the conventionally-understood limit for the ratio of particle to drop size of stable liquid marbles.

In this paper we investigate the hypothesis that when bubbles carrying attached hydrophobic particles arrive at an air-liquid interface, the abrupt change in velocity is sufficient to dislodge attached particles, which fall back into the liquid. For the first time, experiments have demonstrated a case in which the particles do not detach, but move smoothly over the surface of the bubbles. The kinetic energy of arrival is dissipated by the motion of the particles through the liquid, as they move over the surface of the bubble while remaining attached. Some energy is also dissipated by the pulsations of the bubbles. The pulsations themselves do not lead to detachment of particles. A theory has been developed to explain the observed phenomena. © 2014 Published by Elsevier B.V.

Buoyancy-driven convective flows have a substantial effect on the performance of the froth layer in flotation cells, particularly when wash water is applied, but are relatively poorly understood. This study presents some experiments on convective flows in a foam undergoing forced drainage. A flat cell was used to create a planar foam, and a dye tracer was used to reveal the flow patterns, which were digitally imaged. The eddy scales and mixing behaviour of the flows are assessed using several different metrics, and their dependence on liquid and gas flow rates in the foam is assessed and compared. Finally, the implications of these findings for the effectiveness of wash water in flotation froths are discussed. © 2013.

Transport of dry solid particles to a liquid is relevant to a number of emerging applications, including 'liquid marbles'. We report experiments where the transport of dry particles to a pendent water droplet is driven by an external electric field. Both hydrophilic and hydrophobic materials (silica, PMMA) were studied. For silica particles (hydrophilic, poorly conductive), a critical applied voltage initiated transfer, in the form of a rapid 'avalanche' of a large number of particles. The particle-loaded drop then detached, producing a metastable spherical agglomerate. Pure PMMA particles did not display this 'avalanche' behaviour, and when added to silica particles, appeared to cause aggregation and change the nature of the transfer mechanism. This paper is largely devoted to the avalanche process, in which deformation of the drop and radial compaction of the particle bed due to the electric field are thought to have played a central role. Since no direct contact is required between the bed and the drop, we hope to produce liquid marble-type aggregates with layered structures incorporating hydrophilic particles, which has not previously been possible.