Opening and Closing of Particle Shells on Droplets via Electric Fields and Its Applications.

Active, tunable, and reversible opening and closing of particle shells on droplets may facilitate chemical reactions in droplets and enable various small-scale laboratory operations, including online detection, measurement, and adjustment of droplet liquid. Manipulating various types of particle shells in a controlled manner requires new routes. This work provides a new strategy for controlling the spatial arrangement of particle-covered oil droplets using electric fields that expands the application of responsive droplets beyond the abovementioned examples. The behavior of stimulated particle-covered droplets is exploited in multiple ways: to form an active smart device, fabricate Janus and patchy shells, create an online diagnostic tool, and produce a tool for fundamental studies. Electric fields are used here to manipulate particle films on oil droplets through the synergetic action of droplet deformation and electrohydrodynamic liquid flows. First, the effects of electric field strength and liquid viscosity on droplet deformation, surface particle arrangements, and dynamics are examined in detail. Then three examples of applications of responsive particle-covered droplets are demonstrated. Our results show that the reversible opening and closing of the droplet's shells, composed of various types of particles, can be conveniently achieved through electric fields, opening up a new possibility for applications in optics, clinical diagnostics, microfluidics, and material engineering.

Assembly of 1D Granular Structures from Sulfonated Polystyrene Microparticles.

Being able to systematically modify the electric properties of nano- and microparticles opens up new possibilities for the bottom-up fabrication of advanced materials such as the fabrication of one-dimensional (1D) colloidal and granular materials. Fabricating 1D structures from individual particles offers plenty of applications ranging from electronic sensors and photovoltaics to artificial flagella for hydrodynamic propulsion. In this work, we demonstrate the assembly of 1D structures composed of individual microparticles with modified electric properties, pulled out of a liquid environment into air. Polystyrene particles were modified by sulfonation for different reaction times and characterized by dielectric spectroscopy and dipolar force measurements. We found that by increasing the sulfonation time, the values of both electrical conductivity and dielectric constant of the particles increase, and that the relaxation frequency of particle electric polarization changes, causing the measured dielectric loss of the particles to shift towards higher frequencies. We attributed these results to water adsorbed at the surface of the particles. With sulfonated polystyrene particles exhibiting a range of electric properties, we showed how the electric properties of individual particles influence the formation of 1D structures. By tuning applied voltage and frequency, we were able to control the formation and dynamics of 1D structures, including chain bending and oscillation.

Electric Field-Driven Assembly of Sulfonated Polystyrene Microspheres.

A designed assembly of particles at liquid interfaces offers many advantages for development of materials, and can be performed by various means. Electric fields provide a flexible method for structuring particles on drops, utilizing electrohydrodynamic circulation flows, and dielectrophoretic and electrophoretic interactions. In addition to the properties of the applied electric field, the manipulation of particles often depends on the intrinsic properties of the particles to be assembled. Here, we present an easy approach for producing polystyrene microparticles with different electrical properties. These particles are used for investigations into electric field-guided particle assembly in the bulk and on surfaces of oil droplets. By sulfonating polystyrene particles, we produce a set of particles with a range of dielectric constants and electrical conductivities, related to the sulfonation reaction time. The paper presents diverse particle behavior driven by electric fields, including particle assembly at different droplet locations, particle chaining, and the formation of ribbon-like structures with anisotropic properties.

Mechanics of Pickering Drops Probed by Electric Field-Induced Stress.

Fluid drops coated with particles, so-called Pickering drops, play an important role in emulsion and capsule applications. In this context, knowledge of mechanical properties and stability of Pickering drops are essential. Here we prepare Pickering drops via electric field-driven self-assembly. We use direct current (DC) electric fields to induce mechanical stress on these drops, as a possible alternative to the use of, for example, fluid flow fields. Drop deformation is monitored as a function of the applied electric field strength. The deformation of pure silicone oil drops is enhanced when covered by insulating polyethylene (PE) particles, whereas drops covered by conductive clay particles can also change shape from oblate to prolate. We attribute these results to changes in the electric conductivity of the drop interface after adding particles, and have developed a fluid shell description to estimate the conductivity of Pickering particle layers that are assumed to be non-jammed and fluid-like. Retraction experiments in the absence of electric fields are also performed. Particle-covered drops retract slower than particle-free drops, caused by increased viscous dissipation due to the presence of the Pickering particle layer.

Electroformation of Janus and patchy capsules.

Janus and patchy particles have designed heterogeneous surfaces that consist of two or several patches with different materials properties. These particles are emerging as building blocks for a new class of soft matter and functional materials. Here we introduce a route for forming heterogeneous capsules by producing highly ordered jammed colloidal shells of various shapes with domains of controlled size and composition. These structures combine the functionalities offered by Janus or patchy particles, and those given by permeable shells such as colloidosomes. The simple assembly route involves the synergetic action of electro-hydrodynamic flow and electro-coalescence. We demonstrate that the method is robust and straightforwardly extendable to production of multi-patchy capsules. This forms a starting point for producing patchy colloidosomes with domains of anisotropic chemical surface properties, permeability or mixed liquid-solid phase domains, which could be exploited to produce functional emulsions, light and hollow supra-colloidosome structures, or scaffolds.

Active structuring of colloidal armour on liquid drops.

Adsorption and assembly of colloidal particles at the surface of liquid droplets are at the base of particle-stabilized emulsions and templating. Here we report that electrohydrodynamic and electro-rheological effects in leaky-dielectric liquid drops can be used to structure and dynamically control colloidal particle assemblies at drop surfaces, including electric-field-assisted convective assembly of jammed colloidal 'ribbons', electro-rheological colloidal chains confined to a two-dimensional surface and spinning colloidal domains on that surface. In addition, we demonstrate the size control of 'pupil'-like openings in colloidal shells. We anticipate that electric field manipulation of colloids in leaky dielectrics can lead to new routes of colloidosome assembly and design for 'smart armoured' droplets.