ABSTRACT
The objective of this article is to investigate how the electric polarizability manifests on the propulsion and collective dynamics of metallodielectric Janus particles by comparing the velocity spectra under rotating and nonrotating AC fields. Janus particles were fabricated by depositing sequential layers of titanium and SiO2 on spherical cores. Model systems of known polarizability were created by varying the thickness of titanium or by adjusting the concentration of electrolyte. We found that the spectra for propulsion velocity displayed features (amplitude and transition frequencies) that were closely matched in the electrorotation spectra. That is, the transition frequency from dielectric- to metal-side forward matched closely the peak in counterfield rotation, while the minima in propulsion velocity matched the transition frequency from counterfield to cofield rotation. Furthermore, based on electroorientation measurements for prolate Janus ellipsoids, we conclude that the propulsion velocity of spherical Janus particles reflects the real part of their polarizability. Solutions of the Poisson-Nernst-Planck equations confirm the thickness of the metal cap facilitates adjusting the behavior from metal- to dielectric-like. These traits translate into different collective behaviors, such as the ability to traverse or become part of a lattice of nonpatchy silica particles. Overall, these results provide experimental evidence to either challenge or refine existing electrokinetic models of propulsion.
ABSTRACT
Faradaic reactions often lead to undesirable side effects during the application of electric fields. Therefore, experimental designs often avoid faradaic reactions by working at low voltages or at high frequencies, where the electrodes behave as ideally polarizable. In this work, we show how faradaic processes under ac fields can be used advantageously to effect long-range transport, focusing and assembly of charged colloids. Herein, we use confocal microscopy and ratiometric analysis to confirm that ac fields applied in media of low conductivity induce significant pH gradients below and above the electrode charging frequency of the system. At voltages above 1 Vpp, and frequencies below 1.7 kHz, the pH profile becomes highly nonlinear. Charged particles respond to such conditions by migrating towards the point of highest pH, thereby focusing tens of microns away from both electrodes. Under the combination of oscillating electric fields and concentration gradients of electroactive species, particles experience aperiodic electrodiffusiophoresis (EDP). The theory of EDP, along with a mass transport model, describes the dynamics of particles. Furthermore, the high local concentration of particles near the focusing point leads to disorder-order transitions, whereby particles form crystals. The position and order within the levitating crystalline sheet can be readily tuned by adjusting the voltage and frequency. These results not only have significant implications for the fundamental understanding of ac colloidal electrokinetics, but also provide new possibilities for the manipulation and directed assembly of charged colloids.
ABSTRACT
In this work, we present an experimental study of the dynamics of charged colloids under direct currents and gradients of chemical species (electrodiffusiophoresis). In our approach, we simultaneously visualize the development of concentration polarization and the ensuing dynamics of charged colloids near electrodes. With the aid of confocal microscopy and fluorescent probes, we show that the passage of current through water confined between electrodes, separated about a hundred microns, results in significant pH gradients. Depending on the current density and initial conditions, steep pH gradients develop, thus becoming a significant factor in the behavior of charged colloids. Furthermore, we show that steep pH gradients induce the focusing of charged colloids away from both electrodes. Our results provide the experimental basis for further development of models of electrodiffusiophoresis and the design of non-equilibrium strategies for the fabrication of advanced materials.
ABSTRACT
Metallodielectric Janus particles (JPs) and electric fields have been a useful combination for the development of innovative concepts on AC electrokinetics, directed transport and collective dynamics. The polarizability, and its frequency dependence, underlie the rich behavior exhibited by JPs. Nonetheless, direct measurements of polarizability are few and the interplay of different mechanisms remains unclear. This paper discusses measurements and strategies to tailor the magnitude of the polarizability of JPs. Our approach uses electrorotation to measure the polarizability of particles with different thicknesses of metal in electrolyte solutions. On the other hand, we gain further insight into the basic polarization mechanisms through modeling based on the fundamental transport equations. JPs exhibit rich polarization spectra that depend strongly on the thickness of the metal layer, the conductivity of the medium and the surface charge. At low frequencies-around 10 kHz-the results indicate that counter-field rotation stems from the charging of the double layer at the particle-electrolyte interface, while the transition to co-field rotation at high frequencies (above 100 kHz) stems from the Maxwell-Wagner relaxation. The latter polarization mechanism is significantly affected by the conductivity within the electrical double layer. The insights from this study provide helpful quantitative information for the design of colloidal machines with desirable features such as targeted propulsion, and tunable collective dynamics.
ABSTRACT
The production of particles with shape-specific properties is reliant upon the separation of micro-/nanoparticles of particular shapes from particle mixtures of similar volumes. However, compared to a large number of size-based particle separation methods, shape-based separation methods have not been adequately explored. We review various up-to-date approaches to shape-based separation of rigid micro-/nanoparticles in liquid phases including size exclusion chromatography, field flow fractionation, deterministic lateral displacement, inertial focusing, electrophoresis, magnetophoresis, self-assembly precipitation, and centrifugation. We discuss separation mechanisms by classifying them as either changes in surface interactions or extensions of size-based separation. The latter includes geometric restrictions and shape-dependent transport properties.
