Hydration Energy-Dependent Ion Intercalation on Graphite and the Asymmetric Electrowetting.

Ion intercalation in graphite is widely used in desalination, batteries, and graphene stripping; it has high value in the fields of industry and research. However, selective ion transport, particularly (de)hydration energy and the hydration shell effect on the intercalation of ions into the graphite interlayer spaces, is still unclear. Here, we report low-voltage ion intercalation as observed by electrowetting on highly oriented pyrolytic graphite of an aqueous drop containing various inorganic salts. The electrowetting response exhibits asymmetric behavior with no contact angle change for the negative polarity and a threshold voltage for the onset of the contact angle change for the positive polarity. To explain the asymmetric electrowetting behavior and quantitatively predict the threshold voltage, we developed a physical model based on the hydration shell energy and size of the ion that undergoes partial breaking/deformation during the co-intercalation into the spaces between graphite layers. Electrowetting experiments using ions with various hydration energies and hydration radii were performed to confirm the prediction of the model. Further, we show a strategy to make the electrowetting response of LiCl drops symmetric via tuning the hydration energy of the Li+ ions using a binary solvent of a glycerol-water mixture. This article will provide an understanding of the hydration (solvation) energy dependence intercalation mechanism in graphite for electrowetting, which underpins various processes such as ion battery applications and the graphene exfoliation process.

Is there a difference between surfactant-stabilised and Pickering emulsions?

What measurable physical properties allow one to distinguish surfactant-stabilised from Pickering emulsions? Whereas surfactants influence oil/water interfaces by lowering the oil/water interfacial tension, particles are assumed to have little effect on the interfacial tension. Here we perform interfacial tension (IFT) measurements on three different systems: (1) soybean oil and water with ethyl cellulose nanoparticles (ECNPs), (2) silicone oil and water with the globular protein bovine serum albumin (BSA), and (3) sodium dodecyl sulfate (SDS) solutions and air. The first two systems contain particles, while the third system contains surfactant molecules. We observe a significant decrease in interfacial tension with increasing particle/molecule concentration in all three systems. We analyse the surface tension data using the Gibbs adsorption isotherm and the Langmuir equation of state for the surface, resulting in surprisingly high adsorption densities for the particle-based systems. These seem to behave very much like the surfactant system: the decrease in tension is due to the presence of many particles at the interface, each with an adsorption energy of a few kBT. Dynamic interfacial tension measurements show that the systems are in equilibrium, and that the characteristic time scale for adsorption is much longer for particle-based systems than for surfactants, in line with their size difference. In addition, the particle-based emulsion is shown to be less stable against coalescence than the surfactant-stabilised emulsion. This leaves us with the conclusion that we are not able to make a clear distinction between the surfactant-stabilised and Pickering emulsions.

Bubble Manipulation Driven by Alternating Current Electrowetting: Oscillation Modes and Surface Detachment.

In this paper, a millimeter-sized bubble in water pending on a substrate is manipulated by applying an alternating current (AC) electric field, known as electrowetting on dielectric. In this setup, standing waves on the bubble surface are observed. The amplitude of these waves varies with frequency, and three resonance peaks (21, 76, and 134 Hz) can be identified. By incorporating the nonlinear friction force for the contact line to an existing surface mode model, a significant improvement to explain the spectrum of the oscillations is obtained, predicting three peak positions, widths, and heights with good accuracy. We also show that bubble detachment correlates with the low-frequency resonance peak. It is found experimentally that if close enough to this peak, then bubbles at sufficiently high voltages are observed to detach from the substrate. This suggests that inertial effects can effectively promote bubble detachment. To confirm this hypothesis, the bubble dynamics is simulated with COMSOL using the full Navier-Stokes equation with a two-phase field and electrostatic stresses. It was found that the bubble experimental detachment process is quite well-reproduced in the simulation, confirming the role of fluid inertia for the detachment process. Given the nice correspondence between the experimental state diagrams and the theoretical modeling, this work contributes to identify a window for precise and reliable bubble manipulation by means of AC electrowetting.

Transition of interfacial capacitors in electrowetting on a graphite surface by ion intercalation.

The low voltage electrowetting response of a LiCl aqueous solution on a freshly cleaved surface of highly oriented pyrolytic graphite (HOPG) is presented. For applied voltages below 1 V, the energy stored in the electrical double layer (EDL) is insufficient to drive the spreading of the drop due to the pinning of the three phase contact line at the step edges. Electrochemical impedance spectroscopy shows a dramatic increase in capacitance above 1 V, which provides a sufficient electrowetting force for depinning the contact line, resulting in a subsequent decrease of the contact angle. The transition of the interfacial capacitance from the EDL to the many-fold high capacitance of the pseudocapacitor drives the electrowetting transition on the HOPG surface. The observed changes in the capacitances above 1 V are correlated with the cyclic voltammetry and atomic force microscopy results, which show that the Cl- ions intercalate into the graphite galleries upon acquiring sufficient energy to overcome the van der Waals attraction between the graphene layers through the side of the step edge of the basal planes. To the best of our knowledge, this is the first study on the voltage dependent intercalation mediated transition of interfacial capacitance driving the spreading of an aqueous electrolyte drop on the HOPG surface, which provides a fundamental understanding of the mechanism and opens up potential applications in microfluidics and charge storage technologies.

Rotational diffusion affects the dynamical self-assembly pathways of patchy particles.

Predicting the self-assembly kinetics of particles with anisotropic interactions, such as colloidal patchy particles or proteins with multiple binding sites, is important for the design of novel high-tech materials, as well as for understanding biological systems, e.g., viruses or regulatory networks. Often stochastic in nature, such self-assembly processes are fundamentally governed by rotational and translational diffusion. Whereas the rotational diffusion constant of particles is usually considered to be coupled to the translational diffusion via the Stokes-Einstein relation, in the past decade it has become clear that they can be independently altered by molecular crowding agents or via external fields. Because virus capsids naturally assemble in crowded environments such as the cell cytoplasm but also in aqueous solution in vitro, it is important to investigate how varying the rotational diffusion with respect to transitional diffusion alters the kinetic pathways of self-assembly. Kinetic trapping in malformed or intermediate structures often impedes a direct simulation approach of a kinetic network by dramatically slowing down the relaxation to the designed ground state. However, using recently developed path-sampling techniques, we can sample and analyze the entire self-assembly kinetic network of simple patchy particle systems. For assembly of a designed cluster of patchy particles we find that changing the rotational diffusion does not change the equilibrium constants, but significantly affects the dynamical pathways, and enhances (suppresses) the overall relaxation process and the yield of the target structure, by avoiding (encountering) frustrated states. Besides insight, this finding provides a design principle for improved control of nanoparticle self-assembly.

Oil Motion Control by an Extra Pinning Structure in Electro-Fluidic Display.

Oil motion control is the key for the optical performance of electro-fluidic displays (EFD). In this paper, we introduced an extra pinning structure (EPS) into the EFD pixel to control the oil motion inside for the first time. The pinning structure canbe fabricated together with the pixel wall by a one-step lithography process. The effect of the relative location of the EPS in pixels on the oil motion was studied by a series of optoelectronic measurements. EPS showed good control of oil rupture position. The properly located EPS effectively guided the oil contraction direction, significantly accelerated switching on process, and suppressed oil overflow, without declining in aperture ratio. An asymmetrically designed EPS off the diagonal is recommended. This study provides a novel and facile way for oil motion control within an EFD pixel in both direction and timescale.

The role of multivalency in the association kinetics of patchy particle complexes.

Association and dissociation of particles are elementary steps in many natural and technological relevant processes. For many such processes, the presence of multiple binding sites is essential. For instance, protein complexes and regular structures such as virus shells are formed from elementary building blocks with multiple binding sites. Here we address a fundamental question concerning the role of multivalency of binding sites in the association kinetics of such complexes. Using single replica transition interface sampling simulations, we investigate the influence of the multivalency on the binding kinetics and the association mechanism of patchy particles that form polyhedral clusters. When the individual bond strength is fixed, the kinetics naturally is very dependent on the multivalency, with dissociation rate constants exponentially decreasing with the number of bonds. In contrast, we find that when the total bond energy per particle is kept constant, association and dissociation rate constants turn out rather independent of multivalency, although of course still very dependent on the total energy. The association and dissociation mechanisms, however, depend on the presence and nature of the intermediate states. For instance, pathways that visit intermediate states are less prevalent for particles with five binding sites compared to the case of particles with only three bonds. The presence of intermediate states can lead to kinetic trapping and malformed aggregates. We discuss implications for natural forming complexes such as virus shells and for the design of artificial colloidal patchy particles.

Polydispersity and gelation in concentrated colloids with competing interactions.

In colloids with competing short-range attractions and long-range repulsions, microcrystalline gels are experimentally formed under conditions where computer simulations point to a lamellar phase as the ground state. Here, upon applying a low-frequency alternating electric field, we bring the system from an initial gel state to a columnar-like state. While molecular dynamics simulations on monodisperse colloids reveal that a columnar structure spontaneously evolves towards a lamellar phase, the columnar-like state in experiments relaxes back to the initial disordered gel state once the electric field is switched off. Similarly, a columnar phase in molecular dynamics simulations decomposes into finite-size crystalline clusters as the relative polydispersity of the colloids is around 1.0%. We conclude that the experimentally observed melting of the columnar structure is driven by polydispersity. Moreover, further simulations reveal that the critical polydispersity required to destabilize a long-range ordered structure increases with the attraction range, pointing to the possibility of observing periodic structures in experiments if the attraction range is sufficiently long compared to the polydispersity of the colloids.

Surface roughness directed self-assembly of patchy particles into colloidal micelles.

Colloidal particles with site-specific directional interactions, so called "patchy particles", are promising candidates for bottom-up assembly routes towards complex structures with rationally designed properties. Here we present an experimental realization of patchy colloidal particles based on material independent depletion interaction and surface roughness. Curved, smooth patches on rough colloids are shown to be exclusively attractive due to their different overlap volumes. We discuss in detail the case of colloids with one patch that serves as a model for molecular surfactants both with respect to their geometry and their interactions. These one-patch particles assemble into clusters that resemble surfactant micelles with the smooth and attractive sides of the colloids located at the interior. We term these clusters "colloidal micelles". Direct Monte Carlo simulations starting from a homogeneous state give rise to cluster size distributions that are in good agreement with those found in experiments. Important differences with surfactant micelles originate from the colloidal character of our model system and are investigated by simulations and addressed theoretically. Our new "patchy" model system opens up the possibility for self-assembly studies into finite-sized superstructures as well as crystals with as of yet inaccessible structures.

Conformational changes of a single magnetic particle string within gels.

Magnetorheological (MR) gels consist of micron sized magnetic particles inside a gel matrix. Before physical cross-linking, the suspension is subjected to a small magnetic field which creates a particle string structure. After cross-linking, the string is kept within the gel at room temperature. Under an external homogeneous magnetic field and mechanical deformation, the soft swollen gel matrix allows the string to largely rearrange at microscopic scales. With the help of two homemade magneto cells mounted on an optical microscope, we were able to follow the conformational change and instabilities of a single magnetic particle string under the combined influence of shear (or stretch) and the magnetic field. In the absence of mechanical deformation, an external magnetic field, applied in the perpendicular direction to the string, breaks it into small pieces generating periodic structures like sawteeth. When an external magnetic field is applied parallel to the pre-aligned string, it exhibits a length contraction. However, under shear strain perpendicular to the original pre-structured string (and magnetic field), the string breaks and short string segments tilt, making an angle with the original direction that is smaller than that of the applied shear (non-affine). The difference in tilt angle scales with the inverse length of the small segments L-1 and the magnetic flux density B, reflecting the ability of the gel matrix to expel solvents under local stress.

Deformation of confined liquid interfaces by inhomogeneous electric fields and localized particle forces.

HYPOTHESIS: Oil-water interfaces that are created by confining a certain amount of oil in a square shaped pixel (∼200 x 200 µm2 with a height of ∼10 µm) topped by a layer of water, have a curvature that depends on the amount of oil that happens to be present in the confining area. Under the application of an electric field normal to the interface, the interface will deform due to inhomogeneities in the electric field. These inhomogeneities are expected to arise from the initial curvature of the meniscus, from fringe fields that emerge at the confining pixel walls and, if applicable, from interfacially adsorbed particles. MODELING AND EXPERIMENTS: We model the shape of the confined oil-water interface invoking capillarity and electrostatics. Furthermore, we measure the initial curvature by tracking the position of interfacially adsorbed particles depending on sample tilt. FINDINGS: We found that the pixels exhibited meniscus curvature radii ranging from 0.6-7 mm. The corresponding model based minimum oil film thicknesses range between 0.7 and 9 µm. Furthermore, the model shows that the initial meniscus curvature can increase up to 76 percent relative to the initial curvature by the electric field before the oil film becomes unstable. The pixel wall and particles are shown to have minimal impact on the interface deformation.

Interplay of electrokinetic effects in nonpolar solvents for electronic paper displays.

HYPOTHESIS: Electronic paper displays rely on electrokinetic effects in nonpolar solvents to drive the displacement of colloidal particles within a fluidic cell. While Electrophoresis (EP) is a well-established and frequently employed phenomenon, electro-osmosis (EO), which drives fluid flow along charged solid surfaces, has not been studied as extensively. We hypothesize that by exploiting the interplay between these effects, an enhanced particle transport can be achieved. EXPERIMENTS: In this study, we experimentally investigate the combined effects of EP and EO for colloidal particles in non-polar solvents, driven by an electric field. We use astigmatism micro-particle tracking velocimetry (A-µPTV) to measure the motion of charged particles within model fluidic cells. Using a simple approach that relies on basic fluid flow properties we extract the contributions due to EP and EO, finding that EO contributes significantly to particle transport. The validity of our approach is confirmed by measurements on particles with different magnitudes of charge, and by comparison to numerical simulations. FINDINGS: We find that EO flows can play a dominant role in the transport of particles in electrokinetic display devices. This can be exploited to speed up particle transport, potentially yielding displays with significantly faster switching times.

An Edible Humidity Indicator That Responds to Changes in Humidity Mechanically.

Elevated humidity levels in medical, food, and pharmaceutical products may reduce the products' shelf life, trigger bacterial growth, and even lead to complete spoilage. In this study, we report a humidity indicator that mechanically bends and rolls itself irreversibly upon exposure to high humidity conditions. The indicator is made of two food-grade polymer films with distinct ratios of a milk protein, casein, and a plasticizer, glycerol, that are physically attached to each other. Based on the thermogravimetric analysis and microstructural characterization, we hypothesize that the bending mechanism is a result of hygroscopic swelling and consequent counter diffusion of water and glycerol. Guided by this mechanism, we demonstrate that the rolling behavior, including response time and final curvature, can be tuned by the geometric dimensions of the indicator. As the proposed indicator is made of food-grade ingredients, it can be placed directly in contact with perishable products to report exposure to undesirable humidity inside the package, without the risk of contaminating the product or causing oral toxicity in case of accidental digestion, features that commercial inedible electronic and chemo-chromatic sensors cannot provide presently.

Sheet-like assemblies of spherical particles with point-symmetrical patches.

We report a computational study on the spontaneous self-assembly of spherical particles into two-dimensional crystals. The experimental observation of such structures stabilized by spherical objects appeared paradoxical so far. We implement patchy interactions with the patches point-symmetrically (icosahedral and cubic) arranged on the surface of the particle. In these conditions, preference for self-assembly into sheet-like structures is observed. We explain our findings in terms of the inherent symmetry of the patches and the competition between binding energy and vibrational entropy. The simulation results explain why hollow spherical shells observed in some Keplerate-type polyoxometalates (POM) appear. Our results also provide an explanation for the experimentally observed layer-by-layer growth of apoferritin--a quasi-spherical protein.

Photoresponsive Hydrogel Microcrawlers Exploit Friction Hysteresis to Crawl by Reciprocal Actuation.

Mimicking the locomotive abilities of living organisms on the microscale, where the downsizing of rigid parts and circuitry presents inherent problems, is a complex feat. In nature, many soft-bodied organisms (inchworm, leech) have evolved simple, yet efficient locomotion strategies in which reciprocal actuation cycles synchronize with spatiotemporal modulation of friction between their bodies and environment. We developed microscopic (∼100 µm) hydrogel crawlers that move in aqueous environment through spatiotemporal modulation of the friction between their bodies and the substrate. Thermo-responsive poly-n-isopropyl acrylamide hydrogels loaded with gold nanoparticles shrink locally and reversibly when heated photothermally with laser light. The out-of-equilibrium collapse and reswelling of the hydrogel is responsible for asymmetric changes in the friction between the actuating section of the crawler and the substrate. This friction hysteresis, together with off-centered irradiation, results in directional motion of the crawler. We developed a model that predicts the order of magnitude of the crawler motion (within 50%) and agrees with the observed experimental trends. Crawler trajectories can be controlled enabling applications of the crawler as micromanipulator that can push small cargo along a surface.

Oil Conductivity, Electric-Field-Induced Interfacial Charge Effects, and Their Influence on the Electro-Optical Response of Electrowetting Display Devices.

A pixel in an electrowetting display (EWD) can be viewed as a confined water/oil two-phase microfluidic system that can be manipulated by applying an electric field. The phenomenon of charge trapping in the protective dielectric and conductivity of the oil phase reduce the effective electric field that is required to keep the three-phase contact line (TCL) in place. This probably leads to an oil-backflow effect which deteriorates the electro-optical performance of EWD devices. In order to investigate charge trapping and conduction effects on the device electro-optical response, an EWD device was studied, which was fabricated with a black oil, aiming for a high-contrast ratio and color-filter display. For comparison, we also prepared a device containing a purple oil, which had a lower electrical conductivity. As anticipated, the black-oil device showed faster backflow than the purple-oil device. A simple model was proposed to explain the role of oil conductivity in the backflow effect. In addition, the rebound and reopening effects were also observed after the voltage was switched to zero. The above observations were strongly dependent on polarity. By combining observations of the polarity dependence of the oil conductivity and assuming that negative charges trap more strongly in the dielectric than positive charges, our experimental results on rebound and reopening can be explained. In the AC optical response, the pixel closing speed decreased in time for intermediate frequencies. This is likely related to the phenomenon of charge trapping. It was also found that the periodic driving method could not suppress the backflow effect when the driving frequency was above ~10 kHz. Our findings confirm the significance of the above charge-related effects of EWD devices, which need to be investigated further for better understanding in order to properly design/use materials and driving schemes to suppress them.

Approximately symmetric electrowetting on an oil-lubricated surface.

As the most widely used insulator materials in the electrowetting (EW) systems, amorphous fluoropolymers (AFs) provide excellent hydrophobicity, dielectric properties and chemical inertness; however, they suffer from charge trapping during electrowetting with water and the consequent asymmetric phenomenon. In this study, an ultra-thin oil-lubricated AF surface was proposed to release the charge trapping in the dielectric layer and further suppress the polarity-dependent asymmetry during electrowetting. The negative spontaneously trapped charges gathering on the dielectric/water interface with aging time were characterized by various measurements and calculations, which explained the polarity dependence of the asymmetric electrowetting. Approximately symmetric EW curves withstanding water aging were obtained for the oil-lubricated AF surface, confirming the blocking effect on charge trapping induced by the lubricated surface. The improved reversibility of EW with low contact angle hysteresis brought by the oil-lubricated surface was also demonstrated. This study reveals the mechanism behind the asymmetric EW phenomenon and offers an attractive oil-lubricated EW material system for suppressing the charge trapping on the dielectric/water interface, which can significantly improve the manipulation of the EW devices.

Field-Induced Wettability Gradients for No-Loss Transport of Oil Droplets on Slippery Surfaces.

Transporting oil droplets is crucial for a wide range of industrial and biomedical applications but remains highly challenging due to the large contact angle hysteresis on most solid surfaces. A liquid-infused slippery surface has a low hysteresis contact angle and is a highly promising platform if sufficient wettability gradient can be created. Current strategies used to create wettability gradient typically rely on the engineering of the chemical composition or geometrical structure. However, these strategies are inefficient on a slippery surface because the infused liquid tends to conceal the gradient in the chemical composition and small-scale geometrical structure. Magnifying the structure, on the other hand, will significantly distort the surface topography, which is unwanted in practice. In this study, we address this challenge by introducing a field-induced wettability gradient on a flat slippery surface. By printing radial electrodes array, we can pattern the electric field, which induces gradient contact angles. Theoretical analysis and experimental results reveal that the droplet transport behavior can be captured by a nondimensional electric Bond number. Our surface enables no-loss transport of various types of droplets, which we expect to find important applications such as heat transfer, anticontamination, microfluidics, and biochemical analysis.

Predator-prey interactions between droplets driven by non-reciprocal oil exchange.

Chemotactic interactions are ubiquitous in nature and can lead to non-reciprocal and complex emergent behaviour in multibody systems. However, developing synthetic, inanimate embodiments of a chemomechanical framework to generate non-reciprocal interactions of tunable strength and directionality has been challenging. Here we show how chemotactic signalling between microscale oil droplets of different chemistries in micellar surfactant solutions can result in predator-prey-like non-reciprocal chasing interactions. The interactions and dynamic self-organization result from the net directional, micelle-mediated transport of oil between emulsion droplets of differing composition and are powered by the free energy of mixing. We systematically elucidated chemical design rules to tune the interactions between droplets by varying the oil and surfactant chemical structure and concentration. Through the integration of experiment and simulation, we also investigated the active behaviour and dynamic reorganization of multidroplet clusters. Our findings demonstrate how chemically minimal systems can be designed with controllable, non-reciprocal chemotactic interactions to generate emergent self-organization and collective behaviours reminiscent of biological systems.

Ultracentrifugation of single-domain magnetite particles and the De Gennes-Pincus approach to ferromagnetic colloids in the dilute regime.

We report an analytical ultracentrifugation study on sedimentation in dilute stable dispersions of uniform, magnetic iron oxide (Fe3O4) colloids. On increase of the dipolar coupling constant, tuned by the average particle size, the linear concentration dependence of the sedimentation velocity shows an abrupt transition from the hindered sedimentation expected for hard spheres to a marked acceleration already for weak dipolar interactions. This transition is not reproduced by sedimentation theory derived from an effective, isotropic pair correlation function of the type proposed by De Gennes and Pincus, for reasons which are made clear. Accelerated settling, instead, follows a scaling based on the mass action law for dimer formation with dipoles in head-to-tail configuration. Our work illustrates that orientational averaging of dipole interactions of ferromagnetic colloids in the dilute regime is inapplicable, with an obvious implication for the possible existence of isotropic gas-liquid criticality for such colloids.