Thermodynamically controlled multiphase separation of heterogeneous liquid crystal colloids.

Phase separation is a universal physical transition process whereby a homogeneous mixture splits into two distinct compartments that are driven by the component activity, elasticity, or compositions. In the current work, we develop a series of heterogeneous colloidal suspensions that exhibit both liquid-liquid phase separation of semiflexible binary polymers and liquid crystal phase separation of rigid, rod-like nanocellulose particles. The phase behavior of the multicomponent mixture is controlled by the trade-off between thermodynamics and kinetics during the two transition processes, displaying cholesteric self-assembly of nanocellulose within or across the compartmented aqueous phases. Upon thermodynamic control, two-, three-, and four-phase coexistence behaviors with rich liquid crystal stackings are realized. Among which, each relevant multiphase separation kinetics shows fundamentally different paths governed by nucleation and growth of polymer droplets and nanocellulose tactoids. Furthermore, a coupled multiphase transition can be realized by tuning the composition and the equilibrium temperature, which results in thermotropic behavior of polymers within a lyotropic liquid crystal matrix. Finally, upon drying, the multicomponent mixture undergoes a hierarchical self-assembly of nanocellulose and polymers into stratified cholesteric films, exhibiting compartmentalized polymer distribution and anisotropic microporous structure.

Magnetic Quincke rollers with tunable single-particle dynamics and collective states.

Electrohydrodynamically driven active particles based on Quincke rotation have quickly become an important model system for emergent collective behavior in nonequilibrium colloidal systems. Like most active particles, Quincke rollers are intrinsically nonmagnetic, preventing the use of magnetic fields to control their complex dynamics on the fly. Here, we report on magnetic Quincke rollers based on silica particles doped with superparamagnetic iron oxide nanoparticles. We show that their magnetic nature enables the application of both externally controllable forces and torques at high spatial and temporal precision, leading to several versatile control mechanisms for their single-particle dynamics and collective states. These include tunable interparticle interactions, potential energy landscapes, and advanced programmable and teleoperated behaviors, allowing us to discover and probe active chaining, anisotropic active sedimentation-diffusion equilibria, and collective states in various geometries and dimensionalities.

Magnetic field-driven particle assembly and jamming for bistable memory and response plasticity.

Unlike classic synthetic stimulus-responsive and shape-memory materials, which remain limited to fixed responses, the responses of living systems dynamically adapt based on the repetition, intensity, and history of stimuli. Such plasticity is ubiquitous in biology, which is profoundly linked to memory and learning. Concepts thereof are searched for rudimentary forms of "intelligent materials." Here, we show plasticity of electroconductivity in soft ferromagnetic nickel colloidal supraparticles with spiny surfaces, assembling/disassembling to granular conducting micropillars between two electrodes driven by magnetic field B. Colloidal jamming leads to conduction hysteresis and bistable memory upon increasing and subsequently decreasing B. Abrupt B changes induce larger conduction changes than gradual B-changes. Periodic B pulsing drives to frequency-dependent facilitation or suppression of conductivity compared to exposing the same constant field. The concepts allow remotely controlled switching plasticity, illustrated by a rudimentary device. More generally, we foresee adaptive functional materials inspired by response plasticity and learning.

Electroferrofluids with nonequilibrium voltage-controlled magnetism, diffuse interfaces, and patterns.

It has been recognized that driving matter to nonequilibrium states can lead to emergent behaviors and functionalities. Here, we show that uniform colloidal dispersions can be driven into dissipative nonuniform states with emerging behaviors. We experimentally demonstrate this with electrically driven weakly charged superparamagnetic iron oxide nanoparticles in a nonpolar solvent. The driving leads to formation of nonequilibrium concentration gradients that further translate to nonequilibrium magnetism, including voltage-controlled magnetization and susceptibility. The concentration gradients also serve as diffuse interfaces that respond to external magnetic fields, leading to novel dissipative patterns. We identify the closest nondissipative analogs, discuss the differences, and highlight the ability to directly quantify the dissipation and link it to the pattern formation. Beyond voltage-controlled magnetism, we foresee that the concept can be generalized to other functional colloids to create, e.g., optical, electrical, catalytic, and mechanical responses that are not possible in thermodynamic equilibrium.

Division of Ferrofluid Drops Induced by a Magnetic Field.

We report a comprehensive study of the division of ferrofluid drops caused by their interaction with a permanent magnet. As the magnet gradually approaches the sessile drop, the drop deforms into a spiked cone and then divides into two daughter droplets. This process is the result of a complex interplay between the polarizing effect caused by the magnetic field and the magnetic attraction due to the field gradient. As a first attempt to describe it, during each scan we identify two characteristic distances between the magnet and the drop: zmax, corresponding to the drop reaching its maximum height, and zsaddle, corresponding to the formation of a saddle point on the drop peak identifying the beginning of the drop breakup. We have investigated the location of these two points using sessile drops of ferrofluid water solutions at various concentrations and volumes, deposited on four surfaces of different wettability. An empirical scaling law based on dimensionless variables is found to accurately describe these experimental observations. We have also measured the maximum diameter of the drops right before the division and found that it is very close to a critical size, which depends on the magnetic attraction.

Static Magnetowetting of Ferrofluid Drops.

We report results of a comprehensive study of the wetting properties of sessile drops of ferrofluid water solutions at various concentrations deposited on flat substrates and subjected to the action of permanent magnets of different sizes and strengths. The amplitude and the gradient of the magnetic field experienced by the ferrofluid are changed by varying the magnets and their distance to the surface. Magnetic forces up to 100 times the gravitational one and magnetic gradients up to 1 T/cm are achieved. A rich phenomenology is observed, ranging from flattened drops caused by the magnetic attraction to drops extended normally to the substrate because of the normal traction of the magnetic field. We find that the former effect can be conveniently described in terms of an effective Bond number that compares the effective drop attraction with the capillary force, whereas the drop's vertical elongation is effectively expressed by a dimensionless number S, which compares the pressure jump at the ferrofluid interface because of the magnetization with the capillary pressure.