Accessing the free expansion of a crystalline colloidal drop by optical experiments.

We study poly-crystalline spherical drops of an aqueous suspension of highly charged colloidal spheres exposed to a colloid-free aqueous environment. Crystal contours were obtained from standard optical imaging. The crystal spheres first expand to nearly four times their initial volume before slowly shrinking due to dilution-induced melting. Exploiting coherent multiple-scattering by (110) Bragg reflecting crystals, time-dependent density profiles were recorded within the drop interior. These show a continuously flattening radial density gradient and a decreasing central density. Expansion curves and density profiles are qualitatively consistent with theoretical expectations based on dynamical density functional theory for the expansion of a spherical crystallite made of charged Brownian spheres. We anticipate that our study opens novel experimental access to density determination in turbid crystals.

Writing Into Water.

Writing is an ancient communication technique dating back at least 30 000 years. While even sophisticated contemporary writing techniques hinge on solid surfaces for engraving or the deposition of ink, writing within a liquid medium requires a fundamentally different approach. The study here demonstrates the writing of lines, letters, and complex patterns in water by assembling lines of colloidal particles. Unlike established techniques for underwater writing on solid substrates, these lines are fully reconfigurable and do not require any fixation onto the substrate. Exploiting gravity, an ion-exchange bead (pen) is rolled across a layer of sedimented colloidal particles (ink). The pen evokes a hydrodynamic flow collecting ink-particles into a durable, high-contrast line along its trajectory. Deliberate substrate-tilting sequences facilitate pen-steering and thus drawing and writing. The experiments are complemented with a minimal model that quantitatively predicts the observed parameter dependence for writing in fluids and highlights the generic character of writing by line-assembly. Overall, the approach opens a versatile route for writing, drawing, and patterning fluids-even at the micro-scale.

Weak Ion-Exchange Based Magnetic Swarm for Targeted Drug Delivery and Chemotherapy.

Swimming microrobots that are actuated by multiple stimuli/fields display various intriguing collective behaviors, ranging from phase separation to clustering and giant number fluctuation; however, it is still chanllenging to achieve multiple responses and functionalities within one colloidal system to emulate high environmental adaptability and improved tasking capability of natural swarms. In this work, a weak ion-exchange based swarm is presented that can self-organize and reconfigure by chemical, light, and magnetic fields, showing living crystal, amorphous glass, liquid, chain, and wheel-like structures. By changing the frequency and strength of the rotating magnetic field, various well-controlled and fast transformations are obtained. Experiments show the high adaptability and functionality of the microrobot swarm in delivering drugs in confined spaces, such as narrow channels with turns or obstacles. The drug-carrying swarm exhibits excellent chemtherapy for Hela and CT26 cells due to the pH-enhanced drug release and locomotion. This reconfigurable microswarm provides a new platform for biomedical and environmental applications.

Porous crystals in charged sphere suspensions by aggregate-driven phase separation.

The kinetics of phase transition processes often governs the resulting material microstructure. Using optical microscopy, we here investigate the formation and stabilization of a porous crystalline microstructure forming in low-salt suspensions of charged colloidal spheres containing aggregates comprising some 5-10 of these colloids. We observe the transformation of an initially crystalline colloidal solid with homogeneously incorporated aggregates to individual, compositionally refined crystallites of perforated morphology coexisting with an aggregate-enriched fluid phase filling the holes and separating individual crystallites. A preliminary kinetic characterization suggests that the involved processes follow power laws. We show that this route to porous materials is neither restricted to nominally single component systems nor to a particular microstructure to start from. However, it necessitates an early rapid solidification stage during which the aggregates become trapped in the bulk of the host-crystals. The thermodynamic stability of the reconstructed crystalline scaffold against melting under increased salinity was found comparable to that of pure phase crystallites grown very slowly from a melt. Future implications of this novel route to porous colloidal crystals are discussed.

Island hopping of active colloids.

Individual self-propelled colloidal particles, like active Brownian particles (ABP) or run-and-tumble (RT) swimmers, exhibit characteristic and well-known motion patterns. However, their interaction with obstacles remains an open and important problem. We here investigate the two-dimensional motion of silica-gold Janus particles (JP) suspended in a bath of smaller silica passive particles. Actuated by AC electric fields, the JP cruise through passive colloids organized in 'islands' due to attractive electrohydrodynamic (EHD) flows. A typical island contains dozens of particles. The JP travels straight in obstacle-free regions and reorients abruptly upon collision with an island. As an underlying mechanism, we propose that the scattering events are caused by the interplay of EHD flows, self-propulsion and local torques. The combination of directed motion and sudden reorientations leads to active trajectories resembling the RT behavior of biological microswimmers.

Microstructural diversity, nucleation paths, and phase behavior in binary mixtures of charged colloidal spheres.

We study low-salt, binary aqueous suspensions of charged colloidal spheres of size ratio Γ = 0.57, number densities below the eutectic number density nE, and number fractions of p = 1.00-0.40. The typical phase obtained by solidification from a homogeneous shear-melt is a substitutional alloy with a body centered cubic structure. In strictly gas-tight vials, the polycrystalline solid is stable against melting and further phase transformation for extended times. For comparison, we also prepare the same samples by slow, mechanically undisturbed deionization in commercial slit cells. These cells feature a complex but well reproducible sequence of global and local gradients in salt concentration, number density, and composition as induced by successive deionization, phoretic transport, and differential settling of the components, respectively. Moreover, they provide an extended bottom surface suitable for heterogeneous nucleation of the ß-phase. We give a detailed qualitative characterization of the crystallization processes using imaging and optical microscopy. By contrast to the bulk samples, the initial alloy formation is not volume-filling, and we now observe also α- and ß-phases with low solubility of the odd component. In addition to the initial homogeneous nucleation route, the interplay of gradients opens various further crystallization and transformation pathways leading to a great diversity of microstructures. Upon a subsequent increase in salt concentration, the crystals melt again. Wall-based, pebble-shaped ß-phase crystals and facetted α-crystals melt last. Our observations suggest that the substitutional alloys formed in bulk experiments by homogeneous nucleation and subsequent growth are mechanically stable in the absence of solid-fluid interfaces but thermodynamically metastable.

Charging of Dielectric Surfaces in Contact with Aqueous Electrolytes─the Influence of CO2.

The charge state of dielectric surfaces in aqueous environments is of fundamental and technological importance. Here, we study the influence of dissolved molecular CO2 on the charging of three chemically different surfaces (SiO2, Polystyrene, Perfluorooctadecyltrichlorosilane). We determine their charge state from electrokinetic experiments. We compare an ideal, CO2-free reference system to a system equilibrated against ambient CO2 conditions. In the reference system, the salt-dependent decrease of the magnitudes of ζ-potentials follows the expectations for a constant charge scenario. In the presence of CO2, the starting potential is lower by some 50%. The following salt-dependent decrease is weakened for SiO2 and inverted for the organic surfaces. We show that screening and pH-driven charge regulation alone cannot explain the observed effects. As an additional cause, we tentatively suggest dielectric regulation of surface charges due to a diffusively adsorbed thin layer of molecular CO2. The formation of such a dynamic layer, even at the hydrophilic and partially ionized silica surfaces, is supported by a minimal theoretical model and results from molecular simulations.

Shaping the gradients driving phoretic micro-swimmers: influence of swimming speed, budget of carbonic acid and environment.

pH gradient-driven modular micro-swimmers are investigated as a model for a large variety of quasi-two-dimensional chemi-phoretic self-propelled entities. Using three-channel micro-photometry, we obtain a precise large field mapping of pH at a spatial resolution of a few microns and a pH resolution of [Formula: see text] units for swimmers of different velocities propelling on two differently charged substrates. We model our results in terms of solutions of the three-dimensional advection-diffusion equation for a 1:1 electrolyte, i.e. carbonic acid, which is produced by ion exchange and consumed by equilibration with dissolved [Formula: see text]. We demonstrate the dependence of gradient shape and steepness on swimmer speed, diffusivity of chemicals, as well as the fuel budget. Moreover, we experimentally observe a subtle, but significant feedback of the swimmer's immediate environment in terms of a substrate charge-mediated solvent convection. We discuss our findings in view of different recent results from other micro-fluidic or active matter investigations. We anticipate that they are relevant for quantitative modelling and targeted applications of diffusio-phoretic flows in general and artificial micro-swimmers in particular.

Non-monotonic concentration dependence of the electro-phoretic mobility of charged spheres in realistic salt free suspensions.

Using super-heterodyne Doppler velocimetry with multiple scattering correction, we extend the optically accessible range of concentrations in experiments on colloidal electro-kinetics. Here, we measured the electro-phoretic mobility and the DC conductivity of aqueous charged sphere suspensions covering about three orders of magnitude in particle concentrations and transmissions as low as 40%. The extended concentration range for the first time allows the demonstration of a non-monotonic concentration dependence of the mobility for a single particle species. Our observations reconcile previous experimental observations made on other species over restricted concentration ranges. We compare our results to the state-of-the-art theoretical calculations using a constant particle charge and the carefully determined experimental boundary conditions as input. In particular, we consider the so-called realistic salt free conditions, i.e., we respect the release of counterions by the particles, the solvent hydrolysis, and the formation of carbonic acid from dissolved neutral CO2. We also compare our results to previous results obtained under similarly well-defined conditions. This allows identification of three distinct regions of differing density dependence. There is an ascent during the build-up of double layer overlap, which is not expected by theory, an extended plateau region in quantitative agreement with theoretical expectation based on a constant effective charge and a sudden decrease, which occurs way before the expected gradual decrease. Our observations suggest a relation of the non-monotonic behavior to a decrease in particle charge, and we tentatively discuss possibly underlying mechanisms.

Modular approach to microswimming.

The field of active matter in general and microswimming in particular has experienced a rapid and ongoing expansion over the last decade. A particular interesting aspect is provided by artificial autonomous microswimmers constructed from individual active and inactive functional components into self-propelling complexes. Such modular microswimmers may exhibit directed motion not seen for each individual component. In this review, we focus on the establishment and recent developments in the modular approach to microswimming. We introduce the bound and dynamic prototypes, show mechanisms and types of modular swimming and discuss approaches to control the direction and speed of modular microswimmers. We conclude by highlighting some challenges faced by researchers as well as promising directions for future research in the realm of modular swimming.

Correction: Seedless assembly of colloidal crystals by inverted micro-fluidic pumping.

Correction for 'Seedless assembly of colloidal crystals by inverted micro-fluidic pumping' by Ran Niu et al., Soft Matter, 2018, 14, 3435-3442.

Seedless assembly of colloidal crystals by inverted micro-fluidic pumping.

We propose a simple seedless approach to assemble millimeter sized monolayer single colloidal crystals with desired orientations at predetermined locations on an unstructured charged substrate. This approach utilizes the millimeter-ranged fluid flow on the bottom glass substrate induced by an ion exchange resin (IEX) fixed on top of the closed sample cell. The fluid flow increases with decreasing height of the sample cell and increasing radius R of the IEX. For a single inverted pump, millimeter sized monolayer single crystals of hexagonal close packing can be obtained. For two closely spaced (D ∼ 4R) pumps, the formed crystals have a predefined orientation along the line connecting the two IEX. By patterning IEX into different structures, colloidal crystals of different complex patterns form. The present method paves a convenient way for fabricating high quality monolayer colloidal crystals for a variety of applications.

Colloidal electro-phoresis in the presence of symmetric and asymmetric electro-osmotic flow.

We characterize the electro-phoretic motion of charged sphere suspensions in the presence of substantial electro-osmotic flow using a recently introduced small angle super-heterodyne dynamic light scattering instrument (ISASH-LDV). Operation in integral mode gives access to the particle velocity distribution over the complete cell cross-section. Obtained Doppler spectra are evaluated for electro-phoretic mobility, wall electro-osmotic mobility and particle diffusion coefficient. Simultaneous measurements of differing electro-osmotic mobilities leading to asymmetric solvent flow are demonstrated in a custom made electro-kinetic cell fitting standard microscopy slides as exchangeable sidewalls. The scope and range of our approach are discussed demonstrating the possibility of an internal calibration standard and using the simultaneously measured electro-kinetic mobilities in the interpretation of a microfluidic pumping experiment involving an inhomogeneous electric field and a complex solvent flow pattern.

Self-Assembly of Colloidal Molecules due to Self-Generated Flow.

The emergence of structure through aggregation is a fascinating topic and of both fundamental and practical interest. Here we demonstrate that self-generated solvent flow can be used to generate long-range attractions on the colloidal scale, with subpiconewton forces extending into the millimeter range. We observe a rich dynamic behavior with the formation and fusion of small clusters resembling molecules. The dynamics of this assembly is governed by an effective conservative energy that for large separations r decays as 1/r. Breaking the flow symmetry, these clusters can be made active.

Assembly and Speed in Ion-Exchange-Based Modular Phoretic Microswimmers.

We report an experimental study on ion-exchange-based modular microswimmers in low-salt water. Cationic ion-exchange particles and passive cargo particles assemble into self-propelling complexes, showing self-propulsion at speeds of several micrometers per second over extended distances and times. We quantify the assembly and speed of the complexes for different combinations of ion-exchange particles and cargo particles, substrate types, salt types and concentrations, and cell geometries. Irrespective of the experimental boundary conditions, we observe a regular development of the assembly shape with increasing number of cargo. Moreover, the swimming speed increases stepwise upon increasing the number of cargo and then saturates at a maximum speed, indicating the active role of cargo in modular swimming. We propose a geometric model of self-assembly to describe the experimental observations in a qualitative way. Our study also provides some constraints for future theoretical modeling and simulation.

Correction: Polymer-enforced crystallization of a eutectic binary hard sphere mixture.

Correction for 'Polymer-enforced crystallization of a eutectic binary hard sphere mixture' by Anna Kozina et al., Soft Matter, 2012, 8, 627-630.

Microfluidic pumping by micromolar salt concentrations.

An ion-exchange-resin-based microfluidic pump is introduced that utilizes trace amounts of ions to generate fluid flows. We show experimentally that our pump operates in almost deionized water for periods exceeding 24 h and induces fluid flows of µm s-1 over hundreds of µm. This flow displays a far-field, power-law decay which is characteristic of two-dimensional (2D) flow when the system is strongly confined and of three-dimensional (3D) flow when it is not. Using theory and numerical calculations we demonstrate that our observations are consistent with electroosmotic pumping driven by µmol L-1 ion concentrations in the sample cell that serve as 'fuel' to the pump. Our study thus reveals that trace amounts of charge carriers can produce surprisingly strong fluid flows; an insight that should benefit the design of a new class of microfluidic pumps that operate at very low fuel concentrations.

Controlled assembly of single colloidal crystals using electro-osmotic micro-pumps.

We assemble charged colloidal spheres at deliberately chosen locations on a charged unstructured glass substrate utilizing ion exchange based electro-osmotic micro-pumps. Using microscopy, a simple scaling theory and Brownian dynamics computer simulations, we systematically explore the control parameters of crystal assembly and the mechanisms through which they depend on the experimental boundary conditions. We demonstrate that crystal quality depends crucially on the assembly distance of the colloids. This is understood as resulting from the competition between inward transport by the electro-osmotic pump flow and the electro-phoretic outward motion of the colloids. Optimized conditions include substrates of low and colloids of large electro-kinetic mobility. Then a sorting of colloids by size is observed in binary mixtures with larger particles assembling closer to the ion exchanger beads. Moreover, mono-sized colloids form defect free single domain crystals which grow outside a colloid-free void with facetted inner crystal boundaries centered on the ion exchange particle. This works remarkably well, even with irregularly formed ion exchange resin splinters.

An empirical correction for moderate multiple scattering in super-heterodyne light scattering.

Frequency domain super-heterodyne laser light scattering is utilized in a low angle integral measurement configuration to determine flow and diffusion in charged sphere suspensions showing moderate to strong multiple scattering. We introduce an empirical correction to subtract the multiple scattering background and isolate the singly scattered light. We demonstrate the excellent feasibility of this simple approach for turbid suspensions of transmittance T ≥ 0.4. We study the particle concentration dependence of the electro-kinetic mobility in low salt aqueous suspension over an extended concentration regime and observe a maximum at intermediate concentrations. We further use our scheme for measurements of the self-diffusion coefficients in the fluid samples in the absence or presence of shear, as well as in polycrystalline samples during crystallization and coarsening. We discuss the scope and limits of our approach as well as possible future applications.

Overview: Experimental studies of crystal nucleation: Metals and colloids.

Crystallization is one of the most important phase transformations of first order. In the case of metals and alloys, the liquid phase is the parent phase of materials production. The conditions of the crystallization process control the as-solidified material in its chemical and physical properties. Nucleation initiates the crystallization of a liquid. It selects the crystallographic phase, stable or meta-stable. Its detailed knowledge is therefore mandatory for the design of materials. We present techniques of containerless processing for nucleation studies of metals and alloys. Experimental results demonstrate the power of these methods not only for crystal nucleation of stable solids but in particular also for investigations of crystal nucleation of metastable solids at extreme undercooling. This concerns the physical nature of heterogeneous versus homogeneous nucleation and nucleation of phases nucleated under non-equilibrium conditions. The results are analyzed within classical nucleation theory that defines the activation energy of homogeneous nucleation in terms of the interfacial energy and the difference of Gibbs free energies of solid and liquid. The interfacial energy acts as barrier for the nucleation process. Its experimental determination is difficult in the case of metals. In the second part of this work we therefore explore the potential of colloidal suspensions as model systems for the crystallization process. The nucleation process of colloids is observed in situ by optical observation and ultra-small angle X-ray diffraction using high intensity synchrotron radiation. It allows an unambiguous discrimination of homogeneous and heterogeneous nucleation as well as the determination of the interfacial free energy of the solid-liquid interface. Our results are used to construct Turnbull plots of colloids, which are discussed in relation to Turnbull plots of metals and support the hypothesis that colloids are useful model systems to investigate crystal nucleation.