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Thomas Palberg

Publications and source records attributed to Thomas Palberg.

At least 19 recordsLinked to original sources

Active particles in tunable compressible environments

Active particles affect their environment as much as the environment affects their active motion. Here, we present an experimental system where both can be simultaneously adjusted in situ using an external AC electric field. The environment consists in a two-dimensional bath of colloidal silica particles, whereas the active particles are gold-coated Janus spheres. As the electric field orthogonal to the planar layer increases, the former become stiffer and the latter become faster. The active trajectories exhibit enhanced rotational motion where the reorientation frequency increases with the particle speed, an effect that culminates in a chiral active motion. We demonstrate that self sustained reorientations arise from local compressions and interaction asymmetries, revealing a general particle-level mechanism where changes in the mechanical properties of the environment reshape active trajectories.

cond-mat.soft

CO2-induced Drastic Decharging of Dielectric Surfaces in Aqueous Suspensions

We study the influence of airborne CO2 on the charge state of carboxylate stabilized polymer latex particles suspended in aqueous electrolytes. We combine conductometric experiments interpreted in terms of Hessinger's conductivity model with Poisson-Boltzmann cell (PBC) model calculations with charge regulation boundary conditions. Without CO2, a minority of the weakly acidic surface groups are dissociated and only a fraction of the total number of counter-ions actually contribute to conductivity. The remaining counter-ions exchange freely with added other ions like Na+, K+ or Cs+. From the PBC-calculations we infer a corresponding pKa of 4.26 as well as a renormalized charge in reasonably good agreement with the number of freely mobile counter-ions. Equilibration of salt- and CO2-free suspensions against ambient air leads to a drastic de-charging, which exceeds by far the expected effects of to dissolved CO2 and its dissociation products. Further, no counter-ion-exchange is observed. To reproduce the experimental findings, we have to assume an effective pKa of 6.48. This direct influence of CO2 on the state of surface group dissociation explains our recent finding of a CO2-induced decrease of the {\zeta}-potential and supports the suggestion of an additional charge regulation caused by molecular CO2. Given the importance of charged surfaces in contact with aqueous electrolytes, we anticipate that our observations bear substantial theoretical challenges and important implications for applications ranging from desalination to bio-membranes.

cond-mat.soft

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 deep 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 densi-ty determination in turbid crystals.

cond-mat.soft

Writing in 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. We here demonstrate 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, we roll an ion-exchange bead (pen) 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 to draw and write. We complement our experiments 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, our approach opens a versatile route for writing, drawing, and patterning fluids - even at the micro-scale.

cond-mat.soft

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

The kinetics of phase transition processes often governs the resulting material microstruc-ture. Using optical microscopy, we here investigate the formation and stabilization of a po-rous 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 indi-vidual, compositionally refined crystallites of perforated morphology coexisting with an ag-gregate-enriched fluid phase filling the holes and separating individual crystallites. A prelimi-nary 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 melt-ing 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.

cond-mat.soft

Charging of dielectric surfaces in contact with aqueous electrolyte -- the influence of CO$_2$

The charge state of dielectric surfaces in aqueous environments is of fundamental and technological importance. Here, we study the influence of dissolved molecular CO$_2$ on the charging of three, chemically different surfaces (SiO$_2$, Polystyrene, Perfluorooctadecyltrichlorosilane). We determine their charge state from electrokinetic experiments. We compare an ideal, CO$_2$-free reference system to a system equilibrated against ambient CO$_2$ conditions. In the reference system, the salt-dependence is weakened for SiO$_2$ and inverted for the organic surfaces. We show that screening and pH-driven charge regulation alone cannot explain the observed effects. As additional cause, we tentatively suggest dielectric regulation of surface charges due to a diffusively adsorbed thin layer of molecular CO$_2$. 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.

cond-mat.soft

Island Hopping of active colloids

Individual self-propelled colloidal particles, like active Brownian particles (ABP) or run-and-tumble swimmers (RT), 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) actuated by AC electric fields and suspended and cruising through silica particles organized in rafts by mutual phoretic attraction. A typical island contains dozens of particles. The JP travels straight in obstacle-free regions and reorients systematically upon approaching an island. As an underlying mechanism, we tentatively propose a hydrodynamic torque exerted by the solvent flow towards the islands on the JP local flow field, leading to an alignment of respective solvent flow directions. This systematic behavior is in contrast with the reorientation observed for free active Brownian particles and run-and-tumble microswimmers.

cond-mat.soft

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

We study low-salt, binary aqueous suspensions of charged colloidal spheres of size ratio Phi = 0.57, number densities below the eutectic number density n_E, and number fractions of p = 1.00-0.40. The typical phase obtained by solidification from a homogeneous shear-melt is a substitutional alloy of body centred cubic structure. In strictly gas-tight vials, the polycrystalline solid is stable against melting and further phase transformation for extended times. For comparison, we prepare the same samples also by slow and 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 beta-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 in slit cells is not volume-filling, and we now observe also alpha- and beta-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 subsequent increase in salt concentration, crystals melt again. Wall-based, pebble-shaped beta-phase crystals and facetted alpha-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.

cond-mat.soft

Peaked bulk crystal nucleation in charged sphere melts from salt concentration dependent crystallization experiments at very low metastability

We determined bulk crystal nucleation rates in aqueous suspensions of charged spheres at low metastability. Experiments were performed in dependence on electrolyte concen-tration and for two different particle number densities. The time-dependent nucleation rate shows a pronounced initial peak, while post-solidification crystal size distributions are skewed towards larger crystallite sizes. At each concentration, the nucleation rate density initially drops exponentially with increasing salt concentration. The complete data set, however, shows an unexpected scaling of the nucleation rate densities with met-astability times the number density of particles. Parameterization of our results in terms of Classical Nucleation Theory reveals unusually low interfacial free energies of the nu-cleus surfaces and nucleation barriers well below the thermal energy. We tentatively attribute our observations to the presence of doublets introduced by the employed con-ditioning technique and acting as nucleation seeds.

cond-mat.soft

Characterization of active matter in dense suspensions with heterodyne laser Doppler velocimetry

We present a novel approach for characterizing the properties and performance of active matter in dilute suspension as well as in crowded environments. We use Super-Heterodyne Laser-Doppler-Velocimetry (SH-LDV) to study large ensembles of catalytically active Janus particles moving under UV-illumination. SH-LDV facilitates a model-free determination of the swimming speed and direction, with excellent ensemble averaging. In addition we obtain in-formation on the distribution of the catalytic activity. Moreover, SH-LDV operates away from walls and permits a facile correction for multiple scattering contributions. It thus allows for stud-ies of concentrated suspensions of swimmers or of systems where swimmers propel actively in an environment crowded by passive particles. We demonstrate the versatility and the scope of the method with a few selected examples. We anticipate that SH-LDV complements estab-lished methods and paves the way for systematic measurements at previously inaccessible boundary conditions.

cond-mat.soft

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 opti-cally accessible range of concentrations in experiments on colloidal electro-kinetics. We here meas-ured 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 con-centration dependence of the mobility for a single particle species. Our observations reconcile previ-ous experimental observations made on other species over restricted concentration ranges. We com-pare our results to state of the art theoretical calculations using a constant particle charge and the carefully determined experimental boundary conditions as input. In particular, we consider so-called realistic salt free conditions, i.e. we respect the release of counter-ions by the particles, the solvent hydrolysis and the formation of carbonic acid from dissolved neutral CO2. We also compare to previ-ous results obtained under similarly well-defined conditions. This allows identification of three dis-tinct regions of differing density dependence. An ascent during the built 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 of particle charge, and we tentatively discuss possibly underlying mechanisms.

cond-mat.soft

Demonstration of variable angle Super-Heterodyne Dynamic Light Scattering for measuring colloidal dynamics

We demonstrate a prototype light scattering instrument combining a frequency domain approach to the intermediate scattering function from Super-Heterodyning Doppler Velocimetry with the versatility of a standard homodyne Dynamic Light Scattering goniometer setup for investigations over a large range of scattering vectors. Comparing to reference experiments in correlation-time domain, we show that the novel approach can determine diffusion constants and hence hydrodynamic radii with high precision and accuracy. Possible future applications are discussed shortly.

cond-mat.soft

Unraveling Modular Microswimmers: From Self-Assembly to Ion-Exchange Driven Motors

Active systems contain self-propelled particles and can spontaneously self-organize into patterns making them attractive candidates for the self-assembly of smart soft materials. One key limitation of our present understanding of these materials hinges on the complexity of the microscopic mechanisms driving its components forward. Here, by combining experiments, analytical theory and simulations we explore such a mechanism for a class of active system, modular microswimmers, which self-assemble from colloids and ion-exchange resins on charged substrates. Our results unveil the self-assembly processes and the working mechanism of the ion-exchange driven motors underlying modular microswimmers, which have so far been illusive, even qualitatively. We apply these motors to show that modular microswimmers can circumvent corners in complex environments and move uphill. Our work closes a central knowledge gap in modular microswimmers and provides a facile route to extract mechanical energy from ion-exchange processes.

cond-mat.soft

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. 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 microfluidic pumping experiment involving an inhomogeneous electric field and a complex solvent flow pattern.

cond-mat.soft

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.

cond-mat.soft

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. This 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.

cond-mat.soft

Formation of a transient amorphous solid in low density aqueous charged sphere suspensions

Colloidal glasses form from hard spheres, nearly hard spheres, ellipsoids and platelets or their attractive variants have been studied in detail. Complementing and checking theoretical approaches and simulations, the many different types of model systems have significantly advanced our understanding of the glass transition in general. Despite their early prediction, however, no experimental charged sphere glasses have been found at low density, where the competing process of crystallization prevails. We here report the formation of a transient amorphous solid formed from charged polymer spheres suspended in thoroughly deionized water at volume fractions of 0.0002-0.01. From optical experiments, we observe the presence of short-range order and an enhanced shear rigidity as compared to the stable polycrystalline solid of body centred cubic structure. On a density dependent time scale of hours to days, the amorphous solid transforms into this stable structure. We further present preliminary dynamic light scattering data showing the evolution of a second slow relaxation process possibly pointing to a dynamic heterogeneity known from other colloidal glasses and gels.We compare our findings to the predicted phase behaviour of charged sphere suspensions and discuss possible mechanisms for the formation of this peculiar type of colloidal glass.

cond-mat.soft

Large scale Micro-Photometry for high resolution pH-characterization during electro-osmotic pumping and modular micro-swimming

Micro-fluidic pumps as well as artificial micro-swimmers are conveniently realized exploiting phoretic solvent flows based on local gradients of temperature, electrolyte concentration or pH. We here present a facile micro-photometric method for monitoring pH gradients and demonstrate its performance and scope on different experimental situations including an electro-osmotic pump and modular micro-swimmers assembled from ion exchange resin beads and polystyrene colloids. In combination with the present microscope and DSLR camera our method offers a 2 μm spatial resolution at video frame rate over a field of view of 3920x2602 μm^2. Under optimal conditions we achieve a pH-resolution of 0.05 with about equal contributions from statistical and systematical uncertainties. Our quantitative micro-photometric characterization of pH gradients which develop in time and reach out several mm is anticipated to provide valuable input for reliable modeling and simulations of a large variety of complex flow situations involving pH-gradients including artificial micro-swimmers, microfluidic pumping or even electro-convection.

cond-mat.soft