Geometric confinement strongly influences the behavior of microparticles in liquid environments. However, to date, nonspherical particle behaviors close to confining boundaries, even as simple as planar walls, remain largely unexplored. Here, we measure the height distribution and orientation of colloidal dumbbells above walls by means of digital in-line holographic microscopy. We find that while larger dumbbells are oriented almost parallel to the wall, smaller dumbbells of the same material are surprisingly oriented at preferred angles. We determine the total height-dependent force acting on the dumbbells by considering gravitational effects and electrostatic particle-wall interactions. Our modeling reveals that at specific heights both net forces and torques on the dumbbells are simultaneously below the thermal force and energy, respectively, which makes the observed orientations possible. Our results highlight the rich near-wall dynamics of nonspherical particles, and can further contribute to the development of quantitative frameworks for arbitrarily-shaped microparticle dynamics in confinement.
Impurity-induced defects play a crucial role for the properties of crystals, but little is known about impurities with anisotropic shape. Here, we study how colloidal dumbbells distort and interact with a hexagonal crystal of charged colloidal spheres at a fluid interface. We find that subtle changes in the dumbbell length induce a transition from a local distortion to a particle-bound dislocation, and determine how the dumbbell moves inside the repulsive hexagonal lattice. Our results provide new routes towards controlling material properties through particle-bound dislocations.
We investigate the nonequilibrium behavior of dense, plastic-crystalline suspensions of mildly anisotropic colloidal hard dumbbells under the action of an oscillatory shear field by employing Brownian dynamics computer simulations. In particular, we extend previous investigations, where we uncovered novel nonequilibrium phase transitions, to other aspect ratios and to a larger nonequilibrium parameter space, that is, a wider range of strains and shear frequencies. We compare and discuss selected results in the context of novel scattering and rheological experiments. Both simulations and experi…
We investigate the structure and equilibrium linear-response dynamics of suspensions of hard colloidal dumbbells using Brownian Dynamics computer simulations. The focus lies on the dense fluid and plastic crystal states of the colloids with investigated aspect (elongation-to-diameter) ratios varying from the hard sphere limit up to 0.39, which is roughly the stability limit of the plastic crystal phase. We find expected structural changes with larger elongation with respect to the hard sphere reference case and very localized orientational correlations, typically just involving next-neighbor c…
We investigate the behavior of a mixture of asymmetric colloidal dumbbells and emulsion droplets by means of kinetic Monte Carlo simulations. The evaporation of the droplets and the competition between droplet-colloid attraction and colloid-colloid interactions leads to the formation of clusters built up of colloid aggregates with both closed and open structures. We find that stable packings and hence complex colloidal structures can be obtained by changing the relative size of the colloidal spheres and/or their interfacial tension with the droplets.
We investigate thermodynamic properties of anisotropic colloidal dumbbells in the frameworks provided by the Reference Interaction Site Model (RISM) theory and an Optimized Perturbation Theory (OPT), this latter based on a fourth-order high-temperature perturbative expansion of the free energy, recently generalized to molecular fluids. Our model is constituted by two identical tangent hard spheres surrounded by square-well attractions with same widths and progressively different depths. Gas-liquid coexistence curves are obtained by predicting pressures, free energies, and chemical potentials. …
We employ Monte Carlo simulations to investigate the self-assembly of patchy colloidal dumbbells interacting via a modified Kern-Frenkel potential by probing the system concentration and dumbbell shape. We consider dumbbells consisting of one attractive sphere with diameter $σ_1$ and one repulsive sphere with diameter $σ_2$ and center-to-center distance $d$ between the spheres. For three different size ratios, we study the self-assembled structures for different separations $l = 2d/(σ_1+σ_2)$ between the two spheres. In particular, we focus on structures that can be assembled from the homogene…
We investigate thermodynamic and structural properties of colloidal dumbbells in the framework provided by the Reference Interaction Site Model (RISM) theory of molecular fluids and Monte Carlo simulations. We consider two different models: in the first one we set identical square-well attractions on the two tangent spheres composing the molecule (SW-SW model); in the second scheme, one of square-well interactions is switched off (HS-SW model). Appreciable differences emerge between the physical properties of the two models. Specifically, the $k \to 0$ behavior of SW-SW structure factors $S(k)…
We have recently investigated the phase behaviour of model colloidal dumbbells constituted by two identical tangent hard spheres, with the first one being surrounded by an attractive square-well interaction (Janus dumbbells, Munaò G et al 2014 Soft Matter 10 5269). Here we extend our previous analysis by introducing in the model the size asymmetry of the hard-core diameters, and study the enriched phase scenario thereby obtained. By employing standard Monte Carlo simulations we show that in such "heteronuclear Janus dumbbells" a larger hard-sphere site promotes the formation of clusters, where…
Using computer simulations we investigate the homogeneous crystal nucleation in suspensions of colloidal hard dumbbells. The free energy barriers are determined by Monte Carlo simulations using the umbrella sampling technique. We calculate the nucleation rates for the plastic crystal and the aperiodic crystal phase using the kinetic prefactor as determined from event driven molecular dynamics simulations. We find good agreement with the nucleation rates determined from spontaneous nucleation events observed in event driven molecular dynamics simulations within error bars of one order of magnit…
We fabricated thermoresponsive colloidal molecules of ca. 250 nm size. Electron- and scanning force microscopy reveal the dumbbell-shaped morphology. The temperature dependence of the size and aspect ratio (ca. 1.4 to 1.6) is analyzed by depolarized dynamic light scattering and found to be in good agreement with microscopic evidence.
The so-called 'raspberry' model refers to the hybrid lattice-Boltzmann and Langevin molecular dynamics scheme for simulating the dynamics of suspensions of colloidal particles, originally developed by [V. Lobaskin and B. Dünweg, New J. Phys. 6, 54 (2004)], wherein discrete surface points are used to achieve fluid-particle coupling. This technique has been used in many simulation studies on the behavior of colloids. However, there are fundamental questions with regards to the use of this model. In this paper, we examine the accuracy with which the raspberry method is able to reproduce Stokes-le…
From dumbbells to FCC crystals, we study the self-assembly pathway of amphiphatic, spherical colloidal particles as a function of the size of the hydrophobic region using molecular dynamics simulations. Specifically, we analyze how local inter-particle interactions correlate to the final self-assembled aggregate and how they affect the dynamical pathway of structure formation. We present a detailed diagram separating the many phases that we find for different sizes of the hydrophobic area, and uncover a narrow region where particles self-assemble into hollow, faceted cages that could potential…
Bulk phase separation is responsible for the occurrence of stacks of different layers in sedimentation of colloidal mixtures. A recently proposed theory (de las Heras and Schmidt 2013 Soft Matter 9 8636) establishes a unique connection between the bulk phase behaviour and sedimentation-diffusion-equilibrium. The theory constructs a stacking diagram of all possible sequences of stacks under gravity in the limit of very high (infinite) sample heights. Here, we study the stacking diagrams of colloidal mixtures at finite sample height, h. We demonstrate that h plays a vital role in sedimentation-d…
We consider anisotropic colloidal particles immersed in a solution of long, flexible, and nonadsorbing polymers. For the dumbbell shapes of recently synthesized particles consisting of two intersecting spheres and for lens-shaped particles with spherical surfaces we calculate the isotropic and anisotropic interaction parameters that determine the immersion free energy and the orientation-dependent depletion interaction between particles that are induced by the polymers. Exact results are obtained for random-walk like (ideal) polymer chains.
We study experimentally and theoretically the sedimentation of gels made of strongly aggregated colloidal particles, focussing on the long time behavior, when mechanical equilibrium is asymptotically reached. The asymptotic gel height is found to vary linearly with the initial height, a finding in stark contrast with a recent study on similar gels [Manley \textit{et al.} 2005 \textit{Phys. Rev. Lett.} \textbf{94} 218302]. We show that the asymptotic compaction results from the balance between gravity pull, network elasticity, and solid friction between the gel and the container walls. Based on…
We investigate theoretically the effect of gravity on a plate-sphere colloidal mixture by means of an Onsager-like density functional to describe the bulk, and sedimentation path theory to incorporate gravity. We calculate the stacking diagram of the mixture for two sets of buoyant masses and different values of the sample height. Several stacking sequences appear due to the intricate interplay between gravity, the sample height, and bulk phase separation. These include the experimentally observed floating nematic sequence, which consists of a nematic layer sandwiched between two isotropic lay…
A very recent observation on the membrane mediated attraction and ordered aggregation of colloidal particles bound to giant phospholipid vesicles (I. Koltover, J. O. Rädler, C. R. Safinya, Phys. Rev. Lett. {\bf 82}, 1991(1999)) is investigated theoretically within the frame of Helfrich curvature elasticity theory of lipid bilayer fluid membrane. Since the concave or waist regions of the vesicle possess the highest local bending energy density, the aggregation of colloidal beads on these places can reduce the elastic energy in maximum. Our calculation shows that a bead in the concave region low…
We study theoretically the effect of a gravitational field on the equilibrium behaviour of a colloidal suspension of rods with different length-to-width aspect ratios. The bulk phases of the system are described with analytical equations of state. The gravitational field is then incorporated via sedimentation path theory, which assumes a local equilibrium condition at each altitude of the sample. The bulk phenomenology is significantly enriched by the presence of the gravitational field. In a suspension of elongated rods with five stable phases in bulk, the gravitational field stabilizes up to…
Metastable gels formed by weakly attractive colloidal particles display a distinctive two-stage time-dependent settling behavior under their own weight. Initially a space-spanning network is formed that for a characteristic time, which we define as the lag time $\taud$, resists compaction. This solid-like behavior persists only for a limited time. Gels whose age $\tw$ is greater than $\taud$ yield and suddenly collapse. We use a combination of confocal microscopy, rheology and time-lapse video imaging to investigate both the process of sudden collapse and its microscopic origin in an refractiv…
We study the layer-to-layer diffusion in smectic-A liquid crystals of colloidal hard rods with different length-to-diameter ratios using computer simulations. The layered arrangement of the smectic phase yields a hopping-type diffusion due to the presence of permanent barriers and transient cages. Remarkably, we detect stringlike clusters composed of inter-layer rods moving cooperatively along the nematic director. Furthermore, we find that the structural relaxation in equilibrium smectic phases shows interesting similarities with that of out-of-equilibrium supercooled liquids, although there …
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…
Using Brownian dynamics simulations, we systematically study the effective interaction between two parallel hard walls in a 2D suspension of self-propelled (active) colloidal hard spheres, and we find that the effective force between two hard walls can be tuned from a long range repulsion into a long range attraction by changing the density of active particles. At relatively high densities, the active hard spheres can form a dynamic crystalline bridge, which induces a strong oscillating long range dynamic wetting repulsion between the walls. With decreasing density, the dynamic bridge graduall…
Several methods for measuring the compressive strength of strong particulate gels are available, including the centrifuge method, whereby the strength as a function of volume-fraction is obtained parametrically from the dependence of equilibrium sediment height upon acceleration. The analysis used conventionally due to Buscall & White (1987) ignores the possibility that the particulate network might adhere to the walls of the centrifuge tube, even though many types of cohesive particulate gel can be expected to. The neglect of adhesion is justifiable when the ratio of the shear to compressive …
Polymer chains adsorbed onto oppositely charged spherical colloidal particles can significantly modify the particle-particle interactions. For sufficient amounts of added polymers, the original electrostatic repulsion can even turn into an effective attraction and relatively large kinetically stable aggregates can form which display several unexpected and interesting peculiarities and some intriguing biotechnological implications. The attractive interaction contribution between two oppositely particles arises from the correlated adsorption of polyions at the oppositely charged particle surface…
The phase behavior of a model suspension of colloidal polydisperse platelets is studied using density-functional theory. Platelets are modelled as parallel rectangular prisms of square section $l$ and height $h$, with length and height distributions given by different polydispersities $δ_l$ and $δ_h$. We obtain the phase behavior of the model, including nematic, smectic and columnar phases and its dependence with the two polydispersities $δ_l$ and $δ_h$. When $δ_l>δ_h$ we observe that the smectic phase stabilises first with respect to the columnar. If $δ_h>δ_l$ we observe the opposite behavior…
Hypothesis: New dynamic phenomena can be observed in evaporating free liquid films from colloidal solutions with bimodal particle size distribution. Such distributions are formed in a natural way in mixed (slightly turbid) solutions of cationic and anionic surfactants, where nanosized micelles coexist with micronsized precipitated particles. Experiment: Without evaporation of water, the films thin down to thickness < 100 nm. Upon water evaporation from the film, one observes spontaneous film thickening (above 300 nm) and appearance of a dynamic vortex with a spot of thinner film in the center.…
We numerically and experimentally study the segregation dynamics in a binary mixture of microswimmers which move on a two-dimensional substrate in a static periodic triangular-like light intensity field. The motility of the active particles is proportional to the imposed light intensity and they possess a motility contrast, i.e., the prefactor depends on the species. In addition, the active particles also experience a torque aligning their motion towards the direction of the negative intensity gradient. We find a segregation of active particles near the intensity minima where typically one spe…
We apply the method developed in Ref. [S.B.Chernyshuk and B.I.Lev, Phys.Rev.E, \textbf{81}, 041701 (2010)] for theoretical investigation of colloidal elastic interactions between axially symmetric particles in the confined nematic liquid crystal (NLC) near one wall and in the nematic cell with thickness $L$. Both cases of homeotropic and planar director orientations are considered. Particularly dipole-dipole, dipole-quadrupole and quadrupole-quadrupole interactions of the \textit{one} particle with the wall and within the nematic cell are found as well as corresponding \textit{two particle} el…
The effects of contact-line pinning are well-known in macroscopic systems, but are only just beginning to be explored at the microscale in colloidal suspensions. We use digital holography to capture the fast three-dimensional dynamics of micrometer-sized ellipsoids breaching an oil-water interface. We find that the particle angle varies approximately linearly with the height, in contrast to results from simulations based on minimization of the interfacial energy. Using a simple model of the motion of the contact line, we show that the observed coupling between translational and rotational degr…
We review recent progress in the theoretical description of anisotropic hard colloidal particles. The shapes considered range from rods and dumbbells to rounded cubes, polyhedra and to biaxial particles with arbitrary shape. Our focus is on both static and dynamical density functional theory and on computer simulations. We describe recent results for the structure, dynamics and phase behaviour in the bulk and in various confining geometries, e.g. established by two parallel walls which reduce the dimensionality of the system to two dimensions. We also include recent theoretical modelling for a…
We study the short time properties of a two-dimensional film growth model in which incident particles execute advective-diffusive motion with a vertical step followed by $D$ horizontal steps. The model represents some features of the deposition of anisotropic colloidal particles of the experiment in Phys. Rev. Lett. {\bf 110}, 035501 (2013), in which wandering particles are attracted to particle-rich regions in the deposit. Height profiles changing from rough to columnar structure are observed as $D$ increases from $0$ (ballistic deposition) to $8$, with striking similarity to the experimental…
We investigate deposit patterns and associated morphology formed after the evaporation of an aqueous droplet containing mono- and bi-dispersed colloidal particles. In particular, the combined effect of substrate heating and particle diameter is investigated. We employ high-speed visualization, optical microscopy and scanning electron microscopy to characterize the evaporating droplets, particle motion, and deposit morphology, respectively. In the context of mono-dispersed colloidal particles, an inner deposit and a typical ring form for smaller and larger particles, respectively, on a nonheate…
We investigate the hopping dynamics of a colloidal particle across a potential barrier and within a viscoelastic, i.e., non-Markovian bath, and report two clearly separated time scales in the corresponding waiting time distributions. While the longer time scale exponentially depends on the barrier height, the shorter one is similar to the relaxation time of the fluid. This short time scale is a signature of the storage and release of elastic energy inside the bath, that strongly increases the hopping rate. Our results are in excellent agreement with numerical simulations of a simple Maxwell mo…
We experimentally investigate the profile and morphology of the ring-like deposits obtained after evaporation of a sessile water droplet containing polystyrene colloidal particles on a hydrophilic glass substrate. In particular, the coupled effect of particle size and concentration are studied. The deposits were qualitatively visualized under an optical microscope and profile of the ring was measured by an optical profilometer. The profile of the ring resembles a partial torus-like shape for all cases of particles size and concentration. The cracks on the surface of the ring were found to occu…
The present article highlights an approach to generate contrasting patterns from drying droplets in a liquid bridge configuration, different from well-known coffee rings. Reduction of the confinement distance (the gap between the solid surfaces) leads to systematized nano-particle agglomeration yielding to spokes-like patterns similar to those found on scallop shells instead of circumferential edge deposition. Alteration of the confinement length modulates the curvature that entails variations in the evaporation flux across the liquid-vapor interface. Consequently, flow inside different liquid…
Colloidal inclusions suspended in a bath of smaller particles experience an effective bath-mediated attraction at small intersurface separations, which is known as the depletion interaction. In an active bath of nonchiral self-propelled particles, the effective force changes from attraction to repulsion; an effect that is suppressed, when the active bath particles are chiral. Using Brownian Dynamics simulations, we study the effects of channel confinement and bath chirality on the effective forces and torques that are mediated between two inclusions that may be fixed within the channel or may …
In this work we use Monte Carlo simulations to study the phase behavior of spherical caps confined between two parallel hard walls separated by a distance H. The particle model consists of a hard sphere of diameter σcut off by a plane at a height χ, and it is loosely based on mushroom cap-shaped particles whose phase behavior was recently studied experimentally [E. K. Riley and C. M. Liddell, Langmuir, 26, 11648 (2010)]. The geometry of the particles is characterized by the reduced height χ^* = χ/σ, such that the model extrapolates between hard spheres for χ^* \leftarrow 1 and infinitely thin …
We present a linearized shear-transformation-zone (STZ) theory of glassy dynamics in which the internal STZ transition rates are characterized by a broad distribution of activation barriers. For slowly aging or fully aged systems, the main features of the barrier-height distribution are determined by the effective temperature and other near-equilibrium properties of the configurational degrees of freedom. Our theory accounts for the wide range of relaxation rates observed in both structural glasses and soft glassy materials such as colloidal suspensions. We find that the frequency dependent lo…
Colloidal patchy particles with divalent attractive interaction can self-assemble into linear polymer chains. Their equilibrium properties in 2D and 3D are well described by Wertheim's thermodynamic perturbation theory which predicts a well-defined exponentially decaying equilibrium chain length distribution. In experimental realizations, due to gravity, particles sediment to the bottom of the suspension forming a monolayer of particles with a gravitational height smaller than the particle diameter. In accordance with experiments, an anomalously high monomer concentration is observed in simula…
