We present the first direct measurement of three-body interactions in a colloidal system comprised of three charged colloidal particles. Two of the particles have been confined by means of a scanned laser tweezers to a line-shaped optical trap where they diffused due to thermal fluctuations. Upon the approach of a third particle, attractive three-body interactions have been observed. The results are in qualitative agreement with additionally performed nonlinear Poissson-Boltzmann calculations, which also allow us to investigate the microionic density distributions in the neighborhood of the interacting colloidal particles.
Three-body and four-body interactions have been directly measured in a colloidal system comprised of three (or four) charged colloidal particles. Two of the particles have been confined by means of a scanned laser tweezers to a line-shaped optical trap where they diffused due to thermal fluctuations. By means of an additional focused optical trap a third particle has been approached and attractive three-body interactions have been observed. These observations are in qualitative agreement with additionally performed nonlinear Poissson-Boltzmann calculations. Two configurations of four particles…
We study the melting behavior of charged colloidal crystals, using a simulation technique that combines a continuous mean-field Poisson-Boltzmann description for the microscopic electrolyte ions with a Brownian-dynamics simulation for the mesoscopic colloids. This technique ensures that many-body interactions between the colloids are fully taken into account, and thus allows us to investigate how many-body interactions affect the solid-liquid phase behavior of charged colloids. Using the Lindemann criterion, we determine the melting line in a phase-diagram spanned by the colloidal charge and t…
Electrostatic forces between small groups of colloidal particles are measured using blinking optical tweezers. When the electrostatic screening length is significantly larger than the particle radius, forces are found to be non-pairwise additive. Both pair and multi-particle forces are well described by the linearized Poisson-Boltzmann equation with constant potential boundary conditions. These findings may play an important role in understanding the structure and stability of a wide variety of systems, from micron-sized particles in oil to aqueous nanocolloids.
The solid-liquid phase-diagram of charge-stabilized colloidal suspensions is calculated using a technique that combines a continuous Poisson-Boltzmann description for the microscopic electrolyte ions with a molecular-dynamics simulation for the macroionic colloidal spheres. While correlations between the microions are neglected in this approach, many-body interactions between the colloids are fully included. The solid-liquid transition is determined at a high colloid volume fraction where many-body interactions are expected to be strong. With a view to the Derjaguin-Landau-Verwey-Overbeek theo…
We demonstrate a technique for simultaneously measuring each component of the force vectors and mobility tensor of a small collection of colloidal particles based on observing a set of particle trajectories. For a few-body system of micron-sized polymer beads in oil separated by several particle radii, we find that the mobility tensor is well-described by a pairwise Stokeslet model. This stands in contrast to the electrostatic interactions, which were found to deviate significantly from a pairwise model. The measurement technique presented here should be simple to extend to systems of heteroge…
Simulations of colloidal suspensions consisting of mesoscopic particles and smaller species such as ions or depletants are computationally challenging as different length and time scales are involved. Here, we introduce a machine learning (ML) approach in which the degrees of freedom of the microscopic species are integrated out and the mesoscopic particles interact with effective many-body potentials, which we fit as a function of all colloid coordinates with a set of symmetry functions. We apply this approach to a colloid-polymer mixture. Remarkably, the ML potentials can be assumed to be ef…
A numerical method is presented for first-principle simulations of charged colloidal dispersions in electrolyte solutions. Utilizing a smoothed profile for colloid-solvent boundaries, efficient mesoscopic simulations are enabled for modeling dispersions of many colloidal particles exhibiting many-body electrostatic interactions. The validity of the method was examined for simple colloid geometries, and the efficiency was demonstrated by calculating stable structures of two-dimensional dispersions, which resulted in the formation of colloidal crystals.
Spherically-symmetric atom-centered descriptors of atomic environments have been widely used for constructing potential or free energy surfaces of atomistic and colloidal systems and to characterize local structures using machine learning techniques. However, when particle shapes are non-spherical, as in the case of rods and ellipsoids, standard spherically-symmetric structure functions alone produce imprecise descriptions of local environments. In order to account for the effects of orientation, we introduce two- and three-body orientation-dependent particle-centered descriptors for systems c…
Colloidal particles with active boundary layers - regions surrounding the particles where nonequilibrium processes produce large velocity gradients - are common in many physical, chemical and biological contexts. The velocity or stress at the edge of the boundary layer determines the exterior fluid flow and, hence, the many-body interparticle hydrodynamic interaction. Here, we present a method to compute the many-body hydrodynamic interaction between $N$ spherical active particles induced by their exterior microhydrodynamic flow. First, we use a boundary integral representation of the Stokes e…
We investigate a model for colloidal network formation using Brownian Dynamics computer simulations. Hysteretic springs establish transient bonds between particles with repulsive core. If a bonded pair is separated by a cutoff distance, the spring vanishes and reappears only if the two particles contact each other. We present results for the the bond lifetime distribution and investigate the properties of the van Hove dynamical two-body correlation function. The model displays crossover from fluid-like dynamics, via transient network formation, to arrested quasi-static network behavior.
We describe a novel method of tracking the rotational motion of clusters of colloidal particles. Our method utilizes rigid body transfor- mations to determine the rotations of a cluster and extends conventional proven particle tracking techniques in a simple way, thus facilitating the study of rotational dynamics in systems containing or composed of colloidal clusters. We test our method by measuring dynamical properties of simulated Brownian clusters under conditions relevant to microscopy experiments. We then use the technique to track and describe the motions of a real colloidal cluster ima…
A new computational method is presented to resolve hydrodynamic interactions acting on solid particles immersed in incompressible host fluids. In this method, boundaries between solid particles and host fluids are replaced with a continuous interface by assuming a smoothed profile. This enabled us to calculate hydrodynamic interactions both efficiently and accurately, without neglecting many-body interactions. The validity of the method was tested by calculating the drag force acting on a single cylindrical rod moving in an incompressible Newtonian fluid. This method was then applied in order …
Based on Brownian dynamics simulations, we investigate the thermodynamic signatures of non-equilibrium steady states in a confined colloidal suspensions under shear flow. Specifically, we consider a thin film consisting of charged particles in narrow slit-pore confinement, forming two layers with quadratic in-plane structure in equilibrium. This many-body system displays three distinct steady states, characterized by unique dynamical and rheological response to the applied shear flow. Calculating the work and heat, we find that both quantities indicate the different states by their mean and by…
We determine the capillary attraction and equilibrium configurations of particles trapped at a liquid-fluid interface due to the pinning of their contact-line. We calculate analytically the asymptotic interaction energy between two particles and, numerically, the multi-body energy landscape for up to four contacting particles. Our results are consistent with recent experiments. We show that a system composed of a large number of such particles behaves as a jammed system.
Asymmetrically charged, nonspherical colloidal particles in general perform complex rotations and oblique motions under an electric field. The interplay of electrostatic and hydrodynamic forces complicate the prediction of these motions. We demonstrate a method of calculating the body tensors that dictate translational and rotational velocity vectors arising from an external electric field. We treat insulating, rigid bodies in the linear-response regime, with indefinitely small electrostatic screening length. The method represents the body as an assembly of point sources of both hydrodynamic d…
Colloidal interactions in nematic liquid crystals can be described as interactions between elastic multipoles that depend on particle shape, topology, chirality, boundary conditions and induced topological defects. Here, we describe a nematic colloidal system consisting of mesostructures of gold capable of inducing elastic multipoles of different order. Elastic monopoles are formed by relatively large asymmetric mesoflower particles, for which gravity and elastic torque balancing yields monopole-type interactions. High-order multipoles are instead formed by smaller mesoflowers with a myriad of…
Self-assembly of nanoparticles can enable composites with pre-designed properties but remains challenged by reproducing structural diversity of atomic and molecular crystals. We combine anisotropic elastic and weakly screened electrostatic interactions to guide both orientational and triclinic positional self-ordering of inorganic nanocrystals in a nematic fluid host. The lattice periodicity of these low-symmetry colloidal crystals is more than an order of magnitude larger than the nanoparticle size. Orientations of nanocrystals, as well as crystallographic axes of ensuing triclinic colloidal …
Nonreciprocal effective interaction forces can occur between mesoscopic particles in colloidal suspensions that are driven out of equilibrium. These forces violate Newton's third law actio=reactio on coarse-grained length and time scales. Here we explore the statistical mechanics of Brownian particles with nonreciprocal effective interactions. Our model system is a binary fluid mixture of spherically symmetric, diffusiophoretic mesoscopic particles, and we focus on the time-averaged particle pair- and triplet-correlation functions. Based on the many-body Smoluchowski equation we develop a micr…
We measure all nonzero elements of the three-dimensional (3D) diffusion tensor D for clusters of colloidal spheres to a precision of 1% or better using digital holographic microscopy. We study both dimers and triangular trimers of spheres, for which no analytical calculations of the diffusion tensor exist. We observe anisotropic rotational and translational diffusion arising from the asymmetries of the clusters. In the case of the three-particle triangular cluster, we also detect a small but statistically significant difference in the rotational diffusion about the two in-plane axes. We attrib…
We study the fluctuation-induced Casimir interactions in colloidal suspensions, especially between colloids immersed in a binary liquid close to its critical demixing point. To simulate these systems, we present a highly efficient cluster Monte Carlo algorithm based on geometric symmetries of the Hamiltonian. Utilizing the principle of universality, the medium is represented by an Ising system while the colloids are areas of spins with fixed orientation. Our results for the Casimir interaction potential between two particles at the critical point in two dimensions perfectly agree with the exac…
The rotational Brownian motion of colloidal spheres in dense suspensions reflects local hydrodynamics and friction, both key to non-linear rheological phenomena such as shear-thickening and jamming, and transport in crowded environments, including intracellular migration and blood flow. To fully elucidate the role of rotational dynamics experimentally, it is crucial to measure the translational and rotational motion of all spheres simultaneously. Here, we develop compositionally uniform colloidal spheres with an off-centre, fully embedded core with a different fluorophore to the particle body,…
We present a framework to segregate the roles of elastic and non-elastic deformations in the examination of real-space experiments of solid-solid Martensitic transitions. The Martensitic transformation of a body-centred-tetragonal(BCT) to a body-centred-orthorhombic(BCO) crystal structure has been studied in a model system of micron-scale ionic microgel colloids. Non-affine fluctuations, i.e., displacement fluctuations that do not arise from purely elastic(affine) deformations, are detected in particle configurations acquired from the experiment. Tracking these fluctuations serves as a highly …
Recent work on charged colloidal suspensions with very low levels of added salt has suggested that although pairs of the colloidal particles repel, clusters of the particles attract. Motivated by this, we study simple model particles which have many-body attractions. These attractions are generic many-body attractions and are not calculated for any specific colloidal suspension. We find that many-body attractions can stabilise solid phases at low pressures but that the liquid phase is either completely absent from the equilibrium phase diagram or present only within a small region of parameter…
In titration experiments with NaOH we have determined the full phase diagram of charged colloidal spheres in dependence on the particle density n, the particle effective charge Zeff and the concentration of screening electrolyte c using microscopy, light and Ultra Small Angle X-Ray Scattering (USAXS). For sufficiently large n the system crystallizes upon increasing Zeff at constant c and melts upon increasing c at only slightly altered Zeff. In contrast to earlier work equilibrium phase boundaries are consistent with a universal melting line prediction from computer simulation, if the elastici…
We study the effects of the optical binding force on wavelength sized colloidal particles free to move in a counter-propagating beam. This work is motivated by the concept of using optical binding to direct the assembly of large numbers of colloidal particles; previous work has used small numbers of particles and/or 1D or 2D restricted geometries. Utilizing a novel experimental scheme, we describe the general static and dynamic self-organization behaviors for 20--100 particles free to move in 3-dimensional space. We observe the self-organization of the colloids into large optically bound struc…
We discuss the motion of colloidal particles relative to a two component fluid consisting of solvent and solute. Particle motion can result from (i) net body forces on the particle due to external fields such as gravity; (ii) slip velocities on the particle surface due to surface dissipative phenomena. The perturbations of the hydrodynamic flow field exhibits characteristic differences in cases (i) and (ii) which reflect different patterns of momentum flux corresponding to the existence of net forces, force dipoles or force quadrupoles. In the absence of external fields, gradients of concentra…
Three-body distribution functions in classical fluids have been theoretically investigated many times, but have never been measured directly. We present experimental three-point correlation functions that are computed from particle configurations measured by means of video-microscopy in two types of quasi-two-dimensional colloidal model fluids: a system of charged colloidal particles and a system of paramagnetic colloids. In the first system the particles interact via a Yukawa potential, in the second via a potential $Γ/r^{3}$. We find for both systems very similar results: on increasing the c…
At sufficiently low temperatures and high densities, repulsive spherical particles in two-dimensions (2d) form close-packed structures with six-fold symmetry. By contrast, when the interparticle interaction has an attractive anisotropic component, the structure may exhibit the symmetry of the interaction. We consider a suspension of spherical particles interacting through an isotropic repulsive potential and a three-fold symmetric attractive interaction, confined in circular potential traps in 2d. We find that, due to the competition between the interparticle and the external potentials, the p…
Based on primitive model computer simulations with explicit microions, we calculate the effective interactions in a binary mixture of charged colloids with species $A$ and $B$ for different size and charge ratios. An optimal pairwise interaction is obtained by fitting the many-body effective forces. This interaction is close to a Yukawa (or Derjaguin-Landau-Verwey-Overbeek(DLVO)) pair potential but the $AB$ cross-interaction is different from the geometric mean of the two direct $AA$ and $BB$ interactions. As a function of charge asymmetry, the corresponding nonadditivity parameter is first po…
We study the inverse problem of tuning interaction parameters between charged colloidal particles interacting with a hard-core repulsive Yukawa potential, so that they assemble into specified crystal structures. Here, we target the body-centered-cubic (bcc) structure which is only stable in a small region in the phase diagram of charged colloids and is, therefore, challenging to find. In order to achieve this goal, we use the statistical fluctuations in the bond orientational order parameters to tune the interaction parameters for the bcc structure, while initializing the system in the fluid p…
Exploring the role of hydrodynamic interactions in spherically-confined drying colloidal suspensions
Auburn University（奥本大学）；Leibniz-Institut für Polymerforschung Dresden e.V.（德累斯顿莱布尼茨聚合物研究所）；Technische Universität Dresden（德累斯顿工业大学）；Johannes Gutenberg University Mainz（美因茨约翰内斯·古腾堡大学）
Colloidal assembly represents a powerful method for the fabrication of functional materials. In this article, we describe how acoustic radiation forces can guide the assembly of colloidal particles into structures that serve as microscopic elements in novel acoustic metadevices or act as phononic crystals. Using a simple three-dimensional orthogonal system, we show that a diversity of colloidal structures with orthorhombic symmetry can be assembled with megahertz-frequency (MHz) standing pressure waves. These structures allow rapid tuning of acoustic properties and provide a new platform for d…
Silica nanoparticles trapped at air-water interface form a 2D solid state with amorphous order. We propose a theoretical model to describe how this solid-like state deforms under a shear strain ramp up to and beyond a yielding point which leads to plastic flow. The model accounts for all the particle-level and many-body physics of the system: nonaffine displacements, local connectivity and its evolution in terms of cage-breaking, and interparticle interactions mediated by the particle chemistry and colloidal forces. The model is able to reproduce experimental data with only two non-trivial fit…
Colloidal systems find important applications ranging from fabrication of photonic crystals to direct probing of phenomena typically encountered in atomic crystals and glasses. New applications - such as nanoantennas, plasmonic sensors, and nanocircuits - pose a challenge of achieving sparse colloidal assemblies with tunable interparticle separations that can be controlled at will. We demonstrate reconfigurable multiscale interactions and assembly of colloids mediated by defects in cholesteric liquid crystals that are probed by means of laser manipulation and three-dimensional imaging. We find…
Open structures can display a number of unusual properties, including a negative Poisson's ratio, negative thermal expansion, and holographic elasticity, and have many interesting applications in engineering. However, it is a grand challenge to self-assemble open structures at the colloidal scale, where short-range interactions and low coordination number can leave them mechanically unstable. In this paper we discuss the self-assembly of open structures using triblock Janus particles, which have two large attractive patches that can form multiple bonds, separated by a band with purely hard-sph…
The connection between fundamental interactions acting in molecules in a fluid and macroscopically measured properties, such as the viscosity between colloidal particles coated with polymers, is studied here. The role that hydrodynamic and Brownian forces play in colloidal dispersions is also discussed. It is argued that many body systems in which all these interactions take place can be accurately solved using computational simulation tools. One of those modern tools is the technique known as dissipative particle dynamics, which incorporates Brownian and hydrodynamic forces, as well as basic …
Three-body interactions have been measured among three charged colloidal particles in deionized solvent. Two of the particles have been confined to an optical line-trap while the third one was approached by means of a focused laser beam. The experimentally determined three-body interactions are attractive and roughly of the same magnitude and range as the pair-interactions. In addition, numerical calculations have been performed, which show good agreement with the experimental results.
A method for forming permanent three dimensional structures from colloidal particles using holographic optical trapping is described. Holographic optical tweezers (HOT) are used to selectively position charge stabilized colloidal particles within a flow cell. Once the particles are in the desired location an electrolyte solution is pumped into the cell which reduces the Debye length and induces aggregation caused by the van der Waals attraction. This technique allows for the formation of three dimensional structures both on and away from the substrate that can be removed from solution without …
Charge-stabilized colloidal suspensions can be conveniently described by formally reducing the macroion-microion mixture to an equivalent one-component system of pseudo-particles. Within this scheme, the utility of a linear response approximation for deriving effective interparticle interactions has been demonstrated [M. J. Grimson and M. Silbert, Mol. Phys. 74, 397 (1991)]. Here the response approach is extended to suspensions of finite-sized macroions and used to derive explicit expressions for (1) an effective electrostatic pair interaction between pseudo-macroions and (2) an associated vol…
Colloidal spheres driven through water along a circular path by an optical ring trap display unexpected dynamical correlations. We use Stokesian Dynamics simulations and a simple analytical model to demonstrate that the path's curvature breaks the symmetry of the two-body hydrodynamic interaction, resulting in particle pairing. The influence of this effective nonequilibrium attraction diminishes as either the temperature or the stiffness of the radial confinement increases. We find a well defined set of dynamically paired states whose stability relies on hydrodynamic coupling in curving trajec…
Electrostatic interactions play an important role in numerous self-assembly phenomena, including colloidal aggregation. Although colloids typically have a dielectric constant that differs from the surrounding solvent, the effective interactions that arise from inhomogeneous polarization charge distributions are generally neglected in theoretical and computational studies. We introduce an efficient technique to resolve polarization charges in dynamical dielectric geometries, and demonstrate that dielectric effects \emph{qualitatively} alter the predicted self-assembled structures, with surprisi…
Recent experiments performed on a variety of soft glassy materials have demonstrated that any imposed shear flow serves to simultaneously fluidize these systems in all spatial directions [Ovarlez \textit{et al.} (2010)]. When probed with a second shear flow, the viscous response of the experimental system is determined by the rate of the primary, fluidizing flow. Motivated by these findings, we employ a recently developed schematic mode-coupling theory [Brader \textit{et al.} (2009)] to investigate the three dimensional flow of a colloidal glass, subject to a combination of simple shear and un…
To gain insight into the kinetics of colloidal gel evolution at low particle volume fractions $ϕ$, we utilize differential dynamic microscopy to investigate particle aggregation, geometric percolation, and the subsequent transition to nonergodic dynamics. We report the emergence of unexpectedly rich multiscale dynamics upon the onset of nonergodicity, which separates the wave vectors $q$ into three different regimes. In the high-$q$ domain, the gel exhibits $ϕ$-independent internal vibrations of fractal clusters. The intermediate-$q$ domain is dominated by density fluctuations at the length sc…
Hydrodynamic interactions are important for diverse fluids especially those with low Reynold's number such as microbial and particle-laden suspensions, and proteins diffusing in membranes. Unfortunately, while far-field (asymptotic) hydrodynamic interactions are fully understood in two- and three-dimensions, near-field interactions are not, and thus our understanding of motions in dense fluid suspensions is still lacking. In this contribution, we experimentally explore the hydrodynamic correlations between particles in quasi-two-dimensional colloidal fluids in the near-field. Surprisingly, the…
The freezing of colloidal suspensions is encountered in many natural and engineering processes such as the freezing of soils, food engineering, and cryobiology. It can also be used as a bio-inspired, versatile, and environmentally-friendly processing route for porous materials and composites. Yet, it is still a puzzling phenomenon with many unexplained features, due to the complexity of the system and the space and time scales at which the process should be investigated. We demonstrate here the interest of fast X-ray computed tomography to provide time-lapse, three-dimensional, in situ imaging…
In this letter, we investigate several aspects related to the effect of hydrodynamics interactions on phase separation-induced gelation of colloidal particles. We explain physically the observation of Tanaka and Araki[Phys. Rev. Lett. {\bf 85}, 1338 (2000)] of hydrodynamic stabilization of cellular network structures in two dimensions. We demonstrate that hydrodynamic interactions have only a minor quantitative influence on the structure of transient gels in three dimensions. We discuss some experimental implications of our results.
