Using molecular dynamics simulations we study the slow dynamics of a hard sphere fluid confined in a disordered porous matrix. The presence of both discontinuous and continuous glass transitions as well as the complex interplay between single-particle and collective dynamics are well captured by a recent extension of mode-coupling theory for fluids in porous media. The degree of universality of the mode-coupling theory predictions for related models of colloids is studied by introducing size-disparity between fluid and matrix particles, as well as softness in the interactions.
In this paper we explore the self-assembly patterns in a two dimensional colloidal system using extensive Langevin Dynamics simulations. The pair potential proposed to model the competitive interaction have a short range length scale between first neighbors and a second characteristic length scale between third neighbors. We investigate how the temperature and colloidal density will affect the assembled morphologies. The potential shows aggregate patterns similar to observed in previous works, as clusters, stripes and porous phase. Nevertheless, we observe at high densities and temperatures a …
Porous mesophases, where well-defined particle-depleted 'void' spaces are present within a particle-rich background fluid, can be self-assembled from colloidal particles interacting via isotropic pair interactions with competing attractions and repulsions. While such structures could be of wide interest for technological applications (e.g., filtration, catalysis, absorption, etc.), relatively few studies have investigated the interactions that lead to these morphologies and how they compare to those that produce other micro-phase-separated structures, such as clusters. In this work, we use inv…
The effective dynamics of a colloidal particle immersed in a complex medium is often described in terms of an overdamped linear Langevin equation for its velocity with a memory kernel which determines the effective (time-dependent) friction and the correlations of fluctuations. Recently, it has been shown in experiments and numerical simulations that this memory may depend on the possible optical confinement the particle is subject to, suggesting that this description does not capture faithfully the actual dynamics of the colloid, even at equilibrium. Here, we propose a different approach in w…
Colloids held by optical or magnetic tweezers have been used to explore the local rheological properties of a complex medium and to extract work from fluctuations with some appropriate protocols. However, a general theoretical understanding of the interplay between the confinement and the interaction with the environment is still lacking. Here, we explore the statistical properties of the position of a probe confined in a harmonic trap moving at constant velocity and interacting with a bath of colloidal particles maintained at a different temperature. Interactions among particles are accounted…
We consider the sedimentation of a colloidal gel under confinement in the direction of gravity. The confinement allows us to compare directly experiments and computer simulations, for the same system size in the vertical direction. The confinement also leads to qualitatively different behaviour compared to bulk systems: in large systems gelation suppresses sedimentation, but for small systems sedimentation is enhanced relative to non-gelling suspensions, although the rate of sedimentation is reduced when the strength of the attraction between the colloids is strong. We map interaction paramete…
We study indented spherical colloids, interacting via depletion forces. These systems exhibit liquid-vapor phase transitions whose properties are determined by a combination of strong "lock-and-key" bonds and weaker non-specific interactions. As the propensity for lock-and-key binding increases, the critical point moves to significantly lower density, and the coexisting phases change their structure. In particular, the liquid phase is "porous", exhibiting large percolating voids. The properties of this system depend strongly on the topological structure of an underlying bond network: we commen…
We investigate the influence of multiscale aggregation and deposition on the colloidal dynamics in a saturated porous medium. At the pore scale, the aggregation of colloids is modeled by the Smoluchowski equation. Essentially, the colloidal mass is distributed between different size clusters. We treat these clusters as different species involved in a diffusion-advection-reaction mechanism. This modeling procedure allows for different material properties to be varied between the different species, specifically the rates of diffusion, aggregation, deposition as well as the advection velocities. …
Reply to: Comment on `Long-range electrostatic interactions between like-charged colloids: steric and confinement effects'
Mateescu在他对[Phys.Rev.E60，6530（1999）]的评论（cond-mat/0104060）中表明，当通过修正的泊松-玻尔兹曼方程考虑微离子的特定尺寸时，有效相互作用仍然是排斥性的，但是对于完全横向限制的情况，不能得出类似的结论。这一点是正确的，但在更一般的研究中已经考虑过了[Phys. Rev. E 62，R1465（2000），在那里一般得到排斥];此外，我们认为，它说明了在完全受限的配置中对势的概念是无关紧要的，如一个简单的例子所示。
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…
Brownian motion of colloidal particles in the quasi-two-dimensional (qTD) confinement displays distinct kinetic characters from that in bulk. Here we experimentally report a dynamic evolution of Brownian particles in the qTD system. The dynamic system displays a quasi-equilibrium state of colloidal particles performing Brownian motion. In the quasi-equilibrium process, the qTD confinement results in the coupling of particle motions, which slowly dampens the motion and interaction of particles until the final equilibrium state reaches. The theory is developed to explain coupling motions of Brow…
Colloidal particles hold promise for mobilizing and removing trapped immiscible fluids from porous media, with implications for key energy and water applications. Most studies focus on accomplishing this goal using particles that can localize at the immiscible fluid interface. Therefore, researchers typically seek to optimize the surface activity of particles, as well as their ability to freely move through a pore space with minimal deposition onto the surrounding solid matrix. Here, we demonstrate that deposition can, surprisingly, promote mobilization of a trapped fluid from a porous medium …
Patchy colloidal model with three and four equivalent patches, confined in the attractive random porous media, undergo re-entrant gas-liquid phase separation with the possibility for the liquid phase density to approach zero. This unusual behavior is caused by an interplay between strong fluid-fluid bonding interactions and weak fluid-matrix attractions. At high temperature the shape of the phase diagram is determined by the attractive interaction between the fluid particles; weak Yukawa attraction between fluid and obstacles only slightly enhances the fluid-fluid bonding. At low enough temper…
Confined samples of liquid crystals are characterized by a variety of topological defects and can be exposed to external constraints such as extreme confinements with nontrivial topology. Here we explore the intrinsic structure of smectic colloidal layers dictated by the interplay between entropy and an imposed external topology. Considering an annular confinement as a basic example, a plethora of competing states is found with nontrivial defect structures ranging from laminar states to multiple smectic domains and arrays of edge dislocations which we refer to as Shubnikov states in formal ana…
We study the non-equilibrium coarsening dynamics of a binary liquid solvent around a colloidal particle in a presence of a time-dependent temperature gradient that emerges after temperature quench of a suitably coated colloid surface. The solvent is maintained at its critical concentration and the colloid is fixed in space. The coarsening patterns near the surface are shown to be strongly dependent on the colloid surface adsorption properties and on the temperature evolution. The temperature gradient alters the morphology of a binary solvent near the surface of a colloid as compared to the coa…
We study the Brownian motion of a charged colloid, confined between two charged walls, for small separation between the colloid and the walls. The system is embedded in an ionic solution. The combined effect of electrostatic repulsion and reduced diffusion due to hydrodynamic forces results in a specific motion in the direction perpendicular to the confining walls. The apparent diffusion coefficient at short times as well as the diffusion characteristic time are shown to follow a sigmoid curve as function of a dimensionless parameter. This parameter depends on the electrostatic properties and …
Diverse processes -- e.g., environmental pollution, groundwater remediation, oil recovery, filtration, and drug delivery -- involve the transport of colloidal particles in porous media. Using confocal microscopy, we directly visualize this process in situ and thereby identify the fundamental mechanisms by which particles are distributed throughout a medium. At high injection pressures, hydrodynamic stresses cause particles to be continually deposited on and eroded from the solid matrix -- notably, forcing them to be distributed throughout the entire medium. By contrast, at low injection pressu…
Non-monotonic retention profiles (NRP) have been observed in numerous studies of colloidal-nano flows in porous media. For the first time, we explain the phenomenon by distributed particle properties (size, shape, surface charge). We discuss colloidal-nano transport with fines attachment considering stochastically distributed filtration coefficient (particle attachment probability) and the influence of area occupation by particles on the rock surface. The distributed dynamic system allows for exact averaging (up-scaling) yielding a novel 3x3 system of equations for total concentrations. Beside…
Enskog theory is extended for the description of the self-diffusion coefficient of patchy colloidal fluid in disordered porous media. The theory includes the contact values of fluid-fluid and fluid-matrix pair distribution functions that are modified to include the dependence from the so-called probe particle porosity, $ϕ$, in order to correctly describe the effects of trapping the fluid particles by a matrix. The proposed expressions for the modified contact values of fluid-fluid and fluid-matrix pair distribution functions include three terms. Namely, a hard sphere contribution obtained by u…
Understanding how bacteria move in porous media is critical to applications in healthcare, agriculture, environmental remediation, and chemical sensing. Recent work has demonstrated that E. coli, which moves by run-and-tumble dynamics in a homogeneous medium, exhibits a new form of motility when confined in a disordered porous medium: hopping-and-trapping motility, in which cells perform rapid, directed hops punctuated by intervals of slow, undirected trapping. Here, we use direct visualization to shed light on how these processes depend on pore-scale confinement and cellular activity. We find…
Understanding the relationship between colloidal building block shape and self-assembled material structure is important for the development of novel materials by self-assembly. In this regard, colloidal superballs are unique building blocks because their shape can smoothly transition between spherical and cubic. Assembly of colloidal superballs under spherical confinement results in macroscopic clusters with ordered internal structure. By utilizing Small Angle X-Ray Scattering (SAXS), we probe the internal structure of colloidal superball dispersion droplets during confinement. We observe and…
Understanding relaxation of supercooled fluids is a major challenge and confining such systems can lead to bewildering behaviour. Here we exploit an optically confined colloidal model system in which we use reduced pressure as a control parameter. The dynamics of the system are ``Arrhenius'' at low and moderate pressure, but at higher pressures relaxation is faster than expected. We associate this faster relaxation with a decrease in density adjacent to the confining boundary due to local ordering in the system enabled by the flexible wall.
Designing and fabricating self-assembled open colloidal crystals have become one major direction in soft matter community because of many promising applications associated with open colloidal crystals. However, most of the self-assembled crystals found in experiments are not open but close-packed. Here by using computer simulation, we systematically investigate the self-assembly of oppositely charged colloidal hard spheres confined between two parallel hard walls, and we find that the confinement can stabilize multi-layer NaCl-like (simple cubic) open crystals. The maximal layers of stable NaC…
In a system of colloidal inclusions suspended in a thermalized bath of smaller particles, the bath engenders an attractive force between the inclusions, arising mainly from entropic origins, known as the depletion force. In the case of active bath particles, the nature of the bath-mediated force changes dramatically from an attractive to a repulsive one, as the strength of particle activity is increased. We study such bath-mediated effective interactions between colloidal inclusions in a bath of self-propelled Brownian particles, being confined in a narrow planar channel. Confinement is found …
We study the effective electrostatic interactions between a pair of charged colloidal particles without salt ions while the system is confined in two dimensions. In particular we use a simplified model to elucidate the effects of rotational fluctuations in counterion distribution. The results exhibit effective colloidal attractions under appropriate conditions. Meanwhile, long-range repulsions persist over most of our studied cases. The repulsive forces arise from the fact that in two dimensions the charged colloids cannot be perfectly screened by counterions, as the residual quadrupole moment…
Utilizing a 3D mean-field lattice-gas model, we analyze the effect of confinement on the nature of capillary phase transition in granular aggregates with varying disorder and their inverse porous structures obtained by interchanging particles and pores. Surprisingly, the confinement effects are found to be much less pronounced in granular aggregates as opposed to porous structures. We show that this discrepancy can be understood in terms of the surface-surface correlation length with a connected path through the fluid domain, suggesting that this length captures the true degree of confinement.…
We study a dense colloidal suspension confined between two quasiparallel glass plates as a model system for a supercooled liquid in confined geometries. We directly observe the three-dimensional Brownian motion of the colloidal particles using laser scanning confocal microscopy. The particles form dense layers along the walls, but crystallization is avoided as we use a mixture of two particle sizes. A normally liquid-like sample, when confined, exhibits slower diffusive motion. Particle rearrangements are spatially heterogeneous, and the shapes of the rearranging regions are strongly influence…
Recent theories predict that when a supercooled liquid approaches the glass transition, particle clusters with a special "amorphous order" nucleate within the liquid, which lead to static correlations dictating the dramatic slowdown of liquid relaxation. The prediction, however, has yet to be verified in 3D experiments. Here, we design a colloidal system, where particles are confined inside spherical cavities with an amorphous layer of particles pinned at the boundary. Using this novel system, we capture the amorphous-order particle clusters and demonstrate the development of a static correlat…
From suspensions to porous multilayers: microstructure formation and particle packing in drying colloidal films
Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Forschungszentrum Jülich（于利希研究中心埃尔朗根-纽伦堡亥姆霍兹可再生能源研究所（IET-2））；Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡弗里德里希·亚历山大大学）
The bulk phase behavior of a fluid is typically altered when the fluid is brought into confinement by the walls of a random porous medium. Inside the porous medium, phase transition points are shifted, or may disappear altogether. A crucial determinant is how the walls interact with the fluid particles. In this work, we consider the situation whereby the walls are neutral with respect to the liquid and vapor phase. In order to realize the condition of strict neutrality, we use a symmetric binary mixture inside a porous medium that interacts identically with both of the mixture species. Monte C…
Under partial confinement, the motion of colloidal particles is restricted to a plane but their dynamics is influenced by hydrodynamic interactions mediated by the unconfined, three--dimensional flow of the embedding fluid. We demonstrate that this dimensionality mismatch induces a characteristic divergence in the two--dimensional collective diffusion coefficient of the colloidal monolayer. This result, independent from the specific interparticle forces in the monolayer, is solely due to the kinematical constraint on the colloidal particles, and it is different from the known divergence of tra…
Using grand canonical Monte Carlo simulations, we investigate the percolation behavior of a square well fluid with an ultra-short range of attraction in three dimension (3D) and in confined geometry. The latter is defined through two parallel and structureless walls (slit-pore). We focus on temperatures above the critical temperature of the (metastable) condensation transition of the 3D system. Investigating a broad range of systems sizes, we first determine the percolation thresholds, i. e., the critical packing fraction for percolation $η_{c}$. For the slit-pore systems, $η_{c}$ is found to …
Using numerical simulations we study the slow dynamics of a colloidal hard-sphere fluid adsorbed in a matrix of disordered hard-sphere obstacles. We calculate separately the contributions to the single-particle dynamic correlation functions due to free and trapped particles. The separation is based on a Delaunay tessellation to partition the space accessible to the centres of fluid particles into percolating and disconnected voids. We find that the trapping of particles into disconnected voids of the matrix is responsible for the appearance of a nonzero long-time plateau in the single-particle…
The mechanical properties of crystalline materials can be substantially modified under confinement. Such modified macroscopic properties are usually governed by the altered microstructures and internal stress fields. Here, we use a parallel plate geometry to apply a quasi-static squeeze flow crushing a colloidal polycrystal while simultaneously imaging it with confocal microscopy. The confocal images are used to quantify the local structure order and, in conjunction with Stress Assessment from Local Structural Anisotropy (SALSA), determine the stress at the single-particle scale. We find that …
Understanding the correlation between structure and rheology in colloidal suspensions is important as these suspensions are crucial in industrial applications. Moreover, colloids exhibit a wide range of structures under confinement that could considerably alter the viscosity. Here, we use a combination of experiments and simulations to elucidate how confinement induced structures alter the relative contributions of hydrodynamic and repulsive forces to produce up to a ten fold change in the viscosity. We use a custom built confocal rheoscope to image the particle configurations of a colloidal s…
The complex behavior of confined fluids arising due to a competition between layering and local packing can be disentangled by considering quasi-confined liquids, where periodic boundary conditions along the confining direction restore translational invariance. This system provides a means to investigate the interplay of the relevant length scales of the confinement and the local order. We provide a mode-coupling theory of the glass transition (MCT) for quasi-confined liquids and elaborate an efficient method for the numerical implementation. The nonergodicity parameters in MCT are compared to…
We present numerical results for the tagged-particle dynamics by solving the mode-coupling theory in confined geometry for colloidal liquids (cMCT). We show that neither the microscopic dynamics nor the type of intermediate scattering function qualitatively changes the asymptotic dynamics in vicinity of the glass transition. In particular, we find similar characteristics of confinement in the low-frequency susceptibility spectrum which we interpret as footprints of parallel relaxation. We derive predictions for the localization length and the scaling of the diffusion coefficient in the superco…
In colloidal systems, Brownian motion emerges from the massive separation of time and length scales associated to characteristic dynamics of the solute and solvent constituents. This separation of scales produces several temporal regimes in the colloidal dynamics when combined with the effects of the interaction between the particles, confinement conditions, and state variables, such as density and temperature. Some examples are the short- and long-time regimes in two- and three-dimensional open systems and the diffusive and sub-diffusive regimes observed in the single-file dynamics along a st…
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…
Purely entropic systems such as suspensions of hard rods, platelets and spheres show rich phase behavior. Rods and platelets have successfully been used as models to predict the equilibrium properties of liquid crystals for several decades. Over the past years hard particle models have also been studied in the context of non-equilibrium statistical mechanics, in particular regarding the glass transition, jamming, sedimentation and crystallization. Recently suspensions of hard anisotropic particles also moved into the focus of materials scientists who work on conducting soft matter composites. …
