Using numerical simulations, we study the non-equilibrium coarsening dynamics of a binary solvent around spherical colloids in the presence of a temperature gradient. The coarsening dynamics following a temperature quench is studied by solving the coupled modified Cahn-Hilliard-Cook equation and the heat diffusion equation, which describe the concentration profile and the temperature field, respectively. For the temperature field we apply a suitable boundary condition. We observe the formation of circular layers of different phases around the colloid whereas away from the colloid patterns of spinodal decomposition persist. Additionally, we investigate the dependence of the pattern formation on the quench temperature. Our simulation mimics an experimental system where the colloid is heated by laser illumination. Note that we look at the cooling of a solvent with an upper critical temperature, whereas the experimental analogue is the laser-heating of a solvent with a lower critical temperature. We also study a two colloid system. Here, we observe that a bridge of one phase forms connecting the two colloids. Also, we study the force acting on the colloids that is generated by the chemical potential gradient.
We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerab…
We study the phase behavior of colloidal suspensions the solvents of which are considered to be binary liquid mixtures undergoing phase segregation. We focus on the thermodynamic region close to the critical point of the accompanying miscibility gap. There, due to the colloidal particles acting as cavities in the critical medium, the spatial confinements of the critical fluctuations of the corresponding order parameter result in the effective, so-called critical Casimir forces between the colloids. Employing an approach in terms of effective, one-component colloidal systems, we explore the pos…
From experimental studies it is well-known that colloidal particles suspended in a near-critical binary solvent exhibit interesting aggregation phenomena, often associated with colloidal phase transitions, and assumed to be driven by long-ranged solvent mediated (SM) interactions (critical Casimir forces), set by the (diverging) correlation length of the solvent. We present the first simulation and theoretical study of an explicit model of a ternary mixture that mimics this situation. Both the effective SM pair interactions and the full ternary phase diagram are determined for Brownian discs s…
We present a numerical study of the effective potential $V_\mathrm{eff}$ between two hard-sphere colloids dispersed in a solvent of interacting particles, for several values of temperature and solvent density, approaching the solvent gas-liquid critical point. We investigate the stability of a system of particles interacting via $V_\mathrm{eff}$ to evaluate the locus of colloidal aggregation in the solvent phase-diagram, and its dependence on the colloid size. We assess how the excluded volume depletion forces are modified by solvent attraction and discuss under which conditions solvent critic…
We study the phenomenon of self-assembly of silica micro-spheres on a glass plate during evaporation of the solvent from a colloidal suspension. Our experiments unveil an interesting competition between ordering and compaction in a strongly driven, out of equilibrium system arising from a slowing down of dynamics due to an impending glass transition. A suitable choice of experimental conditions minimizing the influence of many other competing phenomena that usually complicate probing of this underlying physics is crucial for our study. A re-entrant behavior in the order-disorder phase diagram …
We consider an ensemble of spherical colloidal particles immersed in a near-critical solvent such as a binary liquid mixture close to its critical demixing point. The emerging long-ranged fluctuations of the corresponding order parameter of the solvent drive the divergence of the correlation length. Spatial confinements of these critical fluctuations by colloidal solute particles, acting as cavities in the fluctuating medium, restrict and modify the fluctuation spectrum in a way which depends on their relative configuration. This results in effective, so-called critical Casimir forces (CCFs) a…
While the important role of electrostatic interactions in aqueous colloidal suspensions is widely known and reasonably well-understood, the relevance of charge in nonpolar suspensions remains mysterious. We demonstrate that particles can have surprisingly strong electrostatic interactions in low dielectric constant environments when ions are solubilized by reverse micelles. A simple thermodynamic model, relating the structure of the micelles to the equilibrium ionic strength, is in good agreement with both conductivity and interaction measurements. Since dissociated ions are solubilized by rev…
We present an experimental and theoretical study of the phase behavior of a binary mixture of colloids with opposite adsorption preferences in a critical solvent. As a result of the attractive and repulsive critical Casimir forces, the critical fluctuations of the solvent lead to a further critical point in the colloidal system, i.e. to a critical colloidal-liquid--colloidal-liquid demixing phase transition which is controlled by the solvent temperature. Our experimental findings are in good agreement with calculations based on a simple approximation for the free energy of the system.
Convection in a colloidal suspension with a large negative separation ratio is studied experimentally by heating from above. Shadowgraph observation at very large solutal Rayleigh numbers are reported as a function of time. Fast relaxation oscillations are reported for the root mean square value of the shadowgraph intensity. While pure fluids exhibit a transition to turbulent convection for Rayleigh number of about 10^6, stable spoke-pattern planform with up and down columnar flows are observed up to solutal Rayleigh numbers of the order of 10^9. It is suggested that the surprising stability o…
We propose a novel actuation mechanism for colloids, which is based on the Seebeck effect of the electrolyte solution: Laser heating of a nonionic particle accumulates in its vicinity a net charge Q, which is proportional to the excess temperature at the particle surface. The corresponding long-range thermoelectric field provides a tool for controlled interactions with nearby beads or with additional molecular solutes. An external field Eext drags the thermocharged particle at a velocity that depends on its size and absorption properties; the latter point could be particularly relevant for sep…
We show how to implement stick boundary conditions for a spherical colloid in a solvent that is coarse-grained by the method of stochastic rotation dynamics. This allows us to measure colloidal rotational velocity auto-correlation functions by direct computer simulation. We find quantitative agreement with Enskog theory for short times and with hydrodynamic mode-coupling theory for longer times. For aqueous colloidal suspensions, the Enskog contribution to the rotational friction is larger than the hydrodynamic one when the colloidal radius drops below 35nm.
We report a study of the structure of droplets of colloidal gels containing dissolved sodium chloride. The components segregate and form intricate patterns. The salt crystalizes in fractal and multi-fractal dendritic forms which are determined by the material which forms the colloidal gel. Here potato starch, gelatine and carboxymethyl cellulose have been used. The substrate also plays a role in some cases. Photographs and micrographs at different level of magnification are shown.
A model is presented for the solution of electrokinetic phenomena of colloidal suspensions in fluid mixtures. We solve the discrete Boltzmann equation with a BGK collision operator using the lattice Boltzmann method to simulate binary fluid flows. Solvent-solvent and solvent-solute interactions are implemented using a pseudopotential model. The Nernst-Planck equation, describing the kinetics of dissolved ion species, is solved using a finite difference discretization based on the link-flux method. The colloids are resolved on the lattice and coupled to the hydrodynamics and electrokinetics thr…
We consider a simplified coarse-grained model for colloid-polymer mixtures, in which polymers are represented as monoatomic molecules interacting by means of pair potentials. We use it to study polymer-colloid segregation in the presence of a quenched matrix of colloidal hard spheres. We fix the polymer-to-colloid size ratio to 0.8 and consider matrices such that the fraction f of the volume that is not accessible to the colloids due to the matrix is equal to 40%. As in the Asakura-Oosawa-Vrij (AOV) case, we find that binodal curves in the polymer and colloid volume-fraction plane have a small…
The drying of a colloidal dispersion can result in a gel phase defined as a porous matrix saturated in solvent. During the drying process, high mechanical stresses are generated. When these stresses exceed the strength of the material, they can be released in the formation of cracks. This process strongly depends on both the mechanical properties of the material and the way the gel consolidates. In this report, we give experimental evidences that the number of cracks formed in the consolidating film depend on the drying rate, the nature of the solvent and the mechanical properties of the collo…
Gel-immobilized colloidal crystals were prepared to obtain hybrid plasmonic-photonic crystals, in which electric field enhancement to a greater extent than that due to localized surface plasmons (LSP) alone was expected due to coupling between LSP and the photonic band. Polystyrene colloidal crystals immobilized by the N-(hydroxymethyl)acrylamide gel were immersed in an aqueous dispersion of gold nanoparticles (AuNPs). Then, the gel-immobilized colloidal crystals were picked out and immersed in an ionic liquid mixture. The surfaces of the gel-immobilized colloidal crystals immersed in the AuNP…
The pattern and profile of a dried colloidal deposit formed after evaporation of a sessile water droplet containing polystyrene particles on a non-uniformly heated glass are investigated experimentally. In particular, the effects of temperature gradient across the substrate and particles size are investigated. The temperature gradient was imposed using Peltier coolers, and side visualization, infrared thermography, optical microscopy, and optical profilometry were employed to collect the data. On a uniformly heated substrate, a ring with an inner deposit is obtained, which is attributed to axi…
The liquid-liquid phase separation of a binary solvent can be arrested by colloidal particles trapped at the interface [K. Stratford et al., Science 309, 5744 (2005)]. We show experimentally that the colloidal network so formed can remain stable after fully remixing the liquids, creating a new type of gel in which colloids in a single-phase solvent have locally planar coordination. We argue that this structure is likely maintained by primary-minimum DLVO bonding of our charged colloids, created under strong compression by capillary forces. We present simulation evidence that the combination of…
We report a numerical investigation of two colloids immersed in a critical solvent, with the aim of quantifying the effective colloid-colloid interaction potential. By turning on an attraction between the colloid and the solvent particles we follow the evolution from the case in which the solvent density close to the colloids changes from values smaller than the bulk to values larger than the bulk. We thus effectively implement the so-called $(+,+)$ and $(-,-)$ boundary conditions defined in field theoretical approaches focused on the description of critical Casimir forces. We find that the ef…
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…
Spatial confinement of a near-critical medium changes its fluctuation spectrum and modifies the corresponding order parameter distribution. These effects result in effective, so-called critical Casimir forces (CCFs) acting on the confining surfaces. These forces are attractive for like boundary conditions of the order parameter at the opposing surfaces of the confinement. For colloidal particles dissolved in a binary liquid mixture acting as a solvent close to its critical point of demixing, one thus expects the emergence of phase segregation into equilibrium colloidal liquid and gas phases. W…
Percolation and critical phenomena show common features such as scaling and universality. Colloidal particles, immersed in a solvent close to criticality, experience long-range effective forces, named critical Casimir forces. %These originate from the confinement of the solvent critical fluctuations between the colloids. Building on the analogy between critical phenomena and percolation, we explore the possibility of observing long-range forces near a percolation threshold. To this aim we numerically evaluate the effective potential between two colloidal particles dispersed in a chemical sol a…
Short colloidal chains are simulated by the slithering-snake-algorithm on a simple cubic lattice. The dipole character of the colloidal particles leads to a long range dipole-dipole interaction. The solvent is simulated by the nearest neighbor Ising model. The aligning of the dipoles under a magnetic field gives rise to the chains to align on their part with the field direction.
We show how the Smoluchowski dynamics of a colloidal Brownian particle suspended in a molecular solvent can be reached starting from the microscopic Liouvillian evolution of the full classical model in the high friction limit. The integration of the solvent degrees of freedom goes through a multiple time scale perturbation expansion which removes the secular divergences. A simple dynamical Monte Carlo scheme is then proposed to solve the resulting evolution equation for the colloid solute particle. In particular we study the approach to the equilibrium Boltzmann distribution at late times and …
We determine the solvent mediated contribution to the effective potentials for model colloidal or nano- particles dispersed in a binary solvent that exhibits fluid-fluid phase separation. Using a simple density functional theory we calculate the density profiles of both solvent species in the presence of the `colloids', which are treated as external potentials, and determine the solvent mediated (SM) potentials. Specifically, we calculate SM potentials between (i) two colloids, (ii) a colloid and a planar fluid-fluid interface, and (iii) a colloid and a planar wall with an adsorbed wetting fil…
We study self-diffusion and sedimentation in colloidal suspensions of nearly-hard spheres using the multiparticle collision dynamics simulation method for the solvent with a discrete mesh model for the colloidal particles (MD+MPCD). We cover colloid volume fractions from 0.01 to 0.40 and compare the MD+MPCD simulations to Brownian dynamics simulations with free-draining hydrodynamics (BD) as well as pairwise far-field hydrodynamics described using the Rotne--Prager--Yamakawa mobility tensor (BD+RPY). The dynamics in MD+MPCD suggest that the colloidal particles are only partially coupled to the…
The critical Casimir effect provides a thermodynamic analogue of the well-known quantum mechanical Casimir effect. It acts between two surfaces immersed in a critical binary liquid mixture, and results from the confinement of concentration fluctuations of the solvent. Unlike the quantum mechanical effect, the magnitude and range of this attraction can be adjusted with temperature via the solvent correlation length, thus offering new opportunities for the assembly of nano and micron-scale structures. Here, we demonstrate the active assembly control of equilibrium phases using critical Casimir f…
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.
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 demonstrate…
Within mean field theory, we investigate the bridging transition between a pair of parallel cylindrical colloids immersed in a binary liquid mixture as a solvent which is close to its critical consolute point $T_c$. We determine the universal scaling functions of the effective potential and of the force between the colloids. For a solvent which is at the critical concentration and close to $T_c$, we find that the critical Casimir force is the dominant interaction at close separations. This agrees very well with the corresponding Derjaguin approximation for the effective interaction between the…
We consider a non-spherical colloidal particle immersed in a fluid close to its critical point. The temperature dependence of the corresponding order parameter profile is calculated explicitly. We perform a systematic expansion of the order parameter profile in powers of the local curvatures of the surface of the colloidal particle. This curvature expansion reduces to the short distance expansion of the order parameter profile in the case that the solvent is at the critical composition.
The analysis of the dynamics of tracer particles in a complex bath can provide valuable information about the microscopic behaviour of the bath. In this work, we study the dynamics of a forced tracer in a colloidal bath by means of Langevin dynamics simulations and a theory model within continuum mechanics. In the simulations, the bath is comprised by quasi-hard spheres with a volume fraction of 50% immersed in a featureless quiescent solvent, and the tracer is pulled with a constant small force (within the linear regime). The theoretical analysis is based on the Navier Stokes equation, where …
Hypothesis: By combining the experimental small- and wide-angle x-ray scattering (SWAXS) method with molecular dynamics simulations and the theoretical 'complemented-system approach' it is possible to obtain detailed information about the intra- and inter-molecular structure and dynamics of the solvation and hydration of the surfactant in organic and mixed solvents, e.g., of the nonionic surfactant Brij 35 (C12E23) in alcohols and aqueous alcohol-rich ternary systems. This first application of the complemented-system approach to the surfactant system will promote the use of this powerful metho…
Stable colloidal dispersions with evenly distributed particles are important for many technological applications. Due to Brownian motion colloidal particles have constant collisions with each other which often lead to their aggregation driven by the long range van der Waals attraction. As a result the colloidal systems often tend to precipitate. A number of methods have been devised to minimize the effect of long-range van der Waals attraction between colloidal particles or to override the influence of the attraction in order to provide the colloidal stability.In the PhD thesis we investigated…
We consider depletion effects of a pear-shaped colloidal particle in a hard-sphere solvent, for two different model realisations of the pear-shaped colloidal particle. The two models are the pear hard Gaussian overlap (PHGO) particles and the hard pears of revolution (HPR). The motivation for this study is to provide a microscopic understanding for the substantially different mesoscopic self-assembly properties of these pear-shaped colloids, in dense suspensions, that have been reported in the first part of this series. This is done by determining the differing depletion attraction via MC simu…
We present a new hybrid lattice-Boltzmann and Langevin molecular dynamics scheme for simulating the dynamics of suspensions of spherical colloidal particles. The solvent is modeled on the level of the lattice-Boltzmann method while the molecular dynamics is done for the solute. The coupling between the two is implemented through a frictional force acting both on the solvent and on the solute, which depends on the relative velocity. A spherical colloidal particle is represented by interaction sites at its surface. We demonstrate that this scheme quantitatively reproduces the translational and r…
We study the pressure-driven flow of concentrated colloids confined in glass micro-channels at the single particle level using fast confocal microscopy. For channel to particle size ratios $a/\bar{D} \lesssim 30$, the flow rate of the suspended particles shows fluctuations. These turn into regular oscillations for higher confinements ($a/\bar{D} \simeq 20$). We present evidence to link these oscillations with the relative flow of solvent and particles (permeation) and the effect of confinement on shear thickening.
The influence of poor solvent quality on fluid demixing of a model mixture of colloids and nonadsorbing polymers is investigated using density functional theory. The colloidal particles are modelled as hard spheres and the polymer coils as effective interpenetrating spheres that have hard interactions with the colloids. The solvent is modelled as a two-component mixture of a primary solvent, regarded as a background theta-solvent for the polymer, and a cosolvent of point particles that are excluded from both colloids and polymers. Cosolvent exclusion favors overlap of polymers, mimicking the e…
We investigate the hydrodynamic properties of a fluid simulated with a mesoscopic solvent model. Two distinct regimes are identified, the `particle regime' in which the dynamics is gas-like, and the `collective regime' where the dynamics is fluid-like. This behavior can be characterized by the Schmidt number, which measures the ratio between viscous and diffusive transport. Analytical expressions for the tracer diffusion coefficient, which have been derived on the basis of a molecular-chaos assumption, are found to describe the simulation data very well in the particle regime, but important de…
If colloidal solute particles are suspended in a solvent close to its critical point, they act as cavities in a fluctuating medium and thereby restrict and modify the fluctuation spectrum in a way which depends on their relative configuration. As a result effective, so-called critical Casimir forces (CCFs) emerge between the colloids. The range and the amplitude of CCFs depend sensitively on the temperature and the composition of the solvent as well as on the boundary conditions of the order parameter of the solvent at the particle surfaces. These remarkable, moreover universal features of the…
The physical behaviour of anisotropic charged colloids is determined by their material dielectric anisotropy, affecting colloidal self-assembly, biological function and even out-of-equilibrium behaviour. However, little is known about anisotropic electrostatic screening, which underlies all electrostatic effective interactions in such soft or biological materials. In this work, we demonstrate anisotropic electrostatic screening for charged colloidal particles in a nematic electrolyte. We show that material anisotropy behaves markedly different from particle anisotropy: The electrostatic potent…
Tannin-tannin and tannin-protein interactions in water-ethanol solvent mixtures are studied in the context of red wine tasting. While tannin self-aggregation is relevant for visual aspect of wine tasting (limpidity and related colloidal phenomena), tannin affinities for salivary proline-rich proteins is fundamental for a wide spectrum of organoleptic properties related to astringency. Tannin-tannin interactions are analyzed in water-ethanol wine-like solvents and the precipitation map is constructed for a typical grape tannin. The interaction between tannins and human salivary proline-rich pro…
Dynamic Light Scattering (DLS) measurements were performed on colloidal suspensions of Laponite\textsuperscript{\textregistered} at different concentrations in the range $C_\text{w}= (1.5÷3.0)$%. The slowing down of the dynamics induced by aging was monitored by following the temporal evolution of autocorrelation functions at different concentrations towards the gel and glass transition. Exploiting analogies with supercooled liquids approaching their glass transitions, an Angell plot for the structural relaxation times was drawn. Finally, the fragility of Laponite\textsuperscript{\textregister…
We study the fingering instability of the interface between two miscible fluids, a colloidal suspension and its own solvent. The temporal evolution of the interface in a Hele-Shaw cell is found to be governed by the competition between the non-linear viscosity of the suspension and an off-equilibrium, effective surface tension $Γ_e$. By studying suspensions in a wide range of volume fractions, $Φ_\mathrm{C}$, we show that $Γ_e \sim Φ_\mathrm{C}^2$, in agreement with Korteweg's theory for miscible fluids. The surface tension exhibits an anomalous increase with particle size, which we account fo…
Thermoresponsive microgels are polymeric colloidal networks that can change their size in response to a temperature variation. This peculiar feature is driven by the nature of the solvent-polymer interactions, which triggers the so-called volume phase transition from a swollen to a collapsed state above a characteristic temperature. Recently, an advanced modelling protocol to assemble realistic, disordered microgels has been shown to reproduce experimental swelling behavior and form factors. In the original framework, the solvent was taken into account in an implicit way, condensing solvent-po…
We demonstrate a novel route of spatially organizing the colloid arrangements on the polymer-grafted substrate by use of self-consistent field and density functional theories. We find that grafting of polymers onto a substrate can effectively control spatial dispersions of deposited colloids as a result of the balance between colloidal settling force and entropically elastic force of brushes, and colloids can form unexpected ordered structures on a grafting substrate. The depositing process of colloidal particles onto the elastic "soft" substrate includes two steps: brush-mediated one-dimensio…
The present study experimentally and numerically investigates the evaporation and resultant patterns of dried deposits of aqueous colloidal sessile droplets, when the droplets are initially elevated to a high temperature before being placed on a substrate held at ambient temperature. The system is then released for natural evaporation without applying any external perturbation. Infrared thermography and optical profilometry were used as essential tools for interfacial temperature measurements and quantification of the coffee-ring dimensions, respectively. Initially, a significant temperature g…
Anisotropic particles oriented in a specific direction can act as artificial atoms and molecules, and their controlled assembly can result in a wide variety of ordered structures. Towards this, we demonstrate the orientation transitions of uncharged peanut-shaped polystyrene colloids, suspended in a non-ionic aprotic polar solvent, near a flat surface whose potential is static or time-varying. The charged surface is coated with an insulating dielectric layer to suppress electric currents. The transition between several orientation states such as random, normal or parallel orientation with resp…
Dynamic density functional theory (DDFT) is a promising approach for predicting the structural evolution of a drying suspension containing one or more types of colloidal particles. The assumed free-energy functional is a key component of DDFT that dictates the thermodynamics of the model and, in turn, the density flux due to a concentration gradient. In this work, we compare several commonly used free-energy functionals for drying hard-sphere suspensions including local-density approximations based on the ideal-gas, virial, and Boublík-Mansoori-Carnahan-Starling-Leland (BMCSL) equations of sta…
Previously, we have proposed a direct simulation scheme for colloidal dispersions in a Newtonian solvent [Phys.Rev.E 71,036707 (2005)]. An improved formulation called the ``Smoothed Profile (SP) method'' is presented here in which simultaneous time-marching is used for the host fluid and colloids. The SP method is a direct numerical simulation of particulate flows and provides a coupling scheme between the continuum fluid dynamics and rigid-body dynamics through utilization of a smoothed profile for the colloidal particles. Moreover, the improved formulation includes an extension to incorporat…
