Within mean-field theory we determine the universal scaling function for the effective force acting on a single colloid located near the interface between two coexisting liquid phases of a binary liquid mixture close to its critical consolute point. This is the first study of critical Casimir forces emerging from the confinement of a fluctuating medium by at least one soft interface, instead by rigid walls only as studied previously. For this specific system, our semi-analytical calculation illustrates that knowledge of the colloid-induced, deformed shape of the interface allows one to accurately describe the effective interaction potential between the colloid and the interface. Moreover, our analysis demonstrates that the critical Casimir force involving a deformable interface is accurately described by a universal scaling function, the shape of which differs from that one for rigid walls.
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.
We investigate colloidal suspensions under shear flow through numerical experiments. By measuring the time-correlation function of a bond-orientational order parameter, we find a divergent time scale near a transition point from a disordered fluid phase to an ordered fluid phase, where the order is characterized by a nonzero value of the bond-orientational order parameter. We also present a phase diagram in the $(ρ, \dotγ^{\mathrm{ex}})$ plane, where $ρ$ is the density of the colloidal particles and $\dotγ^{\mathrm{ex}}$ is the shear rate of the solvent. The transition line in the phase diagra…
Capillary bridges can form between colloids immersed in a two phase fluid, e.g., in a binary liquid mixture, if the surface of the colloids prefers the species other than the one favored in the bulk liquid. Here, we study the formation of liquid bridges induced by confining colloids to a slit, with the slit walls having a preference opposite to the one of the colloid surface. Using mean field theory, we show that there is a line of first-order phase transitions between the bridge and the no-bridge states, which ends at a critical point. By decreasing the slit width, this critical point is shif…
Using video-microscopy imaging we demonstrate the existence of a short-ranged equilibrium attraction between heavy silica colloids diffusing on soft surfaces of cross-linked polymer gels. The inter-colloid potential can be tuned by changing the gel stiffness or by coating the colloids with a polymer layer. On sufficiently soft substrates, the interaction induced by the polymer matrix leads to large-scale colloidal aggregation. We correlate the in-plane interaction with a colloid-surface attraction.
We investigate binary mixtures of large colloids interacting through soft potentials with small, ideal depletants. We show that softness has a dramatic effect on the resulting colloid-colloid effective potential when the depletant-to-colloid size ratio $q$ is small, with significant consequences on the colloidal phase behaviour. We also provide an exact relation that allows us to obtain the effective pair potential for {\it any} type of colloid-depletant interactions in the case of ideal depletants, without having to rely on complicated and expensive full-mixture simulations. We also show that…
Understanding the dynamics of soft colloids, such as star polymers, dendrimers, and microgels, is of scientific and practical importance. It is known that the excluded volume effect plays a key role in colloidal dynamics. Here, we propose a condition of compressibility equivalence that provides a simple method to experimentally evaluate the excluded volume of soft colloids from a thermodynamic view. We apply this condition to survey the dynamics of a series of star polymer dispersions. It is found that as the concentration increases, the slowing of the long-time self-diffusivity of the star po…
Soft colloids allow to explore high density states well beyond random close packing. An important open question is whether softness controls the dynamics under these dense conditions. While experimental works reported conflicting results, numerical studies so far mostly focused on simple models that allow particles to overlap, but neglect particle deformations, thus making the concept of softness in simulations and in experiments very different. To fill this gap here we propose a new model system consisting of polymer rings with internal elasticity. At high packing fractions the system display…
Within mean-field theory we calculate the scaling functions associated with critical Casimir forces for a system consisting of two spherical colloids immersed in a binary liquid mixture near its consolute point and facing a planar, homogeneous substrate. For several geometrical arrangements and boundary conditions we analyze the normal and the lateral critical Casimir forces acting on one of the two colloids. We find interesting features such as a change of sign of these forces upon varying either the position of one of the colloids or the temperature. By subtracting the pairwise forces from t…
The design of complex materials and the formation of specific patterns often arise from the properties of the individual building blocks. In this respect, colloidal systems offer a unique opportunity because nowadays they can be synthesized in the laboratory with many different shapes and features. Hence, an appropriate choice of the particle characteristics makes it possible to generate macroscopic structures with desired properties. The versatility of colloids can also be explored in two dimensions, using liquid-liquid or air-liquid interfaces as privileged substrates where they can adsorb a…
During the jamming of thermal colloids, the first peak of the pair distribution function shows a maximum height $g_1^{\rm max}$. We find that $g_1^{\rm max}$ is accompanied by significant change of material properties and thus signifies the transition from unjammed to jammed glasses. The scaling laws at $g_1^{\rm max}$ lead to scaling collapse of structural and thermodynamic quantities, indicating the criticality of the T=0 jamming transition. The physical significance of $g_1^{\rm max}$ is highlighted by its coincidence with the equality of the kinetic and potential energy and the maximum flu…
We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time $τ_α$ of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of $τ_α$ on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this non-equilibrium regime, …
By means of extensive simulations, we investigate concentrated solutions of globular single-chain nanoparticles (SCNPs), an emergent class of synthetic soft nano-objects. By increasing the concentration, the SCNPs show a reentrant behaviour in their structural and dynamical correlations, as well as a soft caging regime and weak dynamic heterogeneity. The latter is confirmed by validation of the Stokes-Einstein relation up to concentrations far beyond the overlap density. Therefore SCNPs arise as a new class of soft colloids, exhibiting slow dynamics and actualizing in a real system structural …
The rheology near jamming of a suspension of soft colloidal spheres is studied using a custom microfluidic rheometer that provides stress versus strain rate over many decades. We find non-Newtonian behavior below the jamming concentration and yield stress behavior above it. The data may be collapsed onto two branches with critical scaling exponents that agree with expectations based on Hertzian contacts and viscous drag. These results support the conclusion that jamming is similar to a critical phase transition, but with interaction-dependent exponents.
We combine experiments and simulations to study the link between criticality and gelation in sticky spheres. We employ confocal microscopy to image colloid-polymer mixtures, and Monte Carlo simulations of the square-well (SW) potential as a reference model. To this end, we map our experimental samples onto the SW model. We find excellent structural agreement between experiments and simulations, both for locally favored structures at the single particle level and large-scale fluctuations at criticality. We follow in detail the rapid structural change of the critical fluid when approaching the g…
Particle tracking and displacement covariance matrix techniques are employed to investigate the phonon dispersion relations of two-dimensional colloidal glasses composed of soft, thermoresponsive microgel particles whose temperature-sensitive size permits \textit{in situ} variation of particle packing fraction. Bulk, $B$, and shear, $G$, moduli of the colloidal glasses are extracted from the dispersion relations as a function of packing fraction, and variation of the ratio $G/B$ with packing fraction is found to agree quantitatively with predictions for jammed packings of frictional soft parti…
We explore the influence of particle softness and internal structure on both the bulk and interfacial rheological properties of colloidal suspensions. We probe bulk stresses by conventional rheology, by measuring the flow curves, shear stress vs strain rate, for suspensions of soft, deformable microgel particles and suspensions of near hard-sphere-like silica particles. A similar behavior is seen for both kind of particles in suspensions at concentrations up to the random close packing volume fraction, in agreement with recent theoretical predictions for sub-micron colloids. Transient interfac…
The growing interest in the dynamical properties of colloidal suspensions, both in equilibrium and under an external drive such as shear or pressure flow, requires the development of accurate methods to correctly include hydrodynamic effects due to the suspension in a solvent. In the present work, we generalize Multi-Particle Collision Dynamics (MPCD) to be able to deal with soft, polymeric colloids. Our methods build on the knowledge of the monomer density profile that can be obtained from monomer-resolved simulations without hydrodynamics or from theoretical arguments. We hereby propose two …
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…
In this article, we demonstrate a method for inducing reversible crystal-to-crystal transitions in binary mixtures of soft colloidal particles. Through a controlled decrease of salinity and increasingly dominating electrostatic interactions, a single sample is shown to reversibly organize into entropic crystals, electrostatic attraction-dominated crystals or aggregated gels, which we quantify using microscopy and image analysis. We furthermore analyze crystalline structures with bond order analysis to discern between two crystal phases. We observe the different phases using a sample holder geo…
By employing monomer-resolved computer simulations and analytical considerations based on polymer scaling theory, we analyze the conformations and interactions of multiarm star polymers strongly adsorbed on a smooth, two-dimensional plane. We find a stronger stretching of the arms as well as a stronger repulsive, effective interaction than in the three dimensional case. In particular, the star size scales with the number of arms $f$ as $\sim f^{1/4}$ and the effective interaction as $\sim f^{2}$, as opposed to $\sim f^{1/5}$ and $\sim f^{3/2}$, respectively, in three dimensions. Our results de…
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…
Concentrated colloidal suspensions and emulsions are amorphous soft solids, widespread in technological and industrial applications and studied as model systems in physics and material sciences. They are easily fluidized by applying a mechanical stress, undergoing a yielding transition that still lacks a unified description. Here, we investigate yielding in three classes of repulsive soft solids, using analytical and numerical modelling and experiments probing the microscopic dynamics and mechanical response under oscillatory shear. We find that at the microscopic level yielding consists in a …
We discuss the reliability of integral-equation methods based on several commonly used closure relations in determining the phase diagram of coarse-grained models of soft-matter systems characterized by mutually interacting soft and hard-core particles. Specifically, we consider a set of potentials appropriate to describe a system of hard-sphere colloids and linear homopolymers in good solvent, and investigate the behavior when the soft particles are smaller than the colloids, which is the regime of validity of the coarse-grained models. Using computer-simulation results as a benchmark, we fin…
We investigate the dynamics of kinetically frozen block copolymer micelles of different softness across a wide range of particle concentrations, from the fluid to the onset of glassy behavior, through a combination of rheology, dynamic light scattering and pulsed field gradient NMR spectroscopy. We additionally perform Brownian dynamics simulations based on an ultrasoft coarse-grained potential, which are found to be in quantitative agreement with experiments, capturing even the very details of dynamic structure factors S(Q, t) on approaching the glass transition. We provide evidence that for …
Colloidal self-assembly -- the spontaneous organization of colloids into ordered structures -- has been considered key to produce next-generation materials. However, the present-day staggering variety of colloidal building blocks and the limitless number of thermodynamic conditions make a systematic exploration intractable. The true challenge in this field is to turn this logic around, and to develop a robust, versatile algorithm to inverse design colloids that self-assemble into a target structure. Here, we introduce a generic inverse design method to efficiently reverse-engineer crystals, qu…
In complex crystals close to melting or at finite temperatures, different types of defects are ubiquitous and their role becomes relevant in the mechanical response of these solids. Conventional elasticity theory fails to provide a microscopic basis to include and account for the motion of point-defects in an otherwise ordered crystalline structure. We study the elastic properties of a point-defect rich crystal within a first-principles theoretical framework derived from microscopic equations of motion. This framework allows us to make specific predictions pertaining to the mechanical properti…
We study numerically the critical behavior and marginal stability of the shear jamming transition for frictionless soft spheres, observed to occur over a finite range of densities, associated with isotropic jamming for densities above the minimum jamming (J-point) density. Several quantities are shown to scale near the shear jamming point in the same way as the isotropic jamming point. We compute the exponents associated with the small force distribution and the interparticle gap distribution,and show that the corresponding exponents are consistent with the marginal stability condition observe…
Extreme deformation of soft matter is central to our understanding of the effects of shock, fracture, and phase change in a variety of systems. Yet, despite, the increasing interest in this area, far-from-equilibrium behaviours of soft matter remain challenging to probe. Colloidal suspensions are often used to visualise emergent behaviours in soft matter, as they offer precise control of interparticle interactions, and ease of visualisation by optical microscopy. However, previous studies have been limited to deformations that are orders of magnitude too slow to be representative of extreme de…
A basic concept in chain-particle cluster-motion, from frozen glassy state to melt state, is the 2D soft nano-scale mosaic structure formed by 8 orders of 2D interface excitation (IE) loop-flows, from small to large in inverse cascade and re-arrangement structure in cascade along local one direction. IE has additional repulsive energy and extra vacancy volume. IE results from that the instantaneous synchronal polarized electron charge coupling pair is able to parallel transport on the interface between two neighboring chain-particles with antiparallel delocalization. This structure accords wit…
Responsive poly-N-isopropylacrylamide-based microgels are commonly used as model colloids with soft repulsive interactions. It has been shown that the microgel-microgel interaction in solution can be easily adjusted by varying the environmental parameters, e.g., temperature, pH, or salt concentration. Furthermore, microgels readily adsorb to liquid-gas and liquid-liquid interfaces forming responsive foams and emulsions that can be broken on-demand. In this work, we explore the interactions between microgel monolayers at the air-water interface and a hard colloid in the water. Force-distance cu…
Colloidal suspensions have a rich rheology and can exhibit shear-thinning as well as shear-thickening. Numerical simulations recently suggested that shear-thickening may be attributed to the inertia of the colloids, besides the hydrodynamic interactions between them. Here, we consider the ideal limit of a dense bath of soft colloids following an underdamped Langevin dynamics. We use a mean-field equation for the colloidal density to get an analytical expression of the drag force felt by a probe pulled at constant velocity through the suspension. Our results show that inertia can indeed induce …
Limited bonding valence, usually accompanied by well-defined directional interactions and selective bonding mechanisms, is nowadays considered among the key ingredients to create complex structures with tailored properties: even though isotropically interacting units already guarantee access to a vast range of functional materials, anisotropic interactions can provide extra instructions to steer the assembly of specific architectures. The anisotropy of effective interactions gives rise to a wealth of self-assembled structures both in the realm of suitably synthesized nano- and micro-sized buil…
A promising approach in designing composite materials with unusual physical behavior combines solid nanostructures and orientationally ordered soft matter at the mesoscale. Such composites not only inherit properties of their constituents but also can exhibit emergent behavior, such as ferromagnetic ordering of colloidal metal nanoparticles forming mesoscopic magnetization domains when dispersed in a nematic liquid crystal. Here we demonstrate the optical patterning of domain structures and topological defects in such ferromagnetic liquid crystal colloids, which allows for altering their respo…
Within mean-field theory we calculate universal scaling functions associated with critical Casimir forces for a system consisting of three parallel cylindrical colloids immersed in a near-critical binary liquid mixture. For several geometrical arrangements and boundary conditions at the surfaces of the colloids we study the force between two colloidal particles along their center-to-center axis, analyzing the influence of the presence of a third particle on that force. Upon changing temperature or the relative positions of the particles we observe interesting features such as a change of sign …
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…
We consider gelation of colloidal particles in suspension after cessation of shear flow. Particle aggregation is driven by a temperature-tunable attractive potential which controls the growth of clusters under isothermal conditions. A series of frequency resolved time sweeps is used to systematically reconstruct the frequency dependent dynamic moduli as a function of time and temperature or attraction strength. The data display typical hallmarks of gelation with an abrupt transition from a fluid state into a dynamically arrested gel state after a characteristic gelation time $t_g$ that varies …
We consider the link between fragility and elasticity that follows from analysis of the data for a set of soft-colloid materials consisting of deformable spheres reported by Mattsson et. al., in Nature vol 462, 83 (2009). Fragility index for a soft-colloid is obtained from the density dependence of the long time relaxation near a so-called glass transition point. In addition, we fit data for the high frequency shear modulus for the respective soft-colloid to a corresponding theoretical expression for the same modulus. This expression for the elastic constant is in terms of the corresponding pa…
Soft nanocomposites represent both a theoretical and an experimental challenge due to the high number of the microscopic constituents that strongly influence the behaviour of the systems. An effective theoretical description of such systems invokes a reduction of the degrees of freedom to be analysed, hence requiring the introduction of an efficient, quantitative, coarse-grained description. We here report on a novel coarse graining approach based on a set of transferable potentials that quantitatively reproduces properties of mixtures of linear and star-shaped homopolymeric nanocomposites. By…
Computer simulations of bi-continuous two-phase fluids with intersparsed dumbbells show that, unlike rigid colloids, soft dumbbells do not lead to arrested coarsening. However, they significantly alter the curvature dynamics of the fluid-fluid interface, whose probability density distributions are shown to exhibit (i) a universal spontaneous transition from an initial broad-shape distribution towards a highly localized one and (ii) super-diffusive dynamics with long-range effects. Both features may prove useful for the design of novel families of soft porous materials.
The dynamics of soft colloids in solutions is characterized by internal collective motion as well as center-of-mass diffusion. Using neutron scattering we demonstrate that the competition between the relaxation processes associated with these two degrees of freedom results in strong dependence of dynamics and structure on colloid concentration, c, even well below the overlap concentration c*. We show that concurrent with increasing inter-particle collisions, substantial structural dehydration and slowing-down of internal dynamics occur before geometrically defined colloidal overlap develops. W…
We investigate the dynamics of a phase-separating binary fluid, containing colloidal dumbbells anchored to the fluid-fluid interface. Extensive Lattice Boltzmann-Immersed Boundary method simulations reveal that the presence of soft dumbbells can significantly affect the curvature dynamics of the interface between phase-separating fluids, even though the coarsening dynamics is left nearly unchanged. In addition, our results show that the curvature dynamics exhibits distinct non-local effects, which might be exploited for the design of new soft mesoscale materials. We point out that the inspecti…
The implications of soft `patchy' interactions on the orientational disorder-order transition of strongly elongated colloidal rods and flat disks is studied within a simple Onsager-van der Waals density functional theory. The theory provides a generic framework for studying the liquid crystal phase behaviour of highly anisometric cylindrical colloids, which carry a distinct geometrical pattern of repulsive or attractive soft interactions localised on the particle surface. In this paper, we apply our theory to the case of charged rods and disks for which the local electrostatic interactions can…
We explore the microstructure and phase behavior of confined soft colloids which can actively switch their interactions at a predefined kinetic rate. For this, we employ a reaction-diffusion approach based on a reactive dynamical density-functional theory (R-DDFT) and study the effect of a binary (two-state) switching of the size of colloids interacting with a Gaussian pair potential. The rate of switching interpolates between a near-equilibrium binary Gaussian mixture at low rates and an effective monodisperse liquid for large rates, hence strongly affecting the one-body density profiles, ads…
Collective motion in actively propelled particle systems is triggered on the very local scale by nucleation of coherently moving units consisting of just a handful of particles. These units grow and merge over time, ending up in a long-range ordered, coherently-moving state. So far, there exists no bottom-up understanding of how the microscopic dynamics and interactions between the constituents are related to the system's ordering instability. In this paper, we study a class of models for propelled colloids allowing an explicit treatment of the microscopic details of the collision process. Spe…
We study the emergence of critical dynamics in the steady shear rheology of fluidized soft glassy materials. Within a mesoscale elasto-plastic model accounting for a shear band instability, we show how an additional noise can induce a transition from phase separated to homogeneous flow, accompanied by critical-like fluctuations of the macroscopic shear rate. Both macroscopic quantities and fluctuations exhibit power law behaviors in the vicinity of this transition, consistent with previous experimental findings on vibrated granular media. Altogether, our results suggest a generic scenario for …
