Soft Repulsive Particles Research Articles

Memory of shear flow in soft jammed materials.

Cessation of flow in yield stress fluids results in a stress relaxation process that eventually leads to a finite residual stress. Both the rate of stress relaxation and the magnitude of the residual stresses systematically depend on the preceding flow conditions. To assess the microscopic origin of this memory effect, we combine experiments with large-scale computer simulations, exploring the behavior of jammed suspensions of soft repulsive particles. A spatiotemporal analysis of particle motion reveals that memory formation during flow is primarily governed by the emergence of domains of spatially correlated nonaffine displacements. These domains imprint the configuration of stress imbalances that drive dynamics upon flow cessation, as evidenced by a striking equivalence of the spatial correlation patterns in particle displacements observed during flow and upon flow cessation. Additional contributions to stress relaxation result from the particle packing that reorganizes to minimize the resistance to flow by decreasing the number of locally stiffer configurations. Regaining rigidity upon flow cessation drives further relaxation and effectively sets the magnitude of the residual stress. Our findings highlight that flow in yield stress fluids can be seen as a training process during which the material stores information of the flowing state through the development of domains of correlated particle displacements and the reorganization of particle packings optimized to sustain the flow. This encoded memory can then be retrieved in flow cessation experiments.

Gradient descent dynamics and the jamming transition in infinite dimensions

Gradient descent dynamics in complex energy landscapes, i.e. featuring multiple minima, finds application in many different problems, from soft matter to machine learning. Here, we analyze one of the simplest examples, namely that of soft repulsive particles in the limit of infinite spatial dimension d. The gradient descent dynamics then displays a jamming transition: at low density, it reaches zero-energy states in which particles’ overlaps are fully eliminated, while at high density the energy remains finite and overlaps persist. At the transition, the dynamics becomes critical. In the d → ∞ limit, a set of self-consistent dynamical equations can be derived via mean field theory. We analyze these equations and we present some partial progress towards their solution. We also study the random Lorentz gas in a range of d = 2…22, and obtain a robust estimate for the jamming transition in d → ∞. The jamming transition is analogous to the capacity transition in supervised learning, and in the appendix we discuss this analogy in the case of a simple one-layer fully-connected perceptron.

Unjamming in models with analytic pairwise potentials.

Canonical models for studying the unjamming scenario in systems of soft repulsive particles assume pairwise potentials with a sharp cutoff in the interaction range. The sharp cutoff renders the potential nonanalytic but makes it possible to describe many properties of the solid in terms of the coordination number z, which has an unambiguous definition in these cases. Pairwise potentials without a sharp cutoff in the interaction range have not been studied in this context, but should in fact be considered to understand the relevance of the unjamming phenomenology in systems where such a cutoff is not present. In this work we explore two systems with such interactions: an inverse power law and an exponentially decaying pairwise potential, with the control parameters being the exponent (of the inverse power law) for the former and the number density for the latter. Both systems are shown to exhibit the characteristic features of the unjamming transition, among which are the vanishing of the shear-to-bulk modulus ratio and the emergence of an excess of low-frequency vibrational modes. We establish a relation between the pressure-to-bulk modulus ratio and the distance to unjamming in each of our model systems. This allows us to predict the dependence of other key observables on the distance to unjamming. Our results provide the means for a quantitative estimation of the proximity of generic glass-forming models to the unjamming transition in the absence of a clear-cut definition of the coordination number and highlight the general irrelevance of nonaffine contributions to the bulk modulus.

Numerical test of the Edwards conjecture shows that all packings are equally probable at jamming

In the late 1980s, Sam Edwards proposed a possible statistical-mechanical framework to describe the properties of disordered granular materials. A key assumption underlying the theory was that all jammed packings are equally likely. In the intervening years it has never been possible to test this bold hypothesis directly. Here we present simulations that provide direct evidence that at the unjamming point, all packings of soft repulsive particles are equally likely, even though generically, jammed packings are not. Typically, jammed granular systems are observed precisely at the unjamming point since grains are not very compressible. Our results therefore support Edwards' original conjecture. We also present evidence that at unjamming the configurational entropy of the system is maximal.

Liquid-liquid equilibria for soft-repulsive particles: improved equation of state and methodology for representing molecules of different sizes and chemistry in dissipative particle dynamics.

Three developments are presented that significantly expand the applicability of dissipative particle dynamics (DPD) simulations for symmetric and non-symmetric mixtures, where the former contain particles with equal repulsive parameter for self-interactions but a different repulsive parameter for cross-interactions, and the latter contain particles with different repulsive parameters also for the self-interactions. Monte Carlo and molecular dynamics simulations for unary phases covering a wide range of repulsive parameters and of densities for single-bead DPD particles point to deficiencies of the Groot and Warren equation of state (GW-EOS) [J. Chem. Phys. 107, 4423 (1997)]. A revised version, called rGW-EOS, is proposed here that is significantly more accurate over a wider range of parameters/densities. The second development is the generalization of the relationship between the Flory-Huggins χ parameter and the repulsive cross-interaction parameter when the two particles involved have different molecular volumes. The third aspect is an investigation of Gibbs ensemble Monte Carlo simulation protocols, which demonstrates the importance of volume fluctuations and excess volumes of mixing even for equimolar symmetric mixtures of DPD particles. As an illustrative example, the novel DPD methodology is applied to the prediction of the liquid-liquid equilibria for acetic anhydride/(n-hexane or n-octane) binary mixtures.

Diverging viscosity and soft granular rheology in non-Brownian suspensions.

We use large scale computer simulations and finite-size scaling analysis to study the shear rheology of dense three-dimensional suspensions of frictionless non-Brownian particles in the vicinity of the jamming transition. We perform simulations of soft repulsive particles at constant shear rate, constant pressure, and finite system size and carefully study the asymptotic limits of large system sizes and infinitely hard particle repulsion. We first focus on the asymptotic behavior of the shear viscosity in the hard particle limit. By measuring the viscosity increase over about 5 orders of magnitude, we are able to confirm its asymptotic power law divergence close to the jamming transition. However, a precise determination of the critical density and critical exponent is difficult due to the "multiscaling" behavior of the viscosity. Additionally, finite-size scaling analysis suggests that this divergence is accompanied by a growing correlation length scale, which also diverges algebraically. Finally, we study the effect of particle softness and propose a natural extension of the standard granular rheology, which we test against our simulation data. Close to the jamming transition, this "soft granular rheology" offers a detailed description of the nonlinear rheology of soft particles, which differs from earlier empirical scaling forms.

Thinning or thickening? Multiple rheological regimes in dense suspensions of soft particles

The shear rheology of dense colloidal and granular suspensions is strongly nonlinear, as these materials exhibit shear-thinning and shear-thickening, depending on multiple physical parameters. We numerically study the rheology of a simple model of soft repulsive particles at large densities, and show that nonlinear flow curves reminiscent of experiments on real suspensions can be obtained. By using dimensional analysis and basic elements of kinetic theory, we rationalize these multiple rheological regimes and disentangle the relative impact of thermal fluctuations, glass and jamming transitions, inertia and particle softness on the flow curves. We characterize more specifically the shear-thickening regime and show that both particle softness and the emergence of a yield stress at the jamming transition compete with the inertial effects responsible for the observed thickening behaviour. This allows us to construct a dynamic state diagram, which can be used to analyze experiments.

Theory of Localization and Activated Hopping of Nanoparticles in Cross-Linked Networks and Entangled Polymer Melts

We develop a microscopic, force-level statistical dynamical theory for the localization and activated hopping dynamics of dilute spherical particles, both hard and soft, in polymer networks and entangled melts. The main factor controlling localization is the confinement a particle experiences from polymer entanglements and/or chemical cross-links as characterized by the ratio of the effective nanoparticle diameter to the mechanical mesh length, 2Reff/dT. Dynamical localization occurs when the latter ratio is of order unity, and the activated hopping mobility drastically decreases as the confinement parameter even modestly increases past threshold. Local packing correlations slightly enhance the tendency to localize for hard particles and dramatically enhance mobility for soft repulsive particles. The concept of an effective nanoparticle size largely, but not completely, collapses the diverse dynamical results for hard and soft repulsive particles. For hard spheres in entangled polymer melts we find the ex...

Disentangling glass and jamming physics in the rheology of soft materials

The shear rheology of soft particles systems becomes complex at large density because crowding effects may induce a glass transition for Brownian particles, or a jamming transition for non-Brownian systems. Here we successfully explore the hypothesis that the shear stress contributions from glass and jamming physics are `additive'. We show that the experimental flow curves measured in a large variety of soft materials (colloidal hard spheres, microgel suspensions, emulsions, aqueous foams) as well as numerical flow curves obtained for soft repulsive particles in both thermal and athermal limits are well described by a simple model assuming that glass and jamming rheologies contribute linearly to the shear stress, provided that the relevant scales for time and stress are correctly identified in both sectors. Our analysis confirms that the dynamics of colloidal hard spheres is uniquely controlled by glass physics while aqueous foams are only sensitive to jamming effects. We show that for micron-sized emulsions both contributions are needed to successfully account for the flow curves, which reveal distinct signatures of both phenomena. Finally, for two systems of soft microgel particles we show that the flow curves are representative of the glass transition of colloidal systems, and deduce that microgel particles are not well suited to studying the jamming transition experimentally.

Critical scaling of a jammed system after a quench of temperature

Critical behavior of soft repulsive particles after quench of temperature near the jamming transition is numerically investigated. It is found that the plateau of the mean-square displacement of tracer particles and the pressure satisfy critical scaling laws. The critical density for the jamming transition depends on the protocol to prepare the system, while the values of the critical exponents which are consistent with the prediction of a phenomenology are independent of the protocol.

Unified study of glass and jamming rheology in soft particle systems

We explore numerically the shear rheology of soft repulsive particles at large volume fraction. The interplay between viscous dissipation and thermal motion results in multiple rheological regimes encompassing Newtonian, shear-thinning, and yield stress regimes near the "colloidal" glass transition when thermal fluctuations are important, crossing over to qualitatively similar regimes near the "jamming" transition when dissipation dominates. In the crossover regime, glass and jamming sectors coexist and give complex flow curves. Although glass and jamming limits are characterized by similar macroscopic flow curves, we show that they occur over distinct time and stress scales and correspond to distinct microscopic dynamics. We propose a simple rheological model describing the glass-to-jamming crossover in the flow curves, and discuss the experimental implications of our results.

Microscopic theory of the jamming transition of harmonic spheres

We develop a microscopic theory to analyze the phase behavior and compute correlation functions of dense assemblies of soft repulsive particles both at finite temperature, as in colloidal materials, and at vanishing temperature, a situation relevant for granular materials and emulsions. We use a mean-field statistical mechanical approach which combines elements of liquid state theory to replica calculations to obtain quantitative predictions for the location of phase boundaries, macroscopic thermodynamic properties, and microstructure of the system. We focus, in particular, on the derivation of scaling properties emerging in the vicinity of the jamming transition occurring at large density and zero temperature. The new predictions we obtain for pair correlation functions near contact are tested using computer simulations. Our work also clarifies the conceptual nature of the jamming transition and its relation to the phenomenon of the glass transition observed in atomic liquids.

Microscopic Mean-Field Theory of the Jamming Transition

Dense particle packings acquire rigidity through a nonequilibrium jamming transition commonly observed in materials from emulsions to sandpiles. We describe athermal packings and their observed geometric phase transitions by using equilibrium statistical mechanics and develop a fully microscopic, mean-field theory of the jamming transition for soft repulsive spherical particles. We derive analytically some of the scaling laws and exponents characterizing the transition and obtain new predictions for microscopic correlation functions of jammed states that are amenable to experimental verifications and whose accuracy we confirm by using computer simulations.

Scaling of the glassy dynamics of soft repulsive particles: A mode-coupling approach

We combine the hypernetted chain approximation of liquid state theory with the mode-coupling theory of the glass transition to analyze the structure and dynamics of soft spheres interacting via harmonic repulsion. We determine the locus of the fluid-glass dynamic transition in a temperature--volume fraction phase diagram. The zero-temperature (hard-sphere) glass transition influences the dynamics at finite temperatures in its vicinity. This directly implies a form of dynamic scaling for both the average relaxation time and dynamic susceptibilities quantifying dynamic heterogeneity. We discuss several qualitative disagreements between theory and existing simulations at equilibrium. Our theoretical results are, however, very similar to numerical results for the driven athermal dynamics of repulsive spheres, suggesting that "mean-field" mode-coupling approaches might be good starting points to describe these nonequilibrium dynamics.

Large attractive depletion interactions in soft repulsive–sphere binary mixtures

We consider binary mixtures of soft repulsive spherical particles and calculate the depletion interaction between two big spheres mediated by the fluid of small spheres, using different theoretical and simulation methods. The validity of the theoretical approach, a virial expansion in terms of the density of the small spheres, is checked against simulation results. Attention is given to the approach toward the hard-sphere limit and to the effect of density and temperature on the strength of the depletion potential. Our results indicate, surprisingly, that even a modest degree of softness in the pair potential governing the direct interactions between the particles may lead to a significantly more attractive total effective potential for the big spheres than in the hard-sphere case. This might lead to significant differences in phase behavior, structure, and dynamics of a binary mixture of soft repulsive spheres. In particular, a perturbative scheme is applied to predict the phase diagram of an effective system of big spheres interacting via depletion forces for a size ratio of small and big spheres of 0.2; this diagram includes the usual fluid-solid transition but, in the soft-sphere case, the metastable fluid-fluid transition, which is probably absent in hard-sphere mixtures, is close to being stable with respect to direct fluid-solid coexistence. From these results, the interesting possibility arises that, for sufficiently soft repulsive particles, this phase transition could become stable. Possible implications for the phase behavior of real colloidal dispersions are discussed.

Simulation of the gyroid phase in off-lattice models of pure diblock copolymer melts

Particle-based molecular simulations of pure diblock copolymer (DBC) systems were performed in continuum space via dissipative particle dynamics and Monte Carlo methods for a bead-spring chain model. This model consisted of chains of soft repulsive particles often used with dissipative particle dynamics. The gyroid phase was successfully simulated in DBC melts at selected conditions provided that the simulation box size was commensurate with the gyroid lattice spacing. Simulations were concentrated at conditions where the gyroid phase is expected to be stable which allowed us to outline approximate phase boundaries. When more than one phase was observed by varying simulation box size, thermodynamic stability was discerned by comparing the Helmholtz free energy of the competing phases. For this purpose, chemical potentials were efficiently simulated via an expanded ensemble that gradually inserts/deletes a target chain to/from the system. These simulations employed a novel combination of Bennett's [J. Comput. Phys. 22, 245 (1976)] acceptance-ratio method to estimate free-energy differences and a recently proposed method to get biasing weights that maximize the number of times that the target chain is regrown. The analysis of the gyroid nodes revealed clear evidence of packing frustration in the form of an (entropically) unfavorably overstretching of chains, a phenomenon that has been suggested to provide the structural basis for the limited region of stability of the gyroid phase in the DBC phase diagram. Finally, the G phase and nodal chain stretching were also found in simulations with a completely different DBC particle-based model.

Nematic-isotropic interfaces under shear: A molecular-dynamics simulation

We present a large-scale molecular-dynamics study of nematic-paranematic interfaces under shear. We use a model of soft repulsive ellipsoidal particles with well-known equilibrium properties, and consider interfaces which are oriented normal to the direction of the shear gradient (common stress case). The director at the interface is oriented parallel to the interface (planar). A fixed average shear rate is imposed with moving periodic boundary conditions, and the heat is dissipated with a profile-unbiased thermostat. First, we study the properties of the interface at one particular shear rate in detail. The local interfacial profiles and the capillary wave fluctuations of the interfaces are calculated and compared with those of the corresponding equilibrium interface. Under shear, the interfacial width broadens and the capillary wave amplitudes at large wavelengths increase. The strain is distributed inhomogeneously in the system (shear banding), the local shear rate in the nematic region being distinctly higher than in the paranematic region. Surprisingly, we also observe (symmetry-breaking) flow in the vorticity direction, with opposite direction in the nematic and the paranematic state. Finally, we investigate the stability of the interface for other shear rates and construct a nonequilibrium phase diagram.

Long-Time Behavior of the Velocity Autocorrelation Function for a Fluid of Soft Repulsive Particles

By a molecular-dynamics simulation of a three-dimensional system of 4000 particles, we show that the long-time tail of the velocity autocorrelation function has the form ${\ensuremath{\alpha}}_{0}{t}^{\ensuremath{-}\frac{3}{2}}$, where $t$ is the time and ${\ensuremath{\alpha}}_{0}$ a coefficient depending on the kinematic viscosity and on the diffusion coefficient.