Gravitational collapse of colloidal gels

We investigate the phenomenon of gravitational collapse in colloidal gels via dynamic simulation in moderately concentrated gels formed via arrested phase separation. In such gels, rupture and re-formation of bonds of strength O(kT) permit ongoing structural rearrangements that lead to temporal evolution—aging—of structure and rheology [1]. The reversible nature of the bonds permits a transition from solid-like to liquid-like behavior under external forcing, and back to solid-like behavior when forcing is removed. But such gels have also been reported to undergo sudden and catastrophic collapse of the entire structural network, eliminating any intended functionality of the network scaffold. Although the phenomenon is well studied in the experimental literature, the microscopic mechanisms underlying the collapse remain murky [2-18]. Here we conduct large-scale dynamic simulation to model structural and rheological evolution of a gel subjected to gravitational stress. The model comprises 750,000 Brownian particles interacting via a hard-core repulsion and short-range attractive interactions that lead to formation of a gel, periodically replicated to an infinite system [1]. A body force is applied to the gel, and particle positions, velocities, and pressure are measured throughout simulation, as well as the bulk strain of the gel. Three temporal regimes emerge: slow, pre-collapse evolution; collapse and rapid sedimentation; and long-time compaction producing, to our knowledge, the first large-scale dynamic simulation of gravitational gel collapse. We connect the temporal regimes to distinct phases of structural and rheological evolution. A range of attraction strengths, and their effect on the critical force that triggers collapse, are studied. We find that the initial deformation is slow and linear, and the transition to and scaling of the fast strain rate depends on the strength of gravitational forcing, as is the transition to and rate of the final sedimentation regime, in excellent agreement with experimentally reported behavior [3,9,14]: The detailed microstructural evolution is reported here, along with the dependence of the delay time and speed with attraction strength and magnitude of the applied stress relative to Brownian forces. Please click Additional Files below to see the full abstract

Single-particle motion in colloids: force-induced diffusion

We study the fluctuating motion of a Brownian-sized probe particle as it is dragged by a constant external force through a colloidal dispersion. In this nonlinear-microrheology problem, collisions between the probe and the background bath particles, in addition to thermal fluctuations of the solvent, drive a long-time diffusive spread of the probe's trajectory. The influence of the former is determined by the spatial configuration of the bath particles and the force with which the probe perturbs it. With no external forcing the probe and bath particles form an equilibrium microstructure that fluctuates thermally with the solvent. Probe motion through the dispersion distorts the microstructure; the character of this deformation, and hence its influence on the probe's motion, depends on the strength with which the probe is forced, F^(ext), compared to thermal forces, kT/b, defining a Péclet number, Pe = F^(ext)/(kT/b), where kT is the thermal energy and b the bath particle size. It is shown that the long-time mean-square fluctuational motion of the probe is diffusive and the effective diffusivity of the forced probe is determined for the full range of Péclet number. At small Pe Brownian motion dominates and the diffusive behaviour of the probe characteristic of passive microrheology is recovered, but with an incremental flow-induced ‘microdiffusivity’ that scales as D^(micro) ~ D_aPe^2φ_b, where φ_b is the volume fraction of bath particles and D_a is the self-diffusivity of an isolated probe. At the other extreme of high Péclet number the fluctuational motion is still diffusive, and the diffusivity becomes primarily force induced, scaling as (F^(ext)/η)φ_b, where η is the viscosity of the solvent. The force-induced microdiffusivity is anisotropic, with diffusion longitudinal to the direction of forcing larger in both limits compared to transverse diffusion, but more strongly so in the high-Pe limit. The diffusivity is computed for all Pe for a probe of size a in a bath of colloidal particles, all of size b, for arbitrary size ratio a/b, neglecting hydrodynamic interactions. The results are compared with the force-induced diffusion measured by Brownian dynamics simulation. The theory is also compared to the analogous shear-induced diffusion of macrorheology, as well as to experimental results for macroscopic falling-ball rheometry. The results of this analysis may also be applied to the diffusive motion of self-propelled particles

Individual Particle Motion in Colloids: Microviscosity, Microdiffusivity, and Normal Stresses

Colloidal dispersions play an important role in nearly every aspect of life, from paint to biofuels to nano-therapeutics. In the study of these so-called complex fluids, a connection is sought between macroscopic material properties and the micromechanics of the suspended particles. Such properties include viscosity, diffusivity, and the osmotic pressure, for example. But many such systems are themselves only microns in size overall; recent years have thus seen a dramatic growth in demand for exploring microscale systems at a much smaller length scale than can be probed with conventional macroscopic techniques. Microrheology is one approach to such microscale interrogation, in which a Brownian “probe” particle is driven through a complex fluid, and its motion tracked in order to infer the mechanical properties of the embedding material. With no external forcing the probe and background particles form an equilibrium microstructure that fluctuates thermally with the solvent. Probe motion through the dispersion distorts the microstructure; the character of this deformation, and hence its influence on probe motion, depends on the strength with which the probe is forced, F ext , compared to thermal forces, kT/b, defining a P´eclet number, P e = F ext /(kT /b), where kT is the thermal energy and b the bath-particle size. Both the mean and the fluctuating motion of the probe are of interest. Recent studies showed that the reduction in mean probe speed gives the effective material viscosity. But the velocity of the probe also fluctuates due to collisions with the suspended particles, causing the probe to undergo a random walk process. It is shown that the long-time mean-square fluctuational motion of the probe is diffusive and the effective diffusivity of the forced probe is determined for the full range of P´eclet number. At small Pe Brownian motion dominates and the diffusive behavior of the probe characteristic of passive microrheology is recovered, but with an incremental flow-induced “micro-diffusivity” that scales as Dmicro ∼ Da P e 2 φb , where viii φb is the volume fraction of bath particles and Da is the self-diffusivity of an isolated probe. At the other extreme of high P´eclet number the fuctuational motion is still diffusive, and the diffusivity becomes primarily force-induced , scaling as (F ext /η)φb , where η is the viscosity of the solvent. The force-induced “microdiffusivity” is anisotropic, with diffusion longitudinal to the direction of forcing larger in both limits compared to transverse diffusion, but more strongly so in the high-P e limit. Previous work in microrheology defined a scalar viscosity; however, a tensorial expression for the suspension stress in microrheology was still lacking. The notion that diffusive flux is driven by gradients in particle-phase stress leads to the idea that the microdiffusivity can be related directly to the suspension stress. In consequence, the anisotropy of the diffusion tensor may reflect the presence of normal stress differences in non-linear microrheology. While the particle-phase stress tensor can be determined as the second moment of the deformed microstructure, in this study a connection is made between diffusion and stress gradients, and an analytical expression for particle-phase stress as a function of the microdiffusivity and microviscosity is obtained. The two approaches agree, suggesting that normal stresses and normal stress differences can be measured in active microrheological experiments if both the mean and mean-square motion of the probe are monitored. Owing to the axisymmetry of the motion about a spherical probe, the second normal stress difference is zero, while the first normal stress difference is linear in P e for P e ≫ 1 and vanishes as P e 3 for P e ≪ 1. An additional important outcome is that the analytical expression obtained for stress-induced migration can be viewed as a generalized non-equilibrium Stokes-Einstein relation. Studies of steady-state dispersion behavior reveal the hydrodynamic and microstructural mechanisms that underlie non-Newtonian behaviors (e.g. shear-thinning, shear-thickening, and normal stress differences). But an understanding of how the microstructures evolve from the equilibrium state, and how non-equilibrium properties develop in time is much less well understood. Transient suspension behavior in the near-equilibrium, linear response regime has been studied via its connection to low-amplitude oscillatory probe forcing and the complex modulus; at very weak forcing, the microstructural response that drives viscosity is indistinguishable from equilibrium fluctuations. But important information about the basic physical aspects of structural development and relaxation ix in a medium are captured by start-up and cessation of the imposed deformation in the non-linear regime, where the structure is driven far from equilibrium. Here we study the evolution of stress and microstructure in a colloidal dispersion by tracking transient probe motion during start-up and cessation of a strong flow. For large P e, steady state is reached when a boundary layer (in which advection balances diffusion) forms at particle contact on the timescale of the flow, a/U , where a is the probe size and U its speed. On the other hand, relaxation following cessation occurs over several timescales corresponding to distinct physical processes. For very short times, the timescale for relaxation is set by the diffusion over the boundary-layer thickness. Nearly all stress relaxation occurs during this process, owing to the dependence of the bath-particle drag on the contact value of the microstructure. At longer times the collective diffusion of the bath particles acts to close the wake. In this long-time limit as structural isotropy is restored, the majority of the microstructural relaxation occurs with very little change in suspension stress. Theoretical results are presented and compared with Brownian dynamics simulation. Two regimes of probe motion are studied: an externally applied constant force and an imposed constant velocity. The microstructural evolution is qualitatively different for the two regimes, with a longer transient phase and a thinner boundary layer and longer wake at steady state in the latter case. The work is also compared to analogous results for sheared suspensions undergoing start-up and cessation. The study moves next to investigations of dual-probe microrheology. Motivated by the phenomenon of equilibrium depletion interactions, we study the interaction between a pair of probe particles translating with equal velocity through a dispersion with their line of centers transverse to the external forcing. The character of the microstructure surrounding the probes is determined both by the distance R by which the two probes are separated and by the strength of the external forcing, P e = U a/Db , where U is the constant probe velocity and Db the diffusivity of the bath particles. Osmotic pressure gradients develop as the microstructure is deformed, giving rise to an interactive force between the probes. This force is studied for a range of P e and R. For all separations R > 2a, the probes attract when P e is small. As the strength of the forcing increases, a qualitative change in the interactive force occurs: the probes repel each other. The probe separation R at which the x attraction-to-repulsion transition occurs decreases as P e increases, because the entropic depletion attraction becomes weak compared to the force-induced osmotic repulsion. The non-equilibrium interactive force is strictly repulsive for two separated probes. But non-linear microrheology provides far more than a microscale technique for interrogating complex fluids. In 1906, Einstein published the famous thought experiment in which he proposed that if a liquid were indeed composed of atoms, then the motion of a small particle suspended in the fluid would move with the same random trajectories as the solvent atoms. Combining the theories of kinetics, diffusion, and thermodynamics, he showed that the diffusive motion of a small particle is indeed evidence of the existence of the atom. Perrin confirmed the theory with measurement in 1909. This is a profound conclusion, drawn by simply watching a particle move in a liquid. Here, we follow this example and watch a particle move in a complex fluid—but now for a system that is not at equilibrium. In equilibrium systems, the relationship between fluctuation and dissipation is fundamental to our understanding of colloid physics. By studying fluctuations away from equilibrium, we have discovered an analogous non-equilibrium relation between fluctuation and dissipation—and that the balance between the two is stored in the material stress. A final connection can be made between this stress and energy storage.</p

Vitrification is a spontaneous non-equilibrium transition driven by osmotic pressure.

Persistent dynamics in colloidal glasses suggest the existence of a non-equilibrium driving force for structural relaxation during glassy aging. But the implicit assumption in the literature that colloidal glasses form within the metastable state bypasses the search for a driving force for vitrification and glassy aging and its connection with a metastable state. The natural relation of osmotic pressure to number-density gradients motivates us to investigate the osmotic pressure as this driving force. We use dynamic simulation to quench a polydisperse hard-sphere colloidal liquid into the putative glass region while monitoring structural relaxation and osmotic pressure. Following quenches to various depths in volume fractionϕ(whereϕRCP≈ 0.678 for 7% polydispersity), the osmotic pressure overshoots its metastable value, then decreases with age toward the metastable pressure, driving redistribution of coordination number and interparticle voids that smooths structural heterogeneity with age. For quenches to 0.56 ⩽ϕ⩽ 0.58, accessible post-quench volume redistributes with age, allowing the glass to relax into a strong supercooled liquid and easily reach a metastable state. At higher volume fractions, 0.59 ⩽ϕ&lt; 0.64, this redistribution encounters a barrier that is subsequently overcome by osmotic pressure, allowing the system to relax toward the metastable state. But forϕ⩾ 0.64, the overshoot is small compared to the high metastable pressure; redistribution of volume stops as particles acquire contacts and get stuck, freezing the system far from the metastable state. Overall, the osmotic pressure drives structural rearrangements responsible for both vitrification and glassy age-relaxation. The connection of energy, pressure, and structure identifies the glass transition, 0.63 &lt;ϕg⩽ 0.64. We leverage the connection of osmotic pressure to energy density to put forth the mechanistic view that relaxation of structural heterogeneity in colloidal glasses occurs via individual particle motion driven by osmotic pressure, and is a spontaneous energy minimization process that drives the glass off and back to the metastable state

"Dense diffusion" in colloidal glasses: short-ranged long-time self-diffusion as a mechanistic model for relaxation dynamics.

Despite decades of exploration of the colloidal glass transition, mechanistic explanation of glassy relaxation processes has remained murky. State-of-the-art theoretical models of the colloidal glass transition such as random first order transition theory, active barrier hopping theory, and non-equilibrium self-consistent generalized Langevin theory assert that relaxation reported at volume fractions above the ideal mode coupling theory prediction φg,MCT requires some sort of activated process, and that cooperative motion plays a central role. However, discrepancies between predicted and measured values of φg and ambiguity in the role of cooperative dynamics persist. Underlying both issues is the challenge of conducting deep concentration quenches without flow and the difficulty in accessing particle-scale dynamics. These two challenges have led to widespread use of fitting methods to identify divergence, but most a priori assume divergent behavior; and without access to detailed particle dynamics, it is challenging to produce evidence of collective dynamics. We address these limitations by conducting dynamic simulations accompanied by experiments to quench a colloidal liquid into the putative glass by triggering an increase in particle size, and thus volume fraction, at constant particle number density. Quenches are performed from the liquid to final volume fractions 0.56 ≤ φ ≤ 0.63. The glass is allowed to age for long times, and relaxation dynamics are monitored throughout the simulation. Overall, correlated motion acts to release dynamics from the glassy plateau - but only over length scales much smaller than a particle size - allowing self-diffusion to re-emerge; self-diffusion then relaxes the glass into an intransient diffusive state, which persists for φ &lt; 0.60. We observe similar relaxation dynamics up to φ = 0.63 before achieving the intransient state. We find that this long-time self-diffusion is short-ranged: analysis of mean-square displacement reveals a glassy cage size a fraction of a particle size that shrinks with quench depth, i.e. increasing volume fraction. Thus the equivalence between cage size and particle size found in the liquid breaks down in the glass, which we confirm by examining the self-intermediate scattering function over a range of wave numbers. The colloidal glass transition can hence be viewed mechanistically as a shift in the long-time self-diffusion from long-ranged to short-ranged exploration of configurations. This shift takes place without diverging dynamics: there is a smooth transition as particle mobility decreases dramatically with concomitant emergence of a dense local configuration space that permits sampling of many configurations via local particle motion