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Attractive colloidal glasses are unique as their dynamical arrest is a combination of entropic crowding effects and energetic bonds formation. When such systems are subjected to flow, their dynamics are activated in a way which differs from hard-sphere glasses that melt through a "convective cage release mechanism." Here, we investigate the microscopic dynamics by measuring the relaxation spectrum during flow using orthogonal superposition rheometry. A small amplitude oscillatory strain is imposed perpendicularly to a steady shear flow, and superposition moduli are measured. Brownian dynamic simulations are utilized complementary to extract the moduli from mean-squared displacements using the generalized Stokes–Einstein relation. At low Péclet number, a crossover frequency between elastic and viscous moduli is detected, representing the relaxation time associated with shear-induced particles escape from their frustration (localization) under flow. For the repulsive glass, this is related to shear-induced cage renewal of particles. For attractive glasses, however, when particles escape their localized length (bonds), they move with no further hindrance with the escape time, which is independent of attraction strength and interestingly faster than that in the repulsive glass. This is attributed to particle localization at shorter length scales due to bonding. At high Péclet, a second low frequency crossover is observed and a low frequency elastic dominated response emerges. This elastic response may originate from slow relaxation of hydroclusters or be a consequence of more intricate nature of superposition moduli. At high frequencies, both orthogonal moduli increase relative to quiescent state due to shear-induced cage deformation, which slows down in-cage dynamics. [ABSTRACT FROM AUTHOR]

We investigate the phenomenon of delayed yield in reversible colloidal gels via dynamic simulation, with a view toward revealing the microscopic particle dynamics and structural transformations that underlie the rheological behavior before, during, and after yield. Prior experimental studies reveal a pronounced delay period between application of a fixed shear stress and the onset of liquidlike flow, a so-called "delay time." Catastrophic network failure-with sudden, cascading rupture of particle clusters or strands-is the primary model proposed for the structural evolution underlying rheological yield. However, no direct observation of such evolution has been made, owing to the difficulty of obtaining detailed microstructural information during the rapid yield event. Here, we utilize dynamic simulation to examine the microstructural mechanics and rheology of delayed yield. A moderately concentrated dispersion of Brownian hard spheres interacts via a short-range attractive potential of O(kT) that leads to arrested phase separation and the formation of a bicontinuous network of reversibly bonded particles. The linearresponse rheology and coarsening dynamics of this system were characterized in our recent work. In the present study, a step shear stress is imposed on the gel, and its bulk deformation, as well as detailed positions and dynamics of all particles, are monitored over time. Immediately after the stress is imposed, the gel undergoes solidlike creep regardless of the strength of the applied stress. However, a minimum or "critical stress" is required to initiate yield: When the imposed stress is weak compared to the Brownian stress, the gel continues to undergo slow creeping deformation with no transition to liquidlike flow. Under stronger stress, creep is followed by a sudden increase in the strain rate, signaling yield, which then gives way to liquidlike viscous flow. The duration of the creep regime prior to yield is consistent with the delay time identified in prior experimental studies, decreasing monotonically with increasing applied stress. However, when the deformation rate is interrogated as a function of strain (rather than time), we find that a critical strain emerges: Yield occurs at the same extent of deformation regardless of the magnitude of the applied stress. Surprisingly, the gel network can remain fully connected throughout yield, with as few as 0.1% of particle bonds lost during yield, which relieve local glassy frustration and create localized liquidlike regions that enable yield. Brownian motion plays a central role in this behavior: When thermal motion is "frozen out," both the delay time and the critical yield stress increase, showing that Brownian motion facilitates yield. Beyond yield, the long-time behavior depends qualitatively on the strength of the applied stress. In particular, at intermediate stresses, a "re-entrant solid" regime emerges, whereupon a flowing gel resolidifies, owing to flow-enhanced structural coarsening. A nonequilibrium phase diagram is presented that categorizes, and can be used to predict, the ultimate gel fate as a function of imposed stress. We make a connection between these behaviors and the process of ongoing phase separation in arrested colloidal gels. [ABSTRACT FROM AUTHOR]

We use particle level dynamic simulations, ultrasonic characterization, and rheomicroscopy to investigate the yielding behavior of magnetorheological (MR) fluids under oscillatory shear in both dilute and concentrated regimes. Dilute suspensions exhibit a single peak in the elastic stress that is associated to the breaking of the field-induced structures at the flow point (G' = G"). On the other hand, more concentrated suspensions demonstrate a two-step yielding that is associated to the existence of short-ranged attractions between the particles, possibly coming from remnant magnetization or van der Waals forces. This two-step yielding is demonstrated by introducing additives in the formulation of the MR fluids and performing particle level simulations that include R-shifted Lennard-Jones potentials of interaction. [ABSTRACT FROM AUTHOR]

We study via theory and dynamical simulation the evolving structure, particle dynamics, and time-dependent rheological properties of an aging colloidal gel, with a focus on the micro-mechanics that drive coarsening and age-related changes in linear-response behavior. When colloids in suspension attract one another, the attractions can lead to phase separation into particle-rich and particle-poor regions separated by a single interface. But this transition is sometimes interrupted before full separation occurs. With certain particle concentrations and interparticle potentials, the attractions that promote phase separation also inhibit it, frustrating the separation and "freezing in" a nonequilibrium particle configuration, resulting in a space-spanning gel. With attractions on the order of a few kT, gelation can produce nonfractal bicontinuous morphologies. In such "reversible" gels, thermal fluctuations are strong enough to rupture bonds and reform new ones, allowing restructuring of the gel over time. But, because particle diffusion is dramatically slowed by interparticle attractions, the march toward equilibrium is frustrated. Prior studies of colloidal gels have examined evolution of length scales and dynamics such as decorrelation times or heterogeneity. Left open were additional questions such as how the particle-rich regions are structured (liquidlike, glassy, and crystalline), how restructuring takes place (via bulk diffusion, surface migration, and coalescence of large structures), and the impact of the evolution on rheology. In this study, we conduct dynamic simulations to elucidate the post-gelation evolution of a system of 750 000 Brownian spheres interacting via a hard-sphere repulsion and short-range attractions of order kT, as would be generated by a polymer depletant, for example. We find that the network strands comprise a glassy, immobile interior near random-close packing, enclosed by a liquidlike surface along which the diffusive migration of particles drives coarsening. We show that coarsening is a three-step process of cage forming, cage hopping, and cage arrest, where particles migrate to ever-deeper energy wells via "Smoluchowski's ratchet." Both elastic and viscous high-frequency moduli are found to scale with the square-root of the frequency, similar to the perfectly viscoelastic behavior of nonhydrodynamically interacting, purely repulsive dispersions. But here, the behavior is elastic over all frequencies, with a quantitative offset between elastic and viscous moduli which owes its origin to the hindrance of diffusion by particle attractions. Propagation of this elasticity via the network gives rise to age-stiffening as the gel coarsens. This simple phenomenological model suggests a rescaling of the moduli on network length scale which, when carried out, collapses each modulus for all gel ages onto a single universal curve. A theoretical model inspired by the Rouse model is advanced and, from it, we have obtained an analytical expression that captures the effects of (finite) structural aging on rheology: The moduli are linear in the network size, suggesting that linear mechanical response can be determined at any age by measurement of dominant network length scale--or vice versa. [ABSTRACT FROM AUTHOR]

We examine the accuracy of dissipative particle dynamics (DPD) simulations of polymers in dilute solutions with hydrodynamic interaction (HI), at the theta point, modeled by setting the DPD conservative interaction between beads to zero. We compare the first normal-mode relaxation time extracted from the DPD simulations with theoretical predictions from a normal-mode analysis for theta chains. We characterize the influence of bead inertia within the coil by a ratio Lm/Rg, where Lm is the ballistic distance over which bead inertia is lost, and Rg is the radius of gyration of the polymer coil, while the HI strength per bead h* is determined by the ratio of bead hydrodynamic radius (rH) to the equilibrium spring length. We show how to adjust h* through the spring length and monomer mass, and how to optimize the accuracy of DPD for fixed h* by increasing the friction coefficient (γ≥9) and by incorporating a nonlinear distance dependence into the frictional interaction. Even with this optimization, DPD simulations exhibit deviations of over 20% from the theoretical normal-mode predictions for high HI strength with h*≥0.20, for chains with as many as 100 beads, which is a larger deviation than is found for Stochastic rotation dynamics simulations for similar chains lengths and values of h*. [ABSTRACT FROM AUTHOR]