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Michael E. Cates

Publications and source records attributed to Michael E. Cates.

At least 109 records · Page 6Linked to original sources

Size limit for particle-stabilized emulsion droplets under gravity

We demonstrate that emulsion droplets stabilized by interfacial particles become unstable beyond a size threshold set by gravity. This holds not only for colloids but supra-colloidal glass beads, using which we directly observe the ejection of particles near the droplet base. The number of particles acting together in these ejection events decreases with time until a stable acorn-like configuration is reached. Stability occurs when the weight of all remaining particles is less than the interfacial binding force of one particle. We also show the importance of the curvature of the droplet surface in promoting particle ejection.

cond-mat.soft↗

Delayed solidification of soft glasses: New experiments, and a theoretical challenge

When subjected to large amplitude oscillatory shear stress, aqueous Laponite suspensions show an abrupt solidification transition after a long delay time tc. We measure the dependence of tc on stress amplitude, frequency, and on the age-dependent initial loss modulus. At first sight our observations appear quantitatively consistent with a simple soft-glassy rheology (SGR)-type model, in which barrier crossings by mesoscopic elements are purely strain-induced. For a given strain amplitude γ0 each element can be classified as fluid or solid according to whether its local yield strain exceeds γ0. Each cycle, the barrier heights E of yielded elements are reassigned according to a fixed prior distribution ρ(E): this fixes the per-cycle probability R(γ0) of a fluid elements becoming solid. As the fraction of solid elements builds up, γ0 falls (at constant stress amplitude), so R(γ0) increases. This positive feedback accounts for the sudden solidification after a long delay. The model thus appears to directly link macroscopic rheology with mesoscopic barrier height statistics: within its precepts, our data point towards a power law for ρ(E) rather than the exponential form usually assumed in SGR. However, despite this apparent success, closer investigation shows that the assumptions of the model cannot be reconciled with the extremely large strain amplitudes arising in our experiments. The quantitative explanation of delayed solidification in Laponite therefore remains an open theoretical challenge.

cond-mat.soft↗

From compact to fractal crystalline clusters in concentrated systems of monodisperse hard spheres

We address the crystallization of monodisperse hard spheres in terms of the properties of finite- size crystalline clusters. By means of large scale event-driven Molecular Dynamics simulations, we study systems at different packing fractions ϕ ranging from weakly supersaturated state points to glassy ones, covering different nucleation regimes. We find that such regimes also result in different properties of the crystalline clusters: compact clusters are formed in the classical-nucleation-theory regime (ϕ \leq 0.54), while a crossover to fractal, ramified clusters is encountered upon increasing packing fraction (ϕ \geq 0.56), where nucleation is more spinodal-like. We draw an analogy between macroscopic crystallization of our clusters and percolation of attractive systems to provide ideas on how the packing fraction influences the final structure of the macroscopic crystals. In our previous work (Phys. Rev. Lett., 106, 215701, 2011), we have demonstrated how crystallization from a glass (at ϕ > 0.58) happens via a gradual (many-step) mechanism: in this paper we show how the mechanism of gradual growth seems to hold also in super-saturated systems just above freezing showing that static properties of clusters are not much affected by dynamics.

cond-mat.soft↗

Field-Induced Breakup of Emulsion Droplets Stabilized by Colloidal Particles

We simulate the response of a particle-stabilized emulsion droplet in an external force field, such as gravity, acting equally on all $N$ particles. We show that the field strength required for breakup (at fixed initial area fraction) decreases markedly with droplet size, because the forces act cumulatively, not individually, to detach the interfacial particles. The breakup mode involves the collective destabilization of a solidified particle raft occupying the lower part of the droplet, leading to a critical force per particle that scales approximately as $N^{-1/2}$.

cond-mat.soft↗

Thermodynamic Interpretation of Soft Glassy Rheology Models

Mesoscopic models play an important role in our understanding of the deformation and flow of amorphous materials. One such description, based on the Shear Transformation Zone (STZ) theory, has recently been re-formulated within a non-equilibrium thermodynamics framework, and found to be consistent with it. We show here that a similar interpretation can be made for the Soft Glassy Rheology (SGR) model. Conceptually this means that the "noise temperature" x, proposed phenomenologically in the SGR model to control the dynamics of a set of slow mesoscopic degrees of freedom, can consistently be interpreted as their actual thermodynamic temperature. (Because such modes are slow to equilibrate, this generally does not coincide with the temperature of the fast degrees of freedom and/or heat bath.) If one chooses to make this interpretation, the thermodynamic framework significantly constrains extensions of the SGR approach to models in which x is a dynamical variable. We assess in this light some such extensions recently proposed in the context of shear banding.

cond-mat.soft↗

Age-dependent transient shear banding in soft glasses

We study numerically the formation of long-lived transient shear bands during shear startup within two models of soft glasses (a simple fluidity model and an adapted `soft glassy rheology' model). The degree and duration of banding depends strongly on the applied shear rate, and on sample age before shearing. In both models the ultimate steady flow state is homogeneous at all shear rates, consistent with the underlying constitutive curve being monotonic. However, particularly in the SGR case, the transient bands can be extremely long lived. The banding instability is neither `purely viscous' nor `purely elastic' in origin, but is closely associated with stress overshoot in startup flow.

cond-mat.soft↗

Hawkes process as a model of social interactions: a view on video dynamics

We study by computer simulation the "Hawkes process" that was proposed in a recent paper by Crane and Sornette (Proc. Nat. Acad. Sci. USA 105, 15649 (2008)) as a plausible model for the dynamics of YouTube video viewing numbers. We test the claims made there that robust identification is possible for classes of dynamic response following activity bursts. Our simulated timeseries for the Hawkes process indeed fall into the different categories predicted by Crane and Sornette. However the Hawkes process gives a much narrower spread of decay exponents than the YouTube data, suggesting limits to the universality of the Hawkes-based analysis.

physics.soc-ph↗

Colloidal gels assembled via a temporary interfacial scaffold

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 a short-ranged attraction with a repulsive barrier can strongly stabilize such locally planar gels.

cond-mat.soft↗

Hydrodynamic interactions in colloidal ferrofluids: A lattice Boltzmann study

We use lattice Boltzmann simulations, in conjunction with Ewald summation methods, to investigate the role of hydrodynamic interactions in colloidal suspensions of dipolar particles, such as ferrofluids. Our work addresses volume fractions $ϕ$ of up to 0.20 and dimensionless dipolar interaction parameters $λ$ of up to 8. We compare quantitatively with Brownian dynamics simulations, in which many-body hydrodynamic interactions are absent. Monte Carlo data are also used to check the accuracy of static properties measured with the lattice Boltzmann technique. At equilibrium, hydrodynamic interactions slow down both the long-time and the short-time decays of the intermediate scattering function $S(q,t)$, for wavevectors close to the peak of the static structure factor $S(q)$, by a factor of roughly two. The long-time slowing is diminished at high interaction strengths whereas the short-time slowing (quantified via the hydrodynamic factor $H(q)$) is less affected by the dipolar interactions, despite their strong effect on the pair distribution function arising from cluster formation. Cluster formation is also studied in transient data following a quench from $λ= 0$; hydrodynamic interactions slow the formation rate, again by a factor of roughly two.

cond-mat.mes-hall↗

A mode coupling theory for Brownian particles in homogeneous steady shear flow

A microscopic approach is presented for calculating general properties of interacting Brownian particles under steady shearing. We start from exact expressions for shear-dependent steady-state averages, such as correlation and structure functions, in the form of generalized Green-Kubo relations. To these we apply approximations inspired by the mode coupling theory (MCT) for the quiescent system, accessing steady-state properties by integration through the transient dynamics after startup of steady shear. Exact equations of motion, with memory effects, for the required transient density correlation functions are derived next; these can also be approximated within an MCT-like approach. This results in closed equations for the non-equilibrium stationary state of sheared dense colloidal dispersions, with the equilibrium structure factor of the unsheared system as the only input. In three dimensions, these equations currently require further approximation prior to numerical solution. However, some universal aspects can be analyzed exactly, including the discontinuous onset of a yield stress at the ideal glass transition predicted by MCT. Using these methods we additionally discuss the distorted microstructure of a sheared hard-sphere colloid near the glass transition, and consider how this relates to the shear stress. Time-dependent fluctuations around the stationary state are then approximated, and compared to data from experiment and simulation; the correlators for yielding glassy states obey a `time-shear-superposition' principle. The work presented here fully develops an approach first outlined previously (M. Fuchs and M. E. Cates, Phys. Rev. Lett. 89, 248304, (2002)), while incorporating a significant technical change from that work in the choice of mode coupling approximation used, whose advantages are discussed.

cond-mat.soft↗

Rheology of giant micelles

Giant micelles are elongated, polymer-like objects created by the self-assembly of amphiphilic molecules (such as detergents) in solution. Giant micelles are typically flexible, and can become highly entangled even at modest concentrations. The resulting viscoelastic solutions show fascinating flow behaviour (rheology) which we address theoretically in this article at two levels. First, we summarise advances in understanding linear viscoelastic spectra and steady-state nonlinear flows, based on microscopic constitutive models that combine the physics of polymer entanglement with the reversible kinetics of self-assembly. Such models were first introduced two decades ago, and since then have been shown to explain robustly several distinctive features of the rheology in the strongly entangled regime, including extreme shear-thinning. We then turn to more complex rheological phenomena, particularly involving spatial heterogeneity, spontaneous oscillation, instability, and chaos. Recent understanding of these complex flows is based largely on grossly simplified models which capture in outline just a few pertinent microscopic features, such as coupling between stresses and other order parameters such as concentration. The role of `structural memory' (the dependence of structural parameters such as the micellar length distribution on the flow history) in explaining these highly nonlinear phenomena is addressed. Structural memory also plays an intriguing role in the little-understood shear-thickening regime, which occurs in a concentration regime close to but below the onset of strong entanglement, and which is marked by a shear-induced transformation from an inviscid to a gelatinous state.

cond-mat.soft↗

Aging in attraction-driven colloidal glasses

Aging in an attraction-driven colloidal glass is studied by computer simulations. The system is equilibrated without attraction and instantaneously ``quenched'', at constant colloid volume fraction, to one of two states beyond the glass transition; one is close to the transition, and the other one deep in the glass. The evolution of structural properties shows that bonds form in the system, increasing the local density, creating density deficits (holes) elsewhere. This process slows down with the time elapsed since the quench. As a consequence of bond formation, there is a slowing down of the dynamics, as measured by the mean squared displacement and the density, bond, and environment correlation functions. The density correlations can be time-rescaled to collapse their long time (structural) decay. The time scale for structural relaxation shows for both quenches a super-linear dependence on waiting time; it grows faster than the bond lifetime, showing the collective origin of the transition. At long waiting times and high attraction strength, we observe {\rem completely} arrested dynamics for more than three decades in time, although individual bonds are not permanent on this time scale. The localization length decreases as the state moves deeper in the glass; the non-ergodicity parameter oscillates in phase with the structure factor. Our main results are obtained for systems with a barrier in the pair potential that inhibits phase separation. However, when this barrier is removed for the case of a deep quench, we find changes in the static structure but almost none in the dynamics. Hence our results for the aging behavior remain relevant to experiments in which the glass transition competes with phase separation.

cond-mat.soft↗

Dynamical heterogeneities in an attraction driven colloidal glass

The dynamical heterogeneities (DH) in non-ergodic states of an attractive colloidal glass are studied, as a function of the waiting time. Whereas the fluid states close to vitrify showed strong DH, the distribution of squared displacements of the glassy states studied here only present a tail of particles with increased mobility for the lower attraction strength at short waiting times. These particles are in the surface of the percolating cluster that comprises all of the particles, reminiscent of the fastest particles in the fluid. The quench deeper into the attractive glass is dynamically more homogeneous, in agreement with repulsive glasses (i.e. Lennard-Jones glass).

cond-mat.soft↗

Integration through transients for Brownian particles under steady shear

Starting from the microscopic Smoluchowski equation for interacting Brownian particles under stationary shearing, exact expressions for shear-dependent steady-state averages, correlation and structure functions, and susceptibilities are obtained, which take the form of generalized Green-Kubo relations. They require integration of transient dynamics. Equations of motion with memory effects for transient density fluctuation functions are derived from the same microscopic starting point. We argue that the derived formal expressions provide useful starting points for approximations in order to describe the stationary non-equilibrium state of steadily sheared dense colloidal dispersions.

cond-mat.soft↗

Dynamical heterogeneities close to a colloidal gel

Dynamical heterogeneities in a colloidal fluid close to gelation are studied by means of computer simulations. A clear distinction between some fast particles and the rest, slow ones, is observed, yielding a picture of the gel composed by two populations with different mobilities. Analyzing the statics and dynamics of both sets of particles, it is shown that the slow particles form a network of stuck particles, whereas the fast ones are able to move over long distances. Correlation functions show that the environment of the fast particles relaxes much faster than that of the slow ones, but at short times the bonds between fast particles are longer lived due to the flexibility of their structure. No string-like motion is observed for the fast particles, but they occupy preferential sites in the surface of the structure formed by the slow ones.

cond-mat.soft↗

Mode Coupling and Dynamical Heterogeneity in Colloidal Gelation: A Simulation Study

We present simulation results addressing the dynamics of a colloidal system with attractive interactions close to gelation. Our interaction also has a soft, long range repulsive barrier which suppresses liquid-gas type phase separation at long wavelengths. The new results presented here lend further weight to an intriguing picture emerging from our previous simulation work on the same system. Whereas mode coupling theory (MCT) offers quantitatively good results for the decay of correlators, closer inspection of the dynamics reveals a bimodal population of fast and slow particles with a very long exchange timescale. This population split represents a particular form of dynamic heterogeneity (DH). Although DH is usually associated with activated hopping and/or facilitated dynamics in glasses, the form of DH observed here may be more collective in character and associated with static (i.e., structural) heterogeneity.

cond-mat.soft↗

Simulation study of Non-ergodicity Transitions: Gelation in Colloidal Systems with Short Range Attractions

Computer simulations were used to study the gel transition occurring in colloidal systems with short range attractions. A colloid-polymer mixture was modelled and the results were compared with mode coupling theory expectations and with the results for other systems (hard spheres and Lennard Jones). The self-intermediate scattering function and the mean squared displacement were used as the main dynamical quantities. Two different colloid packing fractions have been studied. For the lower packing fraction, $α$-scaling holds and the wave-vector analysis of the correlation function shows that gelation is a regular non-ergodicity transition within MCT. The leading mechanism for this novel non-ergodicity transition is identified as bond formation caused by the short range attraction. The time scale and diffusion coefficient also show qualitatively the expected behaviour, although different exponents are found for the power-law divergences of these two quantities. The non-Gaussian parameter was also studied and very large correction to Gaussian behaviour found. The system with higher colloid packing fraction shows indications of a nearby high-order singularity, causing $α$-scaling to fail, but the general expectations for non-ergodicity transitions still hold.

cond-mat.soft↗

Theory of nonlinear rheology and yielding of dense colloidal suspensions

A first principles approach to the nonlinear flow of dense suspensions is presented which captures shear thinning of colloidal fluids and dynamical yielding of colloidal glasses. The advection of density fluctuations plays a central role, suppressing the caging of particles and speeding up structural relaxation. A mode coupling approach is developed to explore these effects.

cond-mat.soft↗