Soft Glassy Materials Research Articles

Cell Growth Rate Dictates the Onset of Glass to Fluid-Like Transition and Long Time Super-Diffusion in an Evolving Cell Colony

Collective migration dominates many phenomena, from cell movement in living systems to abiotic self-propelling particles. Focusing on the early stages of tumor evolution, we enunciate the principles involved in cell dynamics and highlight their implications in understanding similar behavior in seemingly unrelated soft glassy materials and possibly chemokine-induced migration of CD8$^{+}$ T cells. We performed simulations of tumor invasion using a minimal three dimensional model, accounting for cell elasticity and adhesive cell-cell interactions as well as cell birth and death to establish that cell growth rate-dependent tumor expansion results in the emergence of distinct topological niches. Cells at the periphery move with higher velocity perpendicular to the tumor boundary, while motion of interior cells is slower and isotropic. The mean square displacement, $\Delta(t)$, of cells exhibits glassy behavior at times comparable to the cell cycle time, while exhibiting super-diffusive behavior, $\Delta (t) \approx t^{\alpha}$ ($\alpha > 1$), at longer times. We derive the value of $\alpha \approx 1.33$ using a field theoretic approach based on stochastic quantization. In the process we establish the universality of super-diffusion in a class of seemingly unrelated non-equilibrium systems. Super diffusion at long times arises only if there is an imbalance between cell birth and death rates. Our findings for the collective migration, which also suggests that tumor evolution occurs in a polarized manner, are in quantitative agreement with {\it in vitro} experiments. Although set in the context of tumor invasion the findings should also hold in describing collective motion in growing cells and in active systems where creation and annihilation of particles play a role.

Wall fluidization in two acts: from stiff to soft roughness.

Fluidization of soft glassy materials (SGMs) in microfluidic channels is affected by the wall roughness in the form of microtexturing. When SGMs flow across microgrooves, their constituents are likely trapped within the grooves' gap, and the way they are released locally modifies the fluidization close to the walls. By leveraging a suitable combination of experiments and numerical simulations on concentrated emulsions (a model SGM), we quantitatively report the existence of two physically different scenarios. When the gap is large compared to the droplets in the emulsion, the droplets hit the solid obstacles and easily escape scrambling with their neighbors. Conversely, as the gap spacing is reduced, droplets get trapped inside, creating a "soft roughness" layer, i.e. a complementary series of deformable posts from which overlying droplets are in turn released. In both cases, the induced fluidization scales with the grooves' density, although with a reduced prefactor for narrow gaps, accounting for the softness of the roughness. Both scenarios are also well distinguished via the statistics of the droplets displacement field close to the walls, with large deviations induced by the surface roughness, depending on its stiffness.

Asymmetric soft-hard colloidal mixtures: Osmotic effects, glassy states and rheology

Whereas mixtures of colloids and nonadsorbing polymers have been studied in great detail in the last two decades, binary colloidal mixtures have not received much attention. Yet, fragmental evidence from asymmetric mixtures of hard spheres indicates a wide-ranging, complex behavior from liquid to crystal to single glass and to double glass, and respective rich rheology. Recently, we addressed the question of softness by investigating a mixture of soft and virtually hard colloidal spheres. We found an unprecedented wealth of states including repulsive single glass (RG), liquid, arrested phase separation (APS), and double glass (DG). This is a consequence of the coupling of softness and osmotic forces due to the hard component. We now report on the rheology of the different states with emphasis on the nonlinear response during startup of stress at constant rate, its relaxation upon flow cessation, and large amplitude oscillatory shearing. Distinct features are identified, whereas comparison with single-colloid (soft or hard) glasses reveals some phenomenological universalities in yielding, residual stresses and periodic intracycle stress response. In brief, the DG exhibits much larger yield and residual stresses as compared to the RG and APS, whereas the yield strain is the same for all states. Two-step yielding is unambiguously evidenced for the APS whereas both yield stress and strain exhibit a weak dependence on Péclet number. Large amplitude oscillatory tests reveal large value of the intrinsic nonlinear parameters, reflecting the role of colloidal interactions. Moreover, RG exhibits intracycle stress overshoots, a feature that characterizes most of the soft glassy materials formed by interpenetrable particles and that vanishes as hard (nearly impenetrable) colloids are added in the mixtures. These results demonstrate the sensitivity of linear and nonlinear rheology to colloidal state transitions and, more importantly, the power of entropic mixing as a means to tailor the flow properties, hence performance and handling of soft composites.

Boltzmann superposition principle for a time-dependent soft material: assessment under creep flow field

Variety of time-dependent soft materials that undergo evolution of microstructure are known to follow the Boltzmann superposition principle when appropriately transformed from the real to the effective time domain. This behavior is attributed to obliteration of time dependency in the effective time domain by normalizing the real time by the time-dependent relaxation time. This work is aimed at assessing validity of the Boltzmann superposition principle in the effective time domain under application of step changes and ramps in stress for a time-dependent soft glassy material: an aqueous suspension of Laponite, whose rheological properties are known to show strong time and stress dependency. Interestingly, creep experiments started at different aging times and for different constant stresses indeed lead to a comprehensive time–aging time–stress superposition resulting in time and stress dependence of relaxation time and modulus. Subsequently, we analyze compliance response of the material to different kinds of stress step change and ramp combinations. We observe that except few, most of the compliance data plotted in the effective time domain does not overlap on the comprehensive superposition. We analyze this behavior and attribute the observed mismatch to the history dependence of the time evolution of modulus.

Fluidization and wall slip of soft glassy materials by controlled surface roughness.

We present a comprehensive study of concentrated emulsions flowing in microfluidic channels, one wall of which is patterned with micron-size equally spaced grooves oriented perpendicularly to the flow direction. We find a scaling law describing the roughness-induced fluidization as a function of the density of the grooves, thus fluidization can be predicted and quantitatively regulated. This suggests common scenarios for droplet trapping and release, potentially applicable for other jammed systems as well. Numerical simulations confirm these views and provide a direct link between fluidization and the spatial distribution of plastic rearrangements.

Structure and Rheology of Microgel Monolayers at the Water/Oil Interface

We investigate the rheological property of microgel monolayers at the water/oil interface using passive and active microrheological methods. At low surface coverage, the microgels at the water/oil interface have a tendency to form aggregated structures (networks) with dominating elasticity. At high surface coverage the microgels form densely packed monolayers. Using microsized magnetic particles as the local rheological probes in the dense microgel monolayers, we perform in situ study of their rheological properties and structures. We observe four regimes where the elasticity of the microgel monolayer has different dependence on the microgel concentration at the interface. The rheological properties of the microgel monolayers are not only dependent on the concentration but also strongly correlated with the intermicrogel distance and spacial arrangement of the microgels at the interface. Our results also show that the microgel monolayers act similar to soft glassy materials.

Understanding rheological hysteresis in soft glassy materials.

Motivated by recent experimental studies of rheological hysteresis in soft glassy materials, we study numerically strain rate sweeps in simple yield stress fluids and viscosity bifurcating yield stress fluids. Our simulations of downward followed by upward strain rate sweeps, performed within fluidity models and the soft glassy rheology model, successfully capture the experimentally observed monotonic decrease of the area of the rheological hysteresis loop with sweep time in simple yield stress fluids, and the bell shaped dependence of hysteresis loop area on sweep time in viscosity bifurcating fluids. We provide arguments explaining these two different functional forms in terms of differing tendencies of simple and viscosity bifurcating fluids to form shear bands during the sweeps, and show that the banding behaviour captured by our simulations indeed agrees with that reported experimentally. We also discuss the difference in hysteresis behaviour between inelastic and viscoelastic fluids. Our simulations qualitatively agree with the experimental data discussed here for four different soft glassy materials.

Softening and yielding of soft glassy materials.

Solids deform and fluids flow, but soft glassy materials, such as emulsions, foams, suspensions, and pastes, exhibit an intricate mix of solid- and liquid-like behavior. While much progress has been made to understand their elastic (small strain) and flow (infinite strain) properties, such understanding is lacking for the softening and yielding phenomena that connect these asymptotic regimes. Here we present a comprehensive framework for softening and yielding of soft glassy materials, based on extensive numerical simulations of oscillatory rheological tests, and show that two distinct scenarios unfold depending on the material's packing density. For dense systems, there is a single, pressure-independent strain where the elastic modulus drops and the particle motion becomes diffusive. In contrast, for weakly jammed systems, a two-step process arises: at an intermediate softening strain, the elastic and loss moduli both drop down and then reach a new plateau value, whereas the particle motion becomes diffusive at the distinctly larger yield strain. We show that softening is associated with an extensive number of microscopic contact changes leading to a non-analytic rheological signature. Moreover, the scaling of the softening strain with pressure suggest the existence of a novel pressure scale above which softening and yielding coincide, and we verify the existence of this crossover scale numerically. Our findings thus evidence the existence of two distinct classes of soft glassy materials - jamming dominated and dense - and show how these can be distinguished by their rheological fingerprint.

GPU based detection of topological changes in Voronoi diagrams

The Voronoi diagrams are an important tool having theoretical and practical applications in a large number of fields. We present a new procedure, implemented as a set of CUDA kernels, which detects, in a general and efficient way, topological changes in case of dynamic Voronoi diagrams whose generating points move in time. The solution that we provide has been originally developed to identify plastic events during simulations of soft-glassy materials based on a lattice Boltzmann model with frustrated-short range attractive and mid/long-range repulsive-interactions. Along with the description of our approach, we present also some preliminary physics results.

Molecular Origins of Temperature-Induced Jamming in Self-Suspended Hairy Nanoparticles

Suspensions of solvent-less, polymer-grafted nanoparticles have previously been reported to exhibit enhanced elasticity, glassy dynamics, and jamming as temperature is increased. This so-called thermal jamming behavior is not predicted by current models for soft glassy materials and is opposite to what is normally observed for polymer melts. Here we report results from a detailed study of structural, dynamic, and rheological transitions in solvent-less silica–poly(ethylene glycol) methyl ether (SiO2–PEGME) hybrid particles aimed at understanding the molecular origins of the phenomenon. We find that interdigitated PEGME corona chains enforce coupling between SiO2 cores analogous to cross-links in associating polymer networks leading to elastic behavior at low strains and small deformation rates. Pullout and slippage of interdigitated corona chains is thought to produce yielding of the materials in nonlinear shear flow and stretched exponential relaxation following small amplitude step shear. We show with the help of small-angle X-ray scattering, density functional theoretical calculations, and a constitutive model previously reported for deformation and flow of physically associating polymer networks, that thermal jamming of solvent-less polymer-grafted nanoparticles originates from enhanced cross-linking of the cores produced by increased stretching and interpenetration of particle-tethered polymer molecules to satisfy the space-filling constraint on tethered polymer chains.

Shear Banding of Soft Glassy Materials in Large Amplitude Oscillatory Shear.

We study shear banding in soft glassy materials subject to a large amplitude oscillatory shear flow (LAOS). By numerical simulations of the widely used soft glassy rheology model, supplemented by more general physical arguments, we demonstrate strong banding over an extensive range of amplitudes and frequencies of the imposed shear rate γ[over ˙](t)=γ[over ˙]_{0}cos(ωt), even in materials that do not permit banding as their steady state response to a steadily imposed shear flow γ[over ˙]=γ[over ˙]_{0}=const. Highly counterintuitively, banding persists in LAOS even in the limit of zero frequency ω→0, where one might apriori have expected a homogeneous flow response in a material that does not display banding under conditions of steadily imposed shear. We explain this finding in terms of an alternating competition within each cycle between glassy aging and flow rejuvenation. Our predictions have far-reaching implications for the flow behavior of aging yield stress fluids, suggesting a generic expectation of shear banding in flows of even arbitrarily slow time variation.

Earthquake statistics and plastic events in soft-glassy materials

We propose a new approach for generating synthetic earthquake catalogues based on the physics of soft glasses. The continuum approach produces yield-stress materials based on Lattice-Boltzmann simulations. We show that, if the material is stimulated below yield stress, plastic events occur, which have strong similarities with seismic events. Based on a suitable definition of displacement in the continuum, we show that the plastic events obey a Gutenberg-Richter law with exponents similar to those for real earthquakes. We further find that average acceleration, energy release, stress drop and recurrence times scale with the same exponent. The approach is fully self-consistent and all quantities can be calculated at all scales without the need of ad hoc friction or statistical laws. We therefore suggest that our approach may lead to new insight into understanding of the physics connecting the micro and macro scale of earthquakes.

Understanding soft glassy materials using an energy landscape approach.

Many seemingly different soft materials-such as soap foams, mayonnaise, toothpaste and living cells-display strikingly similar viscoelastic behaviour. A fundamental physical understanding of such soft glassy rheology and how it can manifest in such diverse materials, however, remains unknown. Here, by using a model soap foam consisting of compressible spherical bubbles, whose sizes slowly evolve and whose collective motion is simply dictated by energy minimization, we study the foam's dynamics as it corresponds to downhill motion on an energy landscape function spanning a high-dimensional configuration space. We find that these downhill paths, when viewed in this configuration space, are, surprisingly, fractal. The complex behaviour of our model, including power-law rheology and non-diffusive bubble motion and avalanches, stems directly from the fractal dimension and energy function of these paths. Our results suggest that ubiquitous soft glassy rheology may be a consequence of emergent fractal geometry in the energy landscapes of many complex fluids.

Fluidisation and plastic activity in a model soft-glassy material flowing in micro-channels with rough walls

By means of mesoscopic numerical simulations of a model soft-glassy material, we investigate the role of boundary roughness on the flow behaviour of the material, probing the bulk/wall and global/local rheologies. We show that the roughness reduces the wall slip induced by wettability properties and acts as a source of fluidisation for the material. A direct inspection of the plastic events suggests that their rate of occurrence grows with the fluidity field, reconciling our simulations with kinetic elasto-plastic descriptions of jammed materials. Notwithstanding, we observe qualitative and quantitative differences in the scaling, depending on the distance from the rough wall and on the imposed shear. The impact of roughness on the orientational statistics is also studied.

Shear Banding of Complex Fluids

Even in simple geometries, many complex fluids display nontrivial flow fields, with regions where shear is concentrated. The possibility for such shear banding has been known for several decades, but in recent years, we have seen an upsurge in studies offering an ever-more precise understanding of the phenomenon. The development of new techniques to probe the flow on multiple scales with increasing spatial and temporal resolution has opened the possibility for a synthesis of the many phenomena that could only have been thought of separately before. In this review, we bring together recent research on shear banding in polymeric and soft glassy materials and highlight their similarities and disparities.

Passive microrheology in the effective time domain: analyzing time dependent colloidal dispersions.

We studied the aging dynamics of an aqueous suspension of LAPONITE®, a model time dependent soft glassy material, using a passive microrheology technique. This system is known to undergo physical aging during which its microstructure evolves progressively to explore lower free energy states. Optical microscopy is used to monitor the motion of micron-sized tracer probes embedded in a sample kept between two glass plates. The mean square displacements (MSD) obtained from the motion of the tracer particles show a systematic change from a purely diffusive behavior at short aging times to a subdiffusive behavior as the material ages. Interestingly, the MSDs at all the aging times as well as different LAPONITE® concentrations superpose remarkably to show a time-aging time master curve when the system is transformed from the real time domain to the effective time domain, which is obtained by rescaling the material clock to account for the age dependent relaxation time. The transformation of the master curve from the effective time domain to the real time domain leads to the prediction of the MSD in real time over a span of 5 decades when the measured data at individual aging times are only over 2 decades. Since the MSD obtained from microrheology is proportional to the creep compliance of a material, by using the Boltzmann superposition principle along with the convolution relation in the effective time domain, we predict the stress relaxation behavior of the system in real time. This work shows that the effective time approach applied to microrheology facilitates the prediction of long time creep and relaxation dynamics of a time dependent soft material by carrying out short time experiments at different aging times.

Characteristics of the secondary relaxation process in soft colloidal suspensions

A universal secondary relaxation process, known as the Johari-Goldstein (J-G) β-relaxation process, appears in glass formers. It involves all parts of the molecule and is particularly important in glassy systems because of its very close relationship with the α-relaxation process. However, the absence of a J-G β-relaxation mode in colloidal glasses raises questions regarding its universality. In the present work, we study the microscopic relaxation processes in Laponite suspensions, a model soft glassy material, by dynamic light scattering (DLS) experiments. α- and β-relaxation timescales are estimated from the autocorrelation functions obtained by DLS measurements for Laponite suspensions with different concentrations, salt concentrations and temperatures. Our experimental results suggest that the β-relaxation process in Laponite suspensions involves all parts of the constituent Laponite particle. The ergodicity breaking time is also seen to be correlated with the characteristic time of the β-relaxation process for all Laponite concentrations, salt concentrations and temperatures. The width of the primary relaxation process is observed to be correlated with the secondary relaxation time. The secondary relaxation time is also very sensitive to the concentration of Laponite. We measure primitive relaxation timescales from the α-relaxation time and the stretching exponent (β) by applying the coupling model for highly correlated systems. The order of magnitude of the primitive relaxation time is very close to the secondary relaxation time. These observations indicate the presence of a J-G β-relaxation mode for soft colloidal suspensions of Laponite.

A model for complex flows of soft glassy materials with application to flows through fixed fiber beds

The soft glassy rheology (SGR) model has successfully described the time dependent simple shear rheology of a broad class of complex fluids including foams, concentrated emulsions, colloidal glasses, and solvent-free nanoparticle-organic hybrid materials (NOHMs). The model considers a distribution of mesoscopic fluid elements that hop from trap to trap at a rate which is enhanced by the work done to strain the fluid element. While an SGR fluid has a broad exponential distribution of trap energies, the rheology of NOHMs is better described by a narrower energy distribution and we consider both types of trap energy distributions in this study. We introduce a tensorial version of these models with a hopping rate that depends on the orientation of the element relative to the mean stress field, allowing a range of relative strengths of the extensional and simple shear responses of the fluid. As an application of these models we consider the flow of a soft glassy material through a dilute fixed bed of fibers. The dilute fixed bed exhibits a range of local linear flows which alternate in a chaotic manner with time in a Lagrangian reference frame. It is amenable to an analytical treatment and has been used to characterize the strong flow response of many complex fluids including fiber suspensions, dilute polymer solutions and emulsions. We show that the accumulated strain in the fluid elements has an abrupt nonlinear growth at a Deborah number of order one in a manner similar to that observed for polymer solutions. The exponential dependence of the hopping rate on strain leads to a fluid element deformation that grows logarithmically with Deborah number at high Deborah numbers. SGR fluids having a broad range of trap energies flowing through fixed beds can exhibit a range of rheological behaviors at small Deborah numbers ranging from a yield stress, to a power law response and finally to Newtonian behavior.

Mesoscopic Simulation Study of Wall Roughness Effects in Micro-channel Flows of Dense Emulsions

We study the Poiseuille flow of a soft-glassy material above the jamming point, where the material flows like a complex fluid with Herschel–Bulkley rheology. Microscopic plastic rearrangements and the emergence of their spatial correlations induce cooperativity flow behavior whose effect is pronounced in presence of confinement. With the help of lattice Boltzmann numerical simulations of confined dense emulsions, we explore the role of geometrical roughness in providing activation of plastic events close to the boundaries. We probe also the spatial configuration of the fluidity field, a continuum quantity which can be related to the rate of plastic events, thereby allowing us to establish a link between the mesoscopic plastic dynamics of the jammed material and the macroscopic flow behaviour.

Hyperdiffusive Dynamics in Newtonian Nanoparticle Fluids.

Hyperdiffusive relaxations in soft glassy materials are typically associated with out-of-equilibrium states, and nonequilibrium physics and aging are often invoked in explaining their origins. Here, we report on hyperdiffusive motion in model soft materials comprised of single-component polymer-tethered nanoparticles, which exhibit a readily accessible Newtonian flow regime. In these materials, polymer-mediated interactions lead to strong nanoparticle correlations, hyperdiffusive relaxations, and unusual variations of properties with temperature. We propose that hyperdiffusive relaxations in such materials can arise naturally from nonequilibrium or non-Brownian volume fluctuations forced by equilibrium thermal rearrangements of the particle pair orientations corresponding to equilibrated shear modes.