Soft Glassy Research Articles

Continuum modeling of soft glassy materials under shear

Soft Glassy Materials (SGM) consist in dense amorphous assemblies of colloidal particles of multiple shapes, elasticity, and interactions, which confer upon them solid-like properties at rest. They are ubiquitously encountered in modern engineering, including additive manufacturing, semi-solid flow cells, dip coating, adhesive locomotion, where they are subjected to complex mechanical histories. Such processes often include a solid-to-liquid transition induced by large enough shear, which results in complex transient phenomena such as non-monotonic stress responses, i.e., stress overshoot, and spatially heterogeneous flows, e.g., shear banding or brittle failure. In the present article, we propose a pedagogical introduction to a continuum model based on a spatially resolved fluidity approach that we recently introduced to rationalize shear-induced yielding in SGMs. Our model, which relies upon non-local effects, quantitatively captures salient features associated with such complex flows, including the rate dependence of the stress overshoot, as well as transient shear-banded flows together with non-trivial scaling laws for fluidization times. This approach offers a versatile framework to account for subtle effects, such as avalanche-like phenomena, or the impact of boundary conditions, which we illustrate by including in our model the elasto-hydrodynamic slippage of soft particles compressed against solid surfaces.

Experimental observations of fractal landscape dynamics in a dense emulsion.

Many soft and biological materials display so-called 'soft glassy' dynamics; their constituents undergo anomalous random motions and complex cooperative rearrangements. A recent simulation model of one soft glassy material, a coarsening foam, suggested that the random motions of its bubbles are due to the system configuration moving over a fractal energy landscape in high-dimensional space. Here we show that the salient geometrical features of such high-dimensional fractal landscapes can be explored and reliably quantified, using empirical trajectory data from many degrees of freedom, in a model-free manner. For a mayonnaise-like dense emulsion, analysis of the observed trajectories of oil droplets quantitatively reproduces the high-dimensional fractal geometry of the configuration path and its associated local energy minima generated using a computational model. That geometry in turn drives the droplets' complex random motion observed in real space. Our results indicate that experimental studies can elucidate whether the similar dynamics in different soft and biological materials may also be due to fractal landscape dynamics.

Plastic ridge formation in a compressed thin amorphous film

We demonstrate that surface morphogenesis in compressed thin films may result from spatially correlated plastic activity. A soft glassy film strongly adhering to a smooth and rigid substrate and subjected to uniaxial compression, indeed, does not undergo any global elastic pattern-forming instability, but responds plastically via localized burst events that self-organize, leading to the emergence of a series of parallel ridges transverse to the compression axis. This phenomenon has been completely overlooked, but results from common features of the plastic response of glasses hence should be highly generic for compressed glassy thin films.

Replacement effect with Ni on high-frequency permeability and core loss characteristics for FeNiPBSiC glassy alloys

The paper aims to develop an excellent soft magnetic glassy alloy with a series of (Fe1−xNix)79P5B12Si3C1 (x = 0, 0.2, 0.4, 0.5, 0.6). The annealing at (Tg-20) K for the 0.4Ni-0.5Ni alloys causes an extremely low coercivity below 1 A/m with very high effective permeability above 5·104 at 1 kHz in the maintenance of high saturation magnetic flux density of ⋍ 1.2 T. Good effective permeability characteristics were recognized as is evidenced from high μe values above 6000 at 1 MHz. The core losses at induction of 100 mT are as low as 43 W/kg for 100 kHz and 1150 W/kg at 1 MHz for the annealed 0.6Ni alloy. Excellent soft magnetic properties are presumably due to the achievement of the fully relaxed glassy state which can be obtained only for the glass-type alloys with SCL region. This complex of magnetic properties is promising for future use as high-frequency type soft magnetic materials.

Modulation of soft glassy dynamics in aqueous suspensions of an anisotropic charged swelling clay through pH adjustment

HypothesisSodium-montmorillonite (Na-Mt) particles are geometrically anisometric that carry a pH dependent anisotropic surface charge. Therefore, it should be possible to manipulate the particle–particle interaction of colloidal range Na-Mt suspensions through pH changes which in turn should alter the soft glassy dynamics of Na-Mt suspensions. ExperimentsRheological experiments were used to probe the impact of pH mediated colloidal particle–particle interaction on the physical aging, linear viscoelastic response, and yield stress behavior of Na-Mt suspension. FindingsThe temporal evolution of the storage modulus (G') was stronger in the acid regime (pH < 9.5) than the base (pH ≥ 9.5) pH regime. Horizontal shifting of the aging curves in the acid and base regimes led to aging time–H+ concentration and aging time–OH– concentration superposition. An aging time–Na-Mt concentration superposition was also observed in both pH regimes. The critical stress associated with the viscosity bifurcation behavior increased linearly with G' but with different slopes for acid and base regime. We propose that positively charged patches on the Na-Mt particle edge merge with the characteristic surface as a function of H+ ions in the system. This leads to a strongly associated microstructure at low pH and a relatively weak but associated microstructure at natural pH, hence confirming the hypothesis.

Assessing the Interfacial Activity of Insoluble Asphaltene Layers: Interfacial Rheology versus Interfacial Tension

Asphaltenes have been suggested to play an important role in the remarkable stability of some water-in-crude oil emulsions, although the precise mechanisms by which they act are not yet fully understood. Being one of the more polar fractions in crude oils, asphaltenes are surface active and strongly adsorb at the oil/water interface, and as the interface becomes densely packed, solid-like mechanical properties emerge, which influence many typical interfacial experiments. The present work focuses on purposefully measuring the rheology in the limit of an insoluble, spread Langmuir monolayer in the absence of adsorption/desorption phenomena. Moreover, the changes in surface tension are deconvoluted from the purely mechanical contribution to the surface stress by experiments with precise interfacial kinematics. Compression "isotherms" are combined with the measurement of both shear and dilatational rheological properties to evaluate the relative contributions of mechanical versus thermodynamic aspects, i.e., to evaluate the "interfacial rheological" versus the standard interfacial activity. The experimental results suggest that asphaltene nanoaggregates are not very efficient in lowering interfacial tension but rather impart significant mechanical stresses. Interestingly, physical aging effects are not observed in the spread layers, contrary to results for adsorbed layers. By further studying asphaltene fractions of different polarity, we investigate whether mere packing effects or strong interactions determine the mechanical response of the dense asphaltene systems as either soft glassy or gel-like responses have been reported. The compressional and rheological data reflect the dense packing, and the behavior is captured well by the soft glassy rheology model, but a more complicated multilayer structure may develop as coverage is increased. Potential implications of the experimental observations on these model and insoluble interfaces for water-in-crude oil emulsion stability are briefly discussed.

Criticality at a Finite Strain Rate in Fluidized Soft Glassy Materials.

We study the emergence of critical dynamics in the steady shear rheology of fluidized soft glassy materials. Within a mesoscale elastoplastic model accounting for a shear band instability, we show how additional noise can induce a transition from a phase separated to homogeneous flow, accompanied by critical-like fluctuations of the macroscopic shear rate. Both macroscopic quantities and fluctuations exhibit power law behaviors in the vicinity of this transition, consistent with previous experimental findings on vibrated granular media. Altogether, our results suggest a generic scenario for the emergence of criticality when shear weakening mechanisms compete with a fluidizing noise.

Linear shear rheology of aging β-casein films adsorbing at the air/water interface

In this work, the viscoelasticity of fragile β-casein films has been followed using different macro- and microrheological techniques. The modulus of the complex surface viscosity |η∗| varies with time, allowing for the monitoring of the protein adsorption and annealing. β-casein adsorption creates a soft glassy gel at the interface that experiences an aging process. Macrorheological experiments with multiple probe sizes in addition to microrheological experiments demonstrated the consistency of the surface rheological properties over a broad range of viscosities. Surface pressure measurements were performed to complement the characterization of the processes.

Analyzing aging under oscillatory strain field through the soft glassy rheology model.

In this work, we solve the Soft Glassy Rheology (SGR) model under application of oscillatory deformation field with varying magnitudes of strain as well as frequency for different noise temperatures. In the glassy domain, the SGR model undergoes time evolution of elastic modulus. Increase in strain magnitude beyond the linear regime is observed to enhance the rate of aging as manifested by a faster evolution of elastic modulus with increase in strain amplitude due to overaging. However at higher strain magnitudes, the rejuvenation effect starts dominating over the aging, thereby reducing the rate at which elastic modulus evolves. We also plot the aging phase diagram describing an occurrence of the linear, the overaging, and the rejuvenation regimes as a function of strain and frequency for different noise temperatures. The aging phase diagram suggests that while the linear regime remains unaffected by the changes in frequency and noise temperature, the width of the overaging regime increases with increase in frequency and noise temperature. We also study the time evolution of the shapes of relaxation time spectra as a function of strain amplitude, which renders further insight into the overaging and the rejuvenation behavior. While the phenomenon of overaging is observed to be an inherent character of the SGR model, experimentally not all the materials demonstrate overaging. Such a discrepancy suggests that the energy well depths before and after a yielding event may not be completely uncorrelated as assumed in the SGR formalism.

Motility-driven glass and jamming transitions in biological tissues.

Cell motion inside dense tissues governs many biological processes, including embryonic development and cancer metastasis, and recent experiments suggest that these tissues exhibit collective glassy behavior. To make quantitative predictions about glass transitions in tissues, we study a self-propelled Voronoi (SPV) model that simultaneously captures polarized cell motility and multi-body cell-cell interactions in a confluent tissue, where there are no gaps between cells. We demonstrate that the model exhibits a jamming transition from a solid-like state to a fluid-like state that is controlled by three parameters: the single-cell motile speed, the persistence time of single-cell tracks, and a target shape index that characterizes the competition between cell-cell adhesion and cortical tension. In contrast to traditional particulate glasses, we are able to identify an experimentally accessible structural order parameter that specifies the entire jamming surface as a function of model parameters. We demonstrate that a continuum Soft Glassy Rheology model precisely captures this transition in the limit of small persistence times, and explain how it fails in the limit of large persistence times. These results provide a framework for understanding the collective solid-to-liquid transitions that have been observed in embryonic development and cancer progression, which may be associated with Epithelial-to-Mesenchymal transition in these tissues.

Preparation and characterization of monodisperse solvent-free silica nanofluids

ABSTRACTA series of solvent-free ionic silica (SiO2) nanofluids of 12.3–17.3 nm in diameter were synthesized by surface functionalizing nanoscale SiO2 with a charged corona and ionically tethering with oligomeric chains as canopy. The structure and properties of the nanofluids were systematically characterized by Fourier transform infrared (FTIR), differential scanning calorimeter (DSC), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and rheology tests. The resultant nanofluids with low-molecular-weight oligomeric as canopy are homogeneous, stable yellow-like fluids with no evidence of phase separation at room temperature, while other nanofluids containing high-molecular-weight as canopy behave like a soft glassy, and they exhibit fluidity with still high modulus and viscosity above 60°C. For deeper understanding of the nature of SiO2 nanofluids, the rheological behavior, thermal stability, as well as morphology of SiO2 nanofluids were investigated in details. The flow properties of nanofluids could be easily regulated from soft glassy to free flowing liquids by varying the molecule weight of canopy. Most importantly, the thermal stability, rheological behavior, as well as morphology can be also regulated through varying molecule weight and thickness of canopy, which will guide our future work on synthesis of nanofluids with controllable physical properties.

Boundary conditions for soft glassy flows: slippage and surface fluidization.

We explore the question of surface boundary conditions for the flow of a dense emulsion. We make use of microlithographic tools to create surfaces with well controlled roughness patterns and measure using dynamic confocal microscopy both the slip velocity and the shear rate close to the wall, which we relate to the notion of surface fluidization. Both slippage and wall fluidization depend non-monotonously on the roughness. We interpret this behavior within a simple model in terms of the building of a stratified layer and the activation of plastic events by the surface roughness.

Microscale Rheology of a Soft Glassy Material Close to Yielding

Using confocal microscopy, we study the flow of a model soft glassy material: a concentrated emulsion. We demonstrate the micro-macro link between in situ measured movements of droplets during the flow and the macroscopic rheological response of a concentrated emulsion, in the form of scaling relationships connecting the rheological "fluidity" with local standard deviation of the strain-rate tensor. Furthermore, we measure correlations between these local fluctuations, thereby extracting a correlation length which increases while approaching the yielding transition, in accordance with recent theoretical predictions.

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 theory, has recently been reformulated within a nonequilibrium 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.

How do soft particle glasses yield and flow near solid surfaces?

We use fluorescence microscopy and particle tracking velocimetry to image the motion of concentrated emulsions and microgel suspensions near solid surfaces. The local deformation involves a combination of slip and bulk flow, which are found to be controlled by surface forces. With smooth surfaces, two slip mechanisms are identified depending on whether particle–wall interactions are repulsive or weakly attractive. In the former case, the materials yield uniformly and the local rheology can be mapped on the macroscopic flow curve. In the latter case, yielding is non-uniform which reveals a continuous distribution of states from the immediate vicinity of the smooth surface to the bulk of the material. The effect of the surface is long-ranged and decays exponentially with the distance, which can be described by a non-local fluidity model. Our results establish a link between surface forces, lubrication and yielding in soft glassy or jammed materials and open new routes to manipulate their flow through the surface chemistry of the confining boundaries.

Structure and rheology of nanoparticle–polymer suspensions

Structure and rheology of oligomer-tethered nanoparticles suspended in low molecular weight polymeric host are investigated at various particle sizes and loadings. Strong curvature effects introduced by the small size of the nanoparticle cores are found to be important for understanding both the phase stability and rheology of the materials. Small angle X-ray scattering (SAXS) and transmission electron microscopy measurements indicate that PEG–SiO2/PEG suspensions are more stable against phase separation and aggregation than expected from theory for interacting brushes. SAXS and rheology measurements also reveal that at high particle loadings, the stabilizing oligomer brush is significantly compressed and produces jamming in the suspensions. The jamming transition is accompanied by what appears to be a unique evolution in the transient suspension rheology, along with large increments in the zero-shear, Newtonian viscosity. The linear and nonlinear flow responses of the jammed suspensions are discussed in the framework of the Soft Glassy Rheology (SGR) model, which is shown to predict many features that are consistent with experimental observations, including a two-step relaxation following flow cessation and a facile method for determining the shear-thinning coefficient from linear viscoelastic measurements. Finally, we show that the small sizes of the particles have a significant effect on inter-particle interactions and rheology, leading to stronger deviations from expectations based on planar brushes and hard-sphere suspension theories. In particular, we find that in the high volume fraction limit, tethered nanoparticles interact in their host polymer through short-range forces, which are more analogous to those between soft particles than between spherical polymer brushes.

Squeeze flow behavior of (soft glassy) thixotropic material

We study the flow behavior of a model soft glassy material − an aqueous suspension of Laponite − when it is squeezed between two circular parallel plates of different roughness. Aqueous suspension of Laponite shows a time dependent aging behavior as reflected in increased elastic modulus as well as yield stress, both of which however also decrease with an increase in the strength of deformation field thereby demonstrating typical thixotropic character. In a squeeze flow situation, under both force as well as velocity controlled modes; we find the behavior to be independent of the initial gap between the plates. In a constant force mode, the gap between the plates decreases until it reaches a finite limiting value, which is found to increase with an increase in age of the material as well as with a decrease in the applied force. In constant velocity experiments, at large gaps between the plates, normal force varies inversely with plate separation. The normal force is higher for a sample aged for a longer time as well as for a larger velocity of the top plate. We observe that the experimental behavior follows prediction of Herschel–Bulkley model solved for the squeeze flow (with different friction coefficients at the two plates) reasonably well under weak deformation fields. However, under strong deformation fields, experimental behavior deviates significantly from the prediction of Herschel–Bulkley model. This deviation arises due to melting or partial yielding of Laponite suspension under large deformation fields causing decrease in the viscosity, elastic modulus and the yield stress.

Linear Response Theory for Hard and Soft Glassy Materials

Despite qualitative differences in their underlying physics, both hard and soft glassy materials exhibit almost identical linear rheological behaviors. We show that these nearly universal properties emerge naturally in a shear-transformation-zone theory of amorphous plasticity, extended to include a broad distribution of internal thermal-activation barriers. The principal features of this barrier-height distribution are predicted by nonequilibrium, effective-temperature thermodynamics. Our theoretical loss modulus G''(ω) has a peak at the α relaxation rate, and a power law decay of the form ω(-ζ) for higher frequencies, in quantitative agreement with experimental data.

Thermosensitive, Soft Glassy and Structural Colored Colloidal Array in Ionic Liquid: Colloidal Glass to Gel Transition

A novel soft material comprising thermosensitive poly(benzyl methacrylate)-grafted silica nanoparticles (PBnMA-g-NPs) and the ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)amide ([C(2)mim][NTf(2)]), was fabricated. The thermosensitive properties were studied over a wide range of particle concentrations and temperatures. PBnMA-g-NPs in the IL underwent the lower critical solution temperature (LCST) phase transition at lower temperatures with a broader transition temperature range as compared to the free PBnMA solution. Highly concentrated suspensions formed soft glassy colloidal arrays (SGCAs) exhibiting a soft-solid behavior and angle-independent structural color. For the first time, we report a discrete change in the angle-independent structural color of SGCAs with temperature because of a temperature-induced colloidal glass-to-gel transition. The interparticle interaction changed from repulsive to attractive at the LCST temperature, and it was characterized by a V-shaped rheological response and a direct electron microscope observation of the colloidal suspension in the IL. With unique rheological and optical properties as well as properties derived from the IL itself, the thermosensitive SGCAs may be of interest as a new material for a wide range of applications such as electrochemical devices and color displays.

Soft Glassy Colloidal Arrays in an Ionic Liquid: Colloidal Glass Transition, Ionic Transport, and Structural Color in Relation to Microstructure

The colloidal glass transition, ionic transport, and optical properties of soft glassy colloidal arrays (SGCAs) that consist of poly(methyl methacrylate) (PMMA)-grafted silica nanoparticles (PMMA-g-NPs) and a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)amide ([C(2)mim][NTf(2)]), were investigated. At lower particle concentrations, PMMA-g-NPs were well-suspended in the IL without any aggregation or sedimentation, and the dilute suspensions showed liquid-like behavior. However, above a certain particle concentration, the suspensions became solidified and exhibited different structural colors depending on the particle concentrations. The liquid-solid transition of the SGCAs was essentially caused by colloidal glass transition. Due to the soft repulsive interaction between the particles, the effective volume fraction of the particle (ϕ(eff)) required for colloidal glass transition was higher than that of the hard sphere system and found to be approximately 0.70-0.74. The SGCA had sufficient ionic conductivity, which was greater than 10(-3) S cm(-1) at room temperature, even in the highly concentrated region. For ionic transport of the cation and the anion in the SGCAs, the decrease in diffusivity observed with the addition of the particles (D(g)/D(0)) was slightly greater for the [NTf(2)] anion than that of the [C(2)mim] cation, suggesting that the [NTf(2)] anion preferentially interacts with the PMMA chains. The SGCAs showed homogeneous, nonbrilliant, and angle-independent structural colors above the glass transition volume fraction. In addition, the color of the SGCAs changed from red to green to blue as the particle concentration increased. A linear relationship was found between the maximum wavelength of the reflection spectra and the center-to-center distance in the SGCAs.