Hopper flows of deformable particles.

Numerous experimental and computational studies show that continuous hopper flows of granular materials obey the Beverloo equation that relates the volume flow rate Q and the orifice width w: Q ∼ (w/σavg - k)ß, where σavg is the average particle diameter, kσavg is an offset where Q ∼ 0, the power-law scaling exponent ß = d - 1/2, and d is the spatial dimension. Recent studies of hopper flows of deformable particles in different background fluids suggest that the particle stiffness and dissipation mechanism can also strongly affect the power-law scaling exponent ß. We carry out computational studies of hopper flows of deformable particles with both kinetic friction and background fluid dissipation in two and three dimensions. We show that the exponent ß varies continuously with the ratio of the viscous drag to the kinetic friction coefficient, λ = ζ/µ. ß = d - 1/2 in the λ → 0 limit and d - 3/2 in the λ → ∞ limit, with a midpoint λc that depends on the hopper opening angle θw. We also characterize the spatial structure of the flows and associate changes in spatial structure of the hopper flows to changes in the exponent ß. The offset k increases with particle stiffness until k ∼ kmax in the hard-particle limit, where kmax ∼ 3.5 is larger for λ → ∞ compared to that for λ → 0. Finally, we show that the simulations of hopper flows of deformable particles in the λ → ∞ limit recapitulate the experimental results for quasi-2D hopper flows of oil droplets in water.

Supramolecular DNA Photonic Hydrogels for On-Demand Control of Coloration with High Spatial and Temporal Resolution.

Hydrogels embedded with periodic arrays of nanoparticles display a striking photonic crystal coloration that may be useful for applications such as camouflage, anticounterfeiting, and chemical sensing. Dynamically generating color patterns requires control of nanoparticle organization within a polymer network on-demand, which is challenging. We solve this problem by creating a DNA hydrogel system that shows a 50 000-fold decrease in modulus upon heating by ∼10 °C. Magnetic nanoparticles entrapped within these DNA gels generate a structural color only when the gel is heated and a magnetic field is applied. A spatially controlled photonic crystal coloration was achieved by photopatterning with a near-infrared illumination. Color was "erased" by illuminating or heating the gel in the absence of an external magnetic field. The on-demand assembly technology demonstrated here may be beneficial for the development of a new generation of smart materials with potential applications in erasable lithography, encryption, and sensing.

Rheology finds distinct glass and jamming transitions in emulsions.

We study the rheology of monodisperse and bidisperse emulsions with various droplet sizes (1-2 µm diameter). Above a critical volume fraction φc, these systems exhibit solid-like behavior and a yield stress can be detected. Previous experiments suggest that for small thermal particles, rheology will see a glass transition at φc = φg ≈ 0.58; for large athermal systems, rheology will see a jamming transition at φc = φJ ≈ 0.64. However, simulations point out that at the crossover of thermal and athermal regimes, the glass and jamming transitions may both be observed in the same sample. Here we conduct an experiment by shearing four oil-in-water emulsions with a rheometer. We observe both a glass and a jamming transition for our smaller diameter droplets, and only a jamming transition for our larger diameter droplets. The bidisperse sample behaves similarly to the small droplet sample, with two transitions observed. Our rheology data are well-fit by both the Herschel-Bulkley model and the three component model. Based on the fitting parameters, our raw rheological data would not collapse onto a master curve. Our results show that liquid-solid transitions in dispersions are not universal, but depend on particle size.

Mechanical properties of 2D aggregates of oil droplets as model mono-crystals.

We investigate the elastic and yielding properties of two dimensional defect-free mono-crystals made of highly monodisperse droplets. Crystals are compressed between two parallel boundaries of which one acts as a force sensor. As the available space between boundaries is reduced, the crystal goes through successive row-reduction transitions. For small compression forces, the crystal responds elastically until a critical force is reached and the assembly fractures in a single catastrophic global event. Correspondingly there is a peak in the force measurement associated with each row-reduction. The elastic properties of ideal mono-crystal samples are fully captured by a simple analytical model consisting of an assembly of individual capillary springs. The yielding properties of the crystal are captured with a minimal bond breaking model.

Neglecting polydispersity degrades propensity measurements in supercooled liquids.

We conduct molecular dynamics simulations of a bidisperse Kob-Andersen (KA) glass former, modified to add in additional polydispersity. The original KA system is known to exhibit dynamical heterogeneity. Prior work defined propensity, the mean motion of a particle averaged over simulations reconstructing the initial positions of all particles but with randomized velocities. The existence of propensity shows that structure and dynamics are connected. In this paper, we study systems which mimic problems that would be encountered in measuring propensity in a colloidal glass former, where particles are polydisperse (they have slight size variations). We mimic polydispersity by altering the bidisperse KA system into a quartet consisting of particles both slightly larger and slightly smaller than the parent particles in the original bidisperse system. We then introduce errors into the reconstruction of the initial positions that mimic mistakes one might make in a colloidal experiment. The mistakes degrade the propensity measurement, in some cases nearly completely; one no longer has an iso-configurational ensemble in any useful sense. Our results show that a polydisperse sample is suitable for propensity measurements provided one avoids reconstruction mistakes.

Long-wavelength fluctuations and the glass transition in two dimensions and three dimensions.

Phase transitions significantly differ between 2D and 3D systems, but the influence of dimensionality on the glass transition is unresolved. We use microscopy to study colloidal systems as they approach their glass transitions at high concentrations and find differences between two dimensions and three dimensions. We find that, in two dimensions, particles can undergo large displacements without changing their position relative to their neighbors, in contrast with three dimensions. This is related to Mermin-Wagner long-wavelength fluctuations that influence phase transitions in two dimensions. However, when measuring particle motion only relative to their neighbors, two dimensions and three dimensions have similar behavior as the glass transition is approached, showing that the long-wavelength fluctuations do not cause a fundamental distinction between 2D and 3D glass transitions.

Model-free 3D localization with precision estimates for brightfield-imaged particles.

Volumetric imaging and 3D particle tracking are becoming increasingly common and have a variety of microscopy applications including in situ fluorescent imaging, in-vitro single-molecule characterization, and analysis of colloidal systems. While recent interest has generated discussion of optimal schemes for localizing diffraction-limited fluorescent puncta, there have been relatively few published routines for tracking particles imaged with bright-field illumination. To address this, we outline a simple, look-up-table based 3D tracking strategy, which can be adapted to most commercially available wide-field microscopes, and present two image processing algorithms that together yield high-precision localization and return estimates of statistical accuracy. Under bright-field illumination, a particle's depth can be determined based on the size and shape of its diffractive pattern due to Mie scattering. Contrary to typical "super-resolution" fluorescence tracking routines, which typically fit a diffraction-limited spot to a model point-spread-function, the lateral (XY) tracking routine relies on symmetry to locate a particle without prior knowledge of the form of the particle. At low noise levels (signal:noise > 1000), the symmetry routine estimates particle positions with accuracy better than 0.01 pixel. Depth localization is accomplished by matching images of particles to those in a pre-recorded look-up-table. The routine presented here optimally interpolates between LUT entries with better than 0.05 step accuracy. Both routines are tolerant of high levels of image noise, yielding sub-pixel/step accuracy with signal-to-noise ratios as small as 1, and, by design, return confidence intervals indicating the expected accuracy of each calculated position. The included implementations operate extremely quickly and are amenable to real-time analysis at frame rates exceeding several hundred frames per second.

The role of deformability in determining the structural and mechanical properties of bubbles and emulsions.

We perform computational studies of jammed particle packings in two dimensions undergoing isotropic compression using the well-characterized soft particle (SP) model and deformable particle (DP) model that we developed for bubbles and emulsions. In the SP model, circular particles are allowed to overlap, generating purely repulsive forces. In the DP model, particles minimize their perimeter, while deforming at fixed area to avoid overlap during compression. We compare the structural and mechanical properties of jammed packings generated using the SP and DP models as a function of the packing fraction ρ, instead of the reduced number density φ. We show that near jamming onset the excess contact number Δz = z - zJ and shear modulus G scale as Δρ0.5 in the large system limit for both models, where Δρ = ρ - ρJ and zJ ≈ 4 and ρJ ≈ 0.842 are the values at jamming onset. Δz and G for the SP and DP models begin to differ for ρ ⪆ 0.88. In this regime, Δz ∼ G can be described by a sum of two power-laws in Δρ, i.e. Δz ∼ G ∼ C0Δρ0.5 + C1Δρ1.0 to lowest order. We show that the ratio C1/C0 is much larger for the DP model compared to that for the SP model. We also characterize the void space in jammed packings as a function of ρ. We find that the DP model can describe the formation of Plateau borders as ρ → 1. We further show that the results for z and the shape factor A versus ρ for the DP model agree with recent experimental studies of foams and emulsions.

Cooperative behavior of biased probes in crowded interacting systems.

We study, via extensive numerical simulations, dynamics of a crowded mixture of mutually interacting (with a short-range repulsive potential) colloidal particles immersed in a suspending solvent, acting as a heat bath. The mixture consists of a majority component - neutrally buoyant colloids subject to internal stimuli only, and a minority component - biased probes (BPs) also subject to a constant force. In such a system each of the BPs alters the distribution of the colloidal particles in its vicinity, driving their spatial distribution out of equilibrium. This induces effective long-range interactions and multi-tag correlations between the BPs, mediated by an out-of-equilibrium majority component, and prompts the BPs to move collectively assembling in clusters. We analyse the size-distribution of the self-assembling clusters in the steady-state, their specific force-velocity relations and also properties of the effective interactions emerging between the BPs.

Decoupling of translational and rotational diffusion in quasi-2D colloidal fluids.

We observe the translational and rotational diffusion of dimer tracer particles in quasi-2D colloidal samples. The dimers are in dense samples of two different sizes of spherical colloidal particles, with the area fraction ϕ of the particles varying from dilute to nearly glassy. At low ϕ, rotational and translational diffusion have a ratio set by the dimer size, as expected. At higher ϕ, dimers become caged by their neighboring particles, and both rotational and translational diffusion become slow. For short dimers, we observe rapid reorientations so that the rotational diffusion is faster than the translational diffusion: the two modes of diffusion are decoupled and have different ϕ dependence. Longer dimers do not exhibit fast rotations, and we find that their translational and rotational diffusion stay coupled for all ϕ. Our results bridge prior results that used spheres (very fast rotation) and long ellipsoids (very slow rotation).

Aging near rough and smooth boundaries in colloidal glasses.

We use a confocal microscope to study the aging of a bidisperse colloidal glass near rough and smooth boundaries. Near smooth boundaries, the particles form layers, and particle motion is dramatically slower near the boundary as compared to the bulk. Near rough boundaries, the layers nearly vanish, and particle motion is nearly identical to that of the bulk. The gradient in dynamics near the boundaries is demonstrated to be a function of the gradient in structure for both types of boundaries. Our observations show that wall-induced layer structures strongly influence aging.

Programmable DNA Hydrogels Assembled from Multidomain DNA Strands.

Hydrogels are important in biological and medical applications, such as drug delivery and tissue engineering. DNA hydrogels have attracted significant attention due to the programmability and biocompatibility of the material. We developed a series of low-cost one-strand DNA hydrogels self-assembled from single-stranded DNA monomers containing multiple palindromic domains. This new hydrogel design is simple and programmable. Thermal stability, mechanical properties, and loading capacity of these one-strand DNA hydrogels can be readily regulated by simply adjusting the DNA domains.

Predicting the size of droplets produced through Laplace pressure induced snap-off.

Laplace pressure driven snap-off is a technique that is used to produce droplets for emulsions and microfluidics purposes. Previous predictions of droplet size have assumed a quasi-equilibrium low flow limit. We present a simple model to predict droplet sizes over a wide range of flow rates, demonstrating a rich landscape of droplet stability depending on droplet size and growth rate. The model accounts for the easily adjusted experimental parameters of geometry, interfacial tension, and the viscosities of both phases.

Measurement of Stress Redistribution in Flowing Emulsions.

We study how local rearrangements alter droplet stresses within flowing dense quasi-two-dimensional emulsions at area fractions ϕ≥0.88. Using microscopy, we measure droplet positions while simultaneously using their deformed shape to measure droplet stresses. We find that rearrangements alter nearby stresses in a quadrupolar pattern: stresses on neighboring droplets tend to either decrease or increase depending on location. The stress redistribution is more anisotropic with increasing ϕ. The spatial character of the stress redistribution influences where subsequent rearrangements occur. Our results provide direct quantitative support for rheological theories of dense amorphous materials that connect local rearrangements to changes in nearby stress.

Snap-off production of monodisperse droplets.

We introduce a novel technique to produce monodisperse droplets through the snap-off mechanism. The methodology is simple, versatile, and requires no specialized or expensive components. The droplets produced have polydispersity < 1% and can be as small as 2.5 µm radius. A convenient feature is that the droplet size is constant over a 100-fold change in flow rate, while at higher flows the droplet size can be continuously adjusted.

Decoupling of rotational and translational diffusion in supercooled colloidal fluids.

We use confocal microscopy to directly observe 3D translational and rotational diffusion of tetrahedral clusters, which serve as tracers in colloidal supercooled fluids. We find that as the colloidal glass transition is approached, translational and rotational diffusion decouple from each other: Rotational diffusion remains inversely proportional to the growing viscosity whereas translational diffusion does not, decreasing by a much lesser extent. We quantify the rotational motion with two distinct methods, finding agreement between these methods, in contrast with recent simulation results. The decoupling coincides with the emergence of non-Gaussian displacement distributions for translation whereas rotational displacement distributions remain Gaussian. Ultimately, our work demonstrates that as the glass transition is approached, the sample can no longer be approximated as a continuum fluid when considering diffusion.

Rearrangements during slow compression of a jammed two-dimensional emulsion.

As amorphous materials get jammed, both geometric and dynamic heterogeneity are observed. We investigate the correlation between the local geometric heterogeneity and local rearrangements in a slowly compressed bidisperse quasi-two-dimensional emulsion system. The compression is driven by evaporation of the continuous phase and causes the area packing fraction to increase from 0.88 to 0.99. We quantify the structural heterogeneity of the system using the radical Voronoi tessellation following the method of Rieser et al. [Phys. Rev. Lett. 116, 088001 (2016)]0031-900710.1103/PhysRevLett.116.088001. We define two structural quantities characterizing local structure, the first of which considers nearest neighbors and the second of which includes information from second-nearest neighbors. We find that droplets in heterogeneous local regions are more likely to have local rearrangements. These rearrangements are generally T1 events where two droplets converge toward a void, and two droplets move away from the void to make room for the converging droplets. Thus, the presence of the voids tends to orient the T1 events. The presence of a correlation between the structural quantities and the rearrangement dynamics remains qualitatively unchanged over the entire range of packing fractions observed.

Bounded distributions place limits on skewness and larger moments.

Distributions of strictly positive numbers are common and can be characterized by standard statistical measures such as mean, standard deviation, and skewness. We demonstrate that for these distributions the skewness D3 is bounded from below by a function of the coefficient of variation (CoV) δ as D3 > δ - 1/δ. The results are extended to any distribution that is bounded with minimum value xmin and/or bounded with maximum value xmax. We build on the results to provide bounds for kurtosis D4, and conjecture analogous bounds exists for higher statistical moments.

Compression and fracture of ordered and disordered droplet rafts.

We simulate a two-dimensional array of droplets being compressed between two walls. The droplets are adhesive due to an attractive depletion force. As one wall moves toward the other, the droplet array is compressed and eventually induced to rearrange. The rearrangement occurs via a fracture, where depletion bonds are quickly broken between a subset of droplets. For monodisperse, hexagonally ordered droplet arrays, this fracture is preceded by a maximum force exerted on the walls, which drops rapidly after the fracture occurs. In small droplet arrays a fracture is a single well-defined event, but for larger droplet arrays, competing fractures can be observed. These are fractures nucleated nearly simultaneously in different locations. Finally, we also study the compression of bidisperse droplet arrays. The addition of a second droplet size further disrupts fracture events, showing differences between ideal crystalline arrays, crystalline arrays with a small number of defects, and fully amorphous arrays. These results are in good agreement with previously published experiments.

Local elastic response measured near the colloidal glass transition.

We examine the response of a dense colloidal suspension to a local force applied by a small magnetic bead. For small forces, we find a linear relationship between the force and the displacement, suggesting the medium is elastic, even though our colloidal samples macroscopically behave as fluids. We interpret this as a measure of the strength of colloidal caging, reflecting the proximity of the samples' volume fractions to the colloidal glass transition. The strain field of the colloidal particles surrounding the magnetic probe appears similar to that of an isotropic homogeneous elastic medium. When the applied force is removed, the strain relaxes as a stretched exponential in time. We introduce a model that suggests this behavior is due to the diffusive relaxation of strain in the colloidal sample.