Shear thickening in suspensions of particles with dynamic brush layers.

Control of frictional interactions among liquid-suspended particles has led to tunable, strikingly non-Newtonian rheology via the formation of strong flow constraints as particles come into close proximity under shear. Typically, these frictional interactions have been in the form of physical contact, controllable via particle shape and surface roughness. We investigate a different route, where molecular bridging between nearby particle surfaces generates a controllable constraint to relative particle movement. This is achieved with surface-functionalized colloidal particles capable of forming dynamic covalent bonds with telechelic polymers that comprise the suspending fluid. At low shear stress this results in particles coated with a uniform polymer brush layer. Beyond an onset stress σ* the telechelic polymers become capable of bridging and generate shear thickening. Over the size range investigated, we find that the dynamic brush layer leads to dependence of σ* on particle diameter that closely follows a power law with exponent -1.76. In the shear thickening regime, we observe an enhanced dilation in measurements of the first normal stress difference N1 and reduction in the extrapolated volume fraction required for jamming, both consistent with an effective particle friction that increases with decreasing particle diameter. These results are discussed in light of predictions for suspensions of hard spheres and of polymer-grafted particles.

Faceted wrinkling by contracting a curved boundary.

Single-mode deformations of two-dimensional materials, such as the Miura-ori zig-zag fold, are important to the design of deployable structures because of their robustness; these usually require careful pre-patterning of the material. Here we show that inward contraction of a curved boundary produces a fine wrinkle pattern with a novel structure that suggests similar single-mode characteristics, but with minimal pre-patterning. Using finite-element representation of the contraction of a thin circular annular sheet, we show that these sheets wrinkle into a structure well approximated by an isometric structure composed of conical sectors and flat, triangular facets. Isometry favours the restriction of such deformations to a robust low-bending energy channel that avoids stretching. This class of buckling offers a novel way to manipulate sheet morphology via boundary forces.

Granular convergence as an iterated local map.

Granular convergence is a property of a granular pack as it is repeatedly sheared in a cyclic, quasistatic fashion, as the packing configuration changes via discrete events. Under suitable conditions the set of microscopic configurations encountered converges to a periodic sequence after sufficient shear cycles. Prior work modeled this evolution as the iteration of a pre-determined, random map from a set of discrete configurations into itself. Iterating such a map from a random starting point leads to similar periodic repetition. This work explores the effect of restricting the randomness of such maps in order to account for the local nature of the discrete events. The number of cycles needed for convergence shows similar statistical behavior to that of numerical granular experiments. The number of cycles in a repeating period behaves only qualitatively like these granular studies.

Stochastic synchronization induced by noise.

Random perturbations applied in tandem to an ensemble of oscillating objects can synchronize their motion. We study multiple copies of an arbitrary dynamical system in a stable limit cycle, described via a standard phase reduction picture. The copies differ only in their arbitrary phases ϕ. Weak, randomly timed external impulses applied to all the copies can synchronize these phases over time. Beyond a threshold strength there is no such convergence to a common phase. Instead, the synchronization becomes erratic: successive impulses produce stochastic fluctuations in the phase distribution q(ϕ), ranging from near-perfect to near-random synchronization. Here we show that the sampled entropies of these phase distributions themselves form a steady-state ensemble, whose average can be made arbitrarily negative by tuning the impulse strength. A random-walk description of the entropy's evolution accounts for the observed exponential distribution of entropies and for the stochastic synchronization phenomenon.

A review of shaped colloidal particles in fluids: anisotropy and chirality.

This review treats asymmetric colloidal particles moving through their host fluid under the action of some form of propulsion. The propulsion can come from an external body force or from external shear flow. It may also come from externally-induced stresses at the surface, arising from imposed chemical, thermal or electrical gradients. The resulting motion arises jointly from the driven particle and the displaced fluid. If the objects are asymmetric, every aspect of their motion and interaction depends on the orientation of the objects. This orientation in turn changes in response to the driving. The objects' shape can thus lead to a range of emergent anisotropic and chiral motion not possible with isotropic spherical particles. We first consider what aspects of a body's asymmetry can affect its drift through a fluid, especially chiral motion. We next discuss driving by injecting external force or torque into the particles. Then we consider driving without injecting force or torque. This includes driving by shear flow and driving by surface stresses, such as electrophoresis. We consider how time-dependent driving can induce collective orientational order and coherent motion. We show how a given particle shape can be represented using an assembly of point forces called a Stokeslet object. We next consider the interactions between anisotropic propelled particles, the symmetries governing the interactions, and the possibility of bound pairs of particles. Finally we show how the collective hydrodynamics of a suspension can be qualitatively altered by the particles' shapes. The asymmetric responses discussed here are broadly relevant also for swimming propulsion of active micron-scale objects such as microorganisms.

Chiral motion in colloidal electrophoresis.

Asymmetrically charged, nonspherical colloidal particles in general perform complex rotations and oblique motions under an electric field. The interplay of electrostatic and hydrodynamic forces complicates the prediction of these motions. We demonstrate a method of calculating the body tensors that dictate translational and rotational velocity vectors arising from an external electric field. We treat insulating rigid bodies in the linear-response regime, with indefinitely small electrostatic screening length. The method represents the body as an assembly of point sources of both hydrodynamic drag and surface electric field. We demonstrate agreement with predicted electrophoretic mobility to within a few percent for several shapes with uniform and nonuniform charges. We show that even symmetric shapes can have strong chiral twisting motions. The method applies more generally to active colloidal swimmers.

Nucleation and shape dynamics of model nematic tactoids around adhesive colloids.

Recent experiments have shown how nematically ordered tactoid shaped actin droplets can be reorganized and divided by the action of myosin molecular motors. In this paper, we consider how similar morphological changes can potentially be achieved under equilibrium conditions. Using simulations, both atomistic and continuum, and a simple macroscopic model, we explore how the nucleation dynamics, shape changes, and the final steady state of a nematic tactoid droplet can be modified by interactions with model adhesive colloids that mimic a myosin motor cluster. We show how tactoid reorganization may occur in an equilibrium colloidal-nematic setting. We then suggest based on the simple macroscopic model how the simulation models may be extended to potentially stabilize divided tactoids.

Cyclic annealing as an iterated random map.

Disordered magnets, martensitic mixed crystals, and glassy solids can be irreversibly deformed by subjecting them to external deformation. The deformation produces a smooth, reversible response punctuated by abrupt relaxation "glitches." Under appropriate repeated forward and reverse deformation producing multiple glitches, a strict repetition of a single sequence of microscopic configurations often emerges. We exhibit these features by describing the evolution of the system configuration from glitch to glitch as a mapping of N states into one another. A map U controls forward deformation; a second map D controls reverse deformation. Iteration of a given sequence of forward and reverse maps, e.g., DDDDUUUU necessarily produces a convergence to a fixed cyclic repetition of states covering multiple glitches. The repetition may have a period of more than one strain cycle, as recently observed in simulations. Using numerical sampling, we characterize the convergence properties of four types of random maps implementing successive physical restrictions. The most restrictive is the much-studied Preisach model. These maps show only the most qualitative resemblance to annealing simulations. However, they suggest further properties needed for a realistic mapping scheme.

Self-organizing motors divide active liquid droplets.

The cytoskeleton is a collection of protein assemblies that dynamically impose spatial structure in cells and coordinate processes such as cell division and mechanical regulation. Biopolymer filaments, cross-linking proteins, and enzymatically active motor proteins collectively self-organize into various precise cytoskeletal assemblies critical for specific biological functions. An outstanding question is how the precise spatial organization arises from the component macromolecules. We develop a system to investigate simple physical mechanisms of self-organization in biological assemblies. Using a minimal set of purified proteins, we create droplets of cross-linked biopolymer filaments. Through the addition of enzymatically active motor proteins, we construct composite assemblies, evocative of cellular structures such as spindles, where the inherent anisotropy drives motor self-organization, droplet deformation, and division into two droplets. These results suggest that simple physical principles underlie self-organization in complex biological assemblies and inform bioinspired materials design.

Geometrical frustration yields fiber formation in self-assembly.

Controlling the self-assembly of supramolecular structures is vital for living cells, and a central challenge for engineering at the nano- and microscales [1, 2]. Nevertheless, even particles without optimized shapes can robustly form well-defined morphologies. This is the case in numerous medical conditions where normally soluble proteins aggregate into fibers [3, 4]. Beyond the diversity of molecular mechanisms involved [5, 6], we propose that fibers generically arise from the aggregation of irregular particles with short-range interactions. Using a minimal model of ill-fitting, sticky particles, we demonstrate robust fiber formation for a variety of particle shapes and aggregation conditions. Geometrical frustration plays a crucial role in this process, and accounts for the range of parameters in which fibers form as well as for their metastable character.

Self-folding origami at any energy scale.

Programmable stiff sheets with a single low-energy folding motion have been sought in fields ranging from the ancient art of origami to modern meta-materials research. Despite such attention, only two extreme classes of crease patterns are usually studied; special Miura-Ori-based zero-energy patterns, in which crease folding requires no sheet bending, and random patterns with high-energy folding, in which the sheet bends as much as creases fold. We present a physical approach that allows systematic exploration of the entire space of crease patterns as a function of the folding energy. Consequently, we uncover statistical results in origami, finding the entropy of crease patterns of given folding energy. Notably, we identify three classes of Mountain-Valley choices that have widely varying 'typical' folding energies. Our work opens up a wealth of experimentally relevant self-folding origami designs not reliant on Miura-Ori, the Kawasaki condition or any special symmetry in space.

Screening, Hyperuniformity, and Instability in the Sedimentation of Irregular Objects.

We study the overdamped sedimentation of non-Brownian objects of irregular shape using fluctuating hydrodynamics. The anisotropic response of the objects to flow, caused by their tendency to align with gravity, directly suppresses concentration and velocity fluctuations. This allows the suspension to avoid the anomalous fluctuations predicted for suspensions of symmetric spheroids. The suppression of concentration fluctuations leads to a correlated, hyperuniform structure. For certain object shapes, the anisotropic response may act in the opposite direction, destabilizing uniform sedimentation.

Liquid behavior of cross-linked actin bundles.

The actin cytoskeleton is a critical regulator of cytoplasmic architecture and mechanics, essential in a myriad of physiological processes. Here we demonstrate a liquid phase of actin filaments in the presence of the physiological cross-linker, filamin. Filamin condenses short actin filaments into spindle-shaped droplets, or tactoids, with shape dynamics consistent with a continuum model of anisotropic liquids. We find that cross-linker density controls the droplet shape and deformation timescales, consistent with a variable interfacial tension and viscosity. Near the liquid-solid transition, cross-linked actin bundles show behaviors reminiscent of fluid threads, including capillary instabilities and contraction. These data reveal a liquid droplet phase of actin, demixed from the surrounding solution and dominated by interfacial tension. These results suggest a mechanism to control organization, morphology, and dynamics of the actin cytoskeleton.

Signal transmissibility in marginal granular materials.

We examine the 'transmissibility' of a simulated two-dimensional pack of frictionless disks formed by confining dilute disks in a shrinking, periodic box to the point of mechanical stability. Two opposite boundaries are then removed, thus allowing a set of free motions. Small free displacements on one boundary then induce proportional displacements on the opposite boundary. Transmissibility is the ability to distinguish different perturbations by their distant responses. We assess transmissibility by successively identifying free orthonormal modes of motion that have the smallest distant responses. The last modes to be identified in this 'pessimistic' basis are the most transmissive. The transmitted amplitudes of these most transmissive modes fall off exponentially with mode number. Similar exponential falloff is seen in a simple elastic medium, though the responsible modes differ greatly in structure in the two systems. Thus the marginal pack's transmissibility is qualitatively similar to that of a simple elastic medium. We compare our results with recent findings based on the projection of the space of free motion onto interior sites.

Criterion for noise-induced synchronization: Application to colloidal alignment.

Colloidal bodies of irregular shape rotate as they descend under gravity in solution. This rotational response provides a means of bringing a dispersion of identical bodies into a synchronized rotation with the same orientation using programed forcing. We use the notion of statistical entropy to derive bounds on the rate of synchronization. These bounds apply generally to dynamical systems with stable periodic motion with a phase ϕ(t), when subjected to an impulsive perturbation. The impulse causes a change of phase expressible as a phase map ψ(ϕ). We derive an upper limit on the average change of entropy 〈ΔH〉 in terms of this phase map; when this limit is negative, alignment must occur. For systems that have achieved a low entropy, the 〈ΔH〉 approaches this upper limit.

Self-Organizing Arrays of Size Scalable Nanoparticle Rings.

A central challenge in nano- and mesoscale materials research is facile formation of specific structures for catalysis, sensing, and photonics. Self-assembled equilibrium structures, such as three-dimensional crystals or ordered monolayers, form as a result of the interactions of the constituents. Other structures can be achieved by imposing forces (fields) and/or boundary conditions, which Whitesides termed "self-organization". Here, we demonstrate contact line pinning on locally curved surfaces (i.e., a self-assembled monolayer of SiO2 colloidal particles) as a boundary condition to create extended arrays of uniform rings of Au nanoparticles (NPs) on the SiO2 colloids. The mechanism differs from the well-known "coffee-ring" effect; here the functionalized NPs deposit at the contact line and are not driven by evaporative transport. Thus, NP ring formation depends on the hydrophobicity and wetting of the SiO2 colloids by the chloroform solution, ligands on the NPs, and temperature. The NP rings exhibit size scaling behavior, maintaining a constant ratio of NP ring-to-colloid diameter (from 300 nm to 2 µm). The resultant high-quality NP ring structures are expected to have interesting photonic properties.

Hydrodynamic interactions between two forced objects of arbitrary shape. II. Relative translation.

We study the relative translation of two arbitrarily shaped objects, caused by their hydrodynamic interaction as they are forced through a viscous fluid in the limit of zero Reynolds number. It is well known that in the case of two rigid spheres in an unbounded fluid, the hydrodynamic interaction does not produce relative translation. More generally, such an effective pair-interaction vanishes in configurations with spatial inversion symmetry; for example, an enantiomorphic pair in mirror image positions has no relative translation. We show that the breaking of inversion symmetry by boundaries of the system accounts for the interactions between two spheres in confined geometries, as observed in experiments. The same general principle also provides new predictions for interactions in other object configurations near obstacles. We examine the time-dependent relative translation of two self-aligning objects, extending the numerical analysis of our preceding publication [Goldfriend, Diamant, and Witten, Phys. Fluids 27, 123303 (2015)]PHFLE61070-663110.1063/1.4936894. The interplay between the orientational interaction and the translational one, in most cases, leads over time to repulsion between the two objects. The repulsion is qualitatively different for self-aligning objects compared to the more symmetric case of uniform prolate spheroids. The separation between the two objects increases with time t as t^{1/3} in the former case, and more strongly, as t, in the latter.

Singular electrostatic energy of nanoparticle clusters.

The binding of clusters of metal nanoparticles is partly electrostatic. We address difficulties in calculating the electrostatic energy when high charging energies limit the total charge to a single quantum, entailing unequal potentials on the particles. We show that the energy at small separation h has a singular logarithmic dependence on h. We derive a general form for this energy in terms of the singular capacitance of two spheres in near contact c(h), together with nonsingular geometric features of the cluster. Using this form, we determine the energies of various clusters, finding that more compact clusters are more stable. These energies are proposed to be significant for metal-semiconductor binary nanoparticle lattices found experimentally. We sketch how these effects should dictate the relative abundances of metal nanoparticle clusters in nonpolar solvents.

Shapeable sheet without plastic deformation.

Randomly crumpled sheets have shape memory. In order to understand the basis of this form of memory, we simulate triangular lattices of springs whose lengths are altered to create a topography with multiple potential energy minima. We then deform these lattices into different shapes and investigate their ability to retain the imposed shape when the energy is relaxed. The lattices are able to retain a range of curvatures. Under moderate forcing from a state of local equilibrium, the lattices deform by several percent but return to their retained shape when the forces are removed. By increasing the forcing until an irreversible motion occurs, we find that the transitions between remembered shapes show cooperativity among several springs. For fixed lattice structures, the shape memory tends to decrease as the lattice is enlarged; we propose ways to counter this decrease by modifying the lattice geometry. We survey the energy landscape by displacing individual nodes. An extensive fraction of these nodes proves to be bistable; they retain their displaced position when the energy is relaxed. Bending the lattice to a stable curved state alters the pattern of bistable nodes. We discuss this shapeability in the context of other forms of material memory and contrast it with the shapeability of plastic deformation. We outline the prospects for making real materials based on these principles.

Ion mixing, hydration, and transport in aqueous ionic systems.

The enhancement effect on the ion mobility of fluoride (and that of chloride) in a polycationic system, as the chloride content increases, is shown to also exist in other more simple ionic systems with cations such as the cesium ion and an organic ammonium ion. As the chloride content increases, in addition to the finding that there is more unbound water associated with the cation, we also observe that the average lifetime of a hydrogen bond decreases. This change to the hydrogen bonds is correlated to significant changes to both the structural and dynamical properties of water. The more disordered water structure and faster water dynamics are hypothesized to be also responsible for the enhanced ion mobilities. Furthermore, when either the chloride content or hydration level is changed, the self-diffusion constant of each co-ion changes by almost the same factor, implying the existence of a single universal transport mechanism that determines ion mobilities.