Shear-assisted grain coarsening in colloidal polycrystals.

Grain growth under shear annealing is crucial for controlling the properties of polycrystalline materials. However, their microscopic kinetics are not well understood because individual atomic trajectories are difficult to track. Here, we study grain growth with single-particle kinetics in colloidal polycrystals using video microscopy. Rich grain-growth phenomena are revealed in three shear regimes, including the normal grain growth (NGG) in weak shear melting-recrystallization process in strong shear. For intermediate shear, early stage NGG is arrested by built-up stress and eventually gives way to dynamic abnormal grain growth (DAGG). We find that DAGG occurs via a melting-recrystallization process, which naturally explains the puzzling stress drop at the onset of DAGG in metals. Moreover, we visualize that grain boundary (GB) migration is coupled with shear via disconnection gliding. The disconnection-gliding dynamics and the collective motions of ambient particles are resolved. We also observed that grain rotation can violate the conventional relation [Formula: see text] (R is the grain radius, and θ is the misorientation angle between two grains) by emission and annihilation of dislocations across the grain, resulting in a step-by-step rotation. Besides grain growth, we discover a result in shear-induced melting: The melting volume fraction varies sinusoidally on the angle mismatch between the triangular lattice orientation of the grain and the shear direction. These discoveries hold potential to inform microstructure engineering of polycrystalline materials.

Heterogeneous Activation, Local Structure, and Softness in Supercooled Colloidal Liquids.

We experimentally characterize heterogeneous nonexponential relaxation in bidisperse supercooled colloidal liquids utilizing a recent concept called "softness" [Phys. Rev. Lett. 114, 108001 (2015)PRLTAO0031-900710.1103/PhysRevLett.114.108001]. Particle trajectory and structure data enable classification of particles into subgroups with different local environments and propensities to hop. We determine residence times t_{R} between particle hops and show that t_{R} derived from particles in the same softness subgroup are exponentially distributed. Using the mean residence time t[over ¯]_{R} for each softness subgroup, and a Kramers' reaction rate model, we estimate the activation energy barriers E_{b} for particle hops, and show that both t[over ¯]_{R} and E_{b} are monotonic functions of softness. Finally, we derive information about the combinations of large and small particle neighbors that determine particle softness, and we explicitly show that multiple exponential relaxation channels in the supercooled liquid give rise to its nonexponential behavior.

Different routes into the glass state for soft thermo-sensitive colloids.

We report an experimental and theoretical investigation of glass formation in soft thermo-sensitive colloids following two different routes: a gradual increase of the particle number density at constant temperature and an increase of the radius in a fixed volume at constant particle number density. Confocal microscopy experiments and the non-equilibrium self-consistent generalized Langevin equation (NE-SCGLE) theory consistently show that the two routes lead to a dynamically comparable state at sufficiently long aging times. However, experiments reveal the presence of moderate but persistent structural differences. Successive cycles of radius decrease and increase lead instead to a reproducible glass state, indicating a suitable route to obtain rejuvenation without using shear fields.

Suppression of the coffee-ring effect by shape-dependent capillary interactions.

When a drop of liquid dries on a solid surface, its suspended particulate matter is deposited in ring-like fashion. This phenomenon, known as the coffee-ring effect, is familiar to anyone who has observed a drop of coffee dry. During the drying process, drop edges become pinned to the substrate, and capillary flow outward from the centre of the drop brings suspended particles to the edge as evaporation proceeds. After evaporation, suspended particles are left highly concentrated along the original drop edge. The coffee-ring effect is manifested in systems with diverse constituents, ranging from large colloids to nanoparticles and individual molecules. In fact--despite the many practical applications for uniform coatings in printing, biology and complex assembly-the ubiquitous nature of the effect has made it difficult to avoid. Here we show experimentally that the shape of the suspended particles is important and can be used to eliminate the coffee-ring effect: ellipsoidal particles are deposited uniformly during evaporation. The anisotropic shape of the particles significantly deforms interfaces, producing strong interparticle capillary interactions. Thus, after the ellipsoids are carried to the air-water interface by the same outward flow that causes the coffee-ring effect for spheres, strong long-ranged interparticle attractions between ellipsoids lead to the formation of loosely packed or arrested structures on the air-water interface. These structures prevent the suspended particles from reaching the drop edge and ensure uniform deposition. Interestingly, under appropriate conditions, suspensions of spheres mixed with a small number of ellipsoids also produce uniform deposition. Thus, particle shape provides a convenient parameter to control the deposition of particles, without modification of particle or solvent chemistry.

Dynamics of ordered colloidal particle monolayers at nematic liquid crystal interfaces.

We prepare two-dimensional crystalline packings of colloidal particles on surfaces of the nematic liquid crystal (NLC) 5CB, and we investigate the diffusion and vibrational phonon modes of these particles using video microscopy. Short-time particle diffusion at the air-NLC interface is well described by a Stokes-Einstein model with viscosity similar to that of 5CB. Crystal phonon modes, measured by particle displacement covariance techniques, are demonstrated to depend on the elastic constants of 5CB through interparticle forces produced by LC defects that extend from the interface into the underlying bulk material. The displacement correlations permit characterization of transverse and longitudinal sound velocities of the crystal packings, as well as the particle interactions produced by the LC defects. All behaviors are studied in the nematic phase as a function of increasing temperature up to the nematic-isotropic transition.

Physics in ordered and disordered colloidal matter composed of poly(N-isopropylacrylamide) microgel particles.

This review collects and describes experiments that employ colloidal suspensions to probe physics in ordered and disordered solids and related complex fluids. The unifying feature of this body of work is its clever usage of poly(N-isopropylacrylamide) (PNIPAM) microgel particles. These temperature-sensitive colloidal particles provide experimenters with a 'knob' for in situ control of particle size, particle interaction and particle packing fraction that, in turn, influence the structural and dynamical behavior of the complex fluids and solids. A brief summary of PNIPAM particle synthesis and properties is given, followed by a synopsis of current activity in the field. The latter discussion describes a variety of soft matter investigations including those that explore formation and melting of crystals and clusters, and those that probe structure, rearrangement and rheology of disordered (jammed/glassy) and partially ordered matter. The review, therefore, provides a snapshot of a broad range of physics phenomenology which benefits from the unique properties of responsive microgel particles.

Rheology of soft colloids across the onset of rigidity: scaling behavior, thermal, and non-thermal responses.

We study the rheological behavior of colloidal suspensions composed of soft sub-micron-size hydrogel particles across the liquid-solid transition. The measured stress and strain-rate data, when normalized by thermal stress and time scales, suggest our systems reside in a regime wherein thermal effects are important. In a different vein, critical point scaling predictions for the jamming transition, typical in athermal systems, are tested. Near dynamic arrest, the suspensions exhibit scaling exponents similar to those reported in Nordstrom et al., Phys. Rev. Lett., 2010, 105, 175701. The observation suggests that our system exhibits a glass transition near the onset of rigidity, but it also exhibits a jamming-like scaling further from the transition point. These observations are thought-provoking in light of recent theoretical and simulation findings, which show that suspension rheology across the full range of microgel particle experiments can exhibit both thermal and athermal mechanisms.

Effects of particle shape on growth dynamics at edges of evaporating drops of colloidal suspensions.

We study the influence of particle shape on growth processes at the edges of evaporating drops. Aqueous suspensions of colloidal particles evaporate on glass slides, and convective flows during evaporation carry particles from drop center to drop edge, where they accumulate. The resulting particle deposits grow inhomogeneously from the edge in two dimensions, and the deposition front, or growth line, varies spatiotemporally. Measurements of the fluctuations of the deposition front during evaporation enable us to identify distinct growth processes that depend strongly on particle shape. Sphere deposition exhibits a classic Poisson-like growth process; deposition of slightly anisotropic particles, however, belongs to the Kardar-Parisi-Zhang universality class, and deposition of highly anisotropic ellipsoids appears to belong to a third universality class, characterized by Kardar-Parisi-Zhang fluctuations in the presence of quenched disorder.

In situ observation of coalescence of nuclei in colloidal crystal-crystal transitions.

Coalescence of nuclei in phase transitions significantly influences the transition rate and the properties of product materials, but these processes occur rapidly and are difficult to observe at the microscopic scale. Here, we directly image the coalescence of nuclei with single particle resolution during the crystal-crystal transition from a multilayer square to triangular lattices. The coalescence process exhibits three similar stages across a variety of scenarios: coupled growth of two nuclei, their attachment, and relaxation of the coalesced nucleus. The kinetics vary with nucleus size, interface, and lattice orientation; the kinetics include acceleration of nucleus growth, small nucleus liquefaction, and generation/annihilation of defects. Related mechanisms, such as strain induced by nucleus growth and the lower energy of liquid-crystal versus crystal-crystal interfaces, appear to be common to both atomic and colloidal crystals.

Influence of particle shape on bending rigidity of colloidal monolayer membranes and particle deposition during droplet evaporation in confined geometries.

We investigate the influence of particle shape on the bending rigidity of colloidal monolayer membranes (CMMs) and on evaporative processes associated with these membranes. Aqueous suspensions of colloidal particles are confined between glass plates and allowed to evaporate. Confinement creates ribbonlike air-water interfaces and facilitates measurement and characterization of CMM geometry during drying. Interestingly, interfacial buckling events occur during evaporation. Extension of the description of buckled elastic membranes to our quasi-2D geometry enables the determination of the ratio of CMM bending rigidity to its Young's modulus. Bending rigidity increases with increasing particle anisotropy, and particle deposition during evaporation is strongly affected by membrane elastic properties. During drying, spheres are deposited heterogeneously, but ellipsoids are not. Apparently, increased bending rigidity reduces contact line bending and pinning and induces uniform deposition of ellipsoids. Surprisingly, suspensions of spheres doped with a small number of ellipsoids are also deposited uniformly.

Surfactant-induced Marangoni eddies alter the coffee-rings of evaporating colloidal drops.

The influence of the small ionic surfactant sodium dodecyl sulfate (SDS) on the evaporation of drying colloidal droplets is quantitatively investigated. The addition of SDS leads to a significantly more uniform deposition of colloidal particles after evaporation (i.e., the so-called "coffee-ring effect" is dramatically altered). We understand this phenomenon in the context of circulating radial Marangoni flows induced by the variation of SDS concentration along the air-water interface. Video microscopy permits the direct visualization of the colloidal particles involved in these flows, revealing a surprisingly stable "Marangoni eddy" that prevents particle deposition at the drop perimeter.

Origin of the Acoustic Bandgaps in Hypersonic Colloidal Phononics: The Role of the Elastic Impedance.

How phonons propagate in nanostructures determines the flow of elastic and thermal energy in dielectric materials. However, a reliable theoretical prediction of the phonon dispersion relation requires experimental verification both near to and far from the Brillouin zone of the nanostructure. We report on the experimental hypersonic phonon dispersion of hard (SiO2) and soft (polymer) fcc colloidal crystals infiltrated in liquid polydimethylsiloxane with different elastic impedance contrast using Brillouin light spectroscopy. We discuss the distinct differences with first-principles full elastodynamic calculations involving a multiple-scattering theory. Interparticle contacts strongly impact the long-wavelength speed of sound and the nature of the particle vibration resonance-induced hybridization hypersonic bandgap. The absence of the order-induced Bragg bandgap in SiO2 and its presence in soft opals cannot be fully accounted for by the theory, limiting its predictive power. Bridging the elasticity of the two colloidal crystals with suitable SiO2 core-shell (polymer) particles reveals an unprecedented crossover behavior in the dispersion relation. In view of many conversational parameters, the control tuning of phonon propagation in soft matter-based hypersonic phononics remains challenging.

Diffusive and martensitic nucleation kinetics in solid-solid transitions of colloidal crystals.

Solid-solid transitions between crystals follow diffusive nucleation, or various diffusionless transitions, but these kinetics are difficult to predict and observe. Here we observed the rich kinetics of transitions from square lattices to triangular lattices in tunable colloidal thin films with single-particle dynamics by video microscopy. Applying a small pressure gradient in defect-free regions or near dislocations markedly transform the diffusive nucleation with an intermediate-stage liquid into a martensitic generation and oscillation of dislocation pairs followed by a diffusive nucleus growth. This transformation is neither purely diffusive nor purely martensitic as conventionally assumed but a combination thereof, and thus presents new challenges to both theory and the empirical criterion of martensitic transformations. We studied how pressure, density, grain boundary, triple junction and interface coherency affect the nucleus growth, shape and kinetic pathways. These novel microscopic kinetics cast new light on control solid-solid transitions and microstructural evolutions in polycrystals.

Deposition and drying dynamics of liquid crystal droplets.

Drop drying and deposition phenomena reveal a rich interplay of fundamental science and engineering, give rise to fascinating everyday effects (coffee rings), and influence technologies ranging from printing to genotyping. Here we investigate evaporation dynamics, morphology, and deposition patterns of drying lyotropic chromonic liquid crystal droplets. These drops differ from typical evaporating colloidal drops primarily due to their concentration-dependent isotropic, nematic, and columnar phases. Phase separation occurs during evaporation, and in the process creates surface tension gradients and significant density and viscosity variation within the droplet. As a result, the drying multiphase drops exhibit different convective currents, drop morphologies, and deposition patterns (coffee-rings).

Vibrational properties of quasi-two-dimensional colloidal glasses with varying interparticle attraction.

We measure the vibrational modes and particle dynamics of quasi-two-dimensional colloidal glasses as a function of interparticle interaction strength. The interparticle attractions are controlled via a temperature-tunable depletion interaction. Specifically, the interparticle attraction energy is increased gradually from a very small value (nearly hard-sphere) to moderate strength (∼4k_{B}T), and the variation of colloidal particle dynamics and vibrations are concurrently probed. The particle dynamics slow monotonically with increasing attraction strength, and the particle motions saturate for strengths greater than ∼2k_{B}T, i.e., as the system evolves from a nearly repulsive glass to an attractive glass. The shape of the phonon density of states is revealed to change with increasing attraction strength, and the number of low-frequency modes exhibits a crossover for glasses with weak compared to strong interparticle attraction at a threshold of ∼2k_{B}T. This variation in the properties of the low-frequency vibrational modes suggests a new means for distinguishing between repulsive and attractive glass states.

Tunable depletion potentials driven by shape variation of surfactant micelles.

Depletion interaction potentials between micron-sized colloidal particles are induced by nanometer-scale surfactant micelles composed of hexaethylene glycol monododecyl ether (C_{12}E_{6}), and they are measured by video microscopy. The strength and range of the depletion interaction is revealed to arise from variations in shape anisotropy of the surfactant micelles. This shape anisotropy increases with increasing sample temperature. By fitting the colloidal interaction potentials to theoretical models, we extract micelle length and shape anisotropy as a function of temperature. This work introduces shape anisotropy tuning as a means to control interparticle interactions in colloidal suspensions, and it shows how the interparticle depletion potentials of micron-scale objects can be employed to probe the shape and size of surrounding macromolecules at the nanoscale.

Strain fluctuations and elastic moduli in disordered solids.

Recently there has been a surge in interest in using video-microscopy techniques to infer the local mechanical properties of disordered solids. One common approach is to minimize the difference between particle vibrational displacements in a local coarse-graining volume and the displacements that would result from a best-fit affine deformation. Effective moduli are then inferred under the assumption that the components of this best-fit affine deformation tensor have a Boltzmann distribution. In this paper, we combine theoretical arguments with experimental and simulation data to demonstrate that the above does not reveal information about the true elastic moduli of jammed packings and colloidal glasses.

Diagnosing hyperuniformity in two-dimensional, disordered, jammed packings of soft spheres.

Hyperuniformity characterizes a state of matter for which (scaled) density fluctuations diminish towards zero at the largest length scales. However, the task of determining whether or not an image of an experimental system is hyperuniform is experimentally challenging due to finite-resolution, noise, and sample-size effects that influence characterization measurements. Here we explore these issues, employing video optical microscopy to study hyperuniformity phenomena in disordered two-dimensional jammed packings of soft spheres. Using a combination of experiment and simulation we characterize the possible adverse effects of particle polydispersity, image noise, and finite-size effects on the assignment of hyperuniformity, and we develop a methodology that permits improved diagnosis of hyperuniformity from real-space measurements. The key to this improvement is a simple packing reconstruction algorithm that incorporates particle polydispersity to minimize the free volume. In addition, simulations show that hyperuniformity in finite-sized samples can be ascertained more accurately in direct space than in reciprocal space. Finally, our experimental colloidal packings of soft polymeric spheres are shown to be effectively hyperuniform.

Chiral structures and defects of lyotropic chromonic liquid crystals induced by saddle-splay elasticity.

An experimental and theoretical study of lyotropic chromonic liquid crystals (LCLCs) confined in cylinders with degenerate planar boundary conditions elucidates LCLC director configurations. When the Frank saddle-splay modulus is more than twice the twist modulus, the ground state adopts an inhomogeneous escaped-twisted configuration. Analysis of the configuration yields a large saddle-splay modulus, which violates Ericksen inequalities but not thermodynamic stability. Lastly, we observe point defects between opposite-handed domains, and we explain a preference for point defects over domain walls.