Hard, Soft, and Sticky Spheres for Dynamical Studies of Disordered Colloidal Packings

This thesis describes experiments which explore the role of interparticle interactions as a means to alter, and control, the properties of dense colloidal packings. The first set of experiments studied phonon modes in two-dimensional colloidal crystals composed of soft microgel particles with hard polystyrene particle dopants distributed randomly on the triangular lattice. By mixing hard and soft spheres we obtain close-packed lattices of spheres with random bond strength disorder, \textit{i.e.,} the effective springs coupling nearest-neighbors are either very stiff, very soft, or of intermediate stiffness. Video microscopy, particle tracking, and covariance matrix techniques are employed to derive the phonon modes of the corresponding ``shadow\u27\u27 crystals, thereby enabling us to study how bond strength disorder affects vibrational properties. Hard and soft particles participate equally in low frequency phonon modes, and the samples exhibit Debye-like density of states behavior characteristic of crystals at low frequency. For mid- and high-frequency phonons, the relative participation of hard versus soft particles in each mode is found to vary systematically with dopant concentration. The second set of experiments investigated depletion interaction potentials between micron-size colloidal particles induced by nanometer-scale micelles composed of the surfactant hexaethylene glycol monododecyl ether (C$_{12}$E$_{6}$). The strength and range of the depletion interaction is revealed to arise from variations in shape anisotropy of the rod-like surfactant micelles. This shape anisotropy increases with increasing sample temperature. By fitting the colloidal interaction potentials to theoretical models, we extract the rod-like micelle length and shape anisotropy as a function of temperature. This work introduces micelle shape anisotropy as a means to control interparticle interactions in colloidal suspensions, and shows how interparticle depletion potentials of micron-scale objects can be employed to probe the shape and size of surrounding macromolecules at the nano-scale. The third set of experiments explored variation in the vibrational properties of colloidal glasses induced by changes in interparticle interactions. In particular, we study the vibrational phonons of quasi-2D colloidal glasses whose interparticle interactions are controlled via the temperature tunable depletion interaction described in the aforementioned experimental work. This tunable attraction enables us to study the changes in the properties of a colloidal glass as the interparticle attraction strength is gradually increased from weak (nearly hard-sphere) to strong. We observed that particle dynamics slow monotonically with increasing attraction strength and eventually plateau at very high attraction strength. The shape of the phonon density of states is also revealed to change with increasing attraction strength; specifically, glasses with low interparticle attraction strength exhibit comparatively more low frequency modes than glasses with high interparticle attraction strength

Relationship Between Neighbor Number and Vibrational Spectra in disordered colloidal clusters with attractive interactions

We study connections between vibrational spectra and average nearest neighbor number in disordered clusters of colloidal particles with attractive interactions. Measurements of displacement covariances between particles in each cluster permit calculation of the stiffness matrix, which contains effective spring constants linking pairs of particles. From the cluster stiffness matrix, we derive vibrational properties of corresponding “shadow” glassy clusters, with the same geometric configuration and interactions as the “source” cluster but without damping. Here, we investigate the stiffness matrix to elucidate the origin of the correlations between the median frequency of cluster vibrational modes and average number of nearest neighbors in the cluster. We find that the mean confining stiffness of particles in a cluster, i.e., the ensemble-averaged sum of nearest neighbor spring constants, correlates strongly with average nearest neighbor number, and even more strongly with median frequency. Further, we find that the average oscillation frequency of an individual particle is set by the total stiffness of its nearest neighbor bonds; this average frequency increases as the square root of the nearest neighbor bond stiffness, in a manner similar to the simple harmonic oscillator

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

Vibrational and structural signatures of the crossover between dense glassy and sparse gel-like attractive colloidal packings

We investigate the vibrational modes of quasi-two-dimensional disordered colloidal packings of hard colloidal spheres with short-range attractions as a function of packing fraction. Certain properties of the vibrational density of states (vDOS) are shown to correlate with the density and structure of the samples (i.e., in sparsely versus densely packed samples). Specifically, a crossover from dense glassy to sparse gel-like states is suggested by an excess of phonon modes at low frequency and by a variation in the slope of the vDOS with frequency at low frequency. This change in phonon mode distribution is demonstrated to arise largely from localized vibrations that involve individual and/or small clusters of particles with few local bonds. Conventional order parameters and void statistics did not exhibit obvious gel-glass signatures as a function of volume fraction. These mode behaviors and accompanying structural insights offer a potentially new set of indicators for identification of glass-gel transitions and for assignment of gel-like versus glass-like character to a disordered solid material

Advanced Colloids Experiment (ACE) Science Overview

The Advanced Colloids Experiment is being conducted on the International Space Station (ISS) using the Light Microscopy Module (LMM) in the Fluids Integrated Rack (FIR). Work to date will be discussed and future plans and opportunities will be highlighted. The LMM is a microscope facility designed to allow scientists to process, manipulate, and characterize colloidal samples in micro-gravity where the absence of gravitational settling and particle jamming enables scientists to study such things as:a.The role that disordered and ordered-packing of spheres play in the phase diagram and equation of state of hard sphere systems,b.crystal nucleation and growth, growth instabilities, and the glass transition, c.gelation and phase separation of colloid polymer mixtures,d.crystallization of colloidal binary alloys,e.competition between crystallization and phase separation,f.effects of anisotropy and specific interactions on packing, aggregation, frustration and crystallization,g.effects of specific reversible and irreversible interactions mediated in the first case by hybridization of complementary DNA strands attached to separate colloidal particles,h.Lock and key interactions between colloids with dimples and spheres which match the size and shape of the dimples,i.finding the phase diagrams of isotropic and interacting particles,j.new techniques for complex self-assembly including scenarios for self-replication, k.critical Casimir forces,l.biology (real and model systems) in microgravity,m.etc. By adding additional microscopy capabilities to the existing LMM, NASA will increase the tools available for scientists that fly experiments on the ISS enabling scientists to observe directly what is happening at the particle level. Presently, theories are needed to bridge the gap between what is being observed (at a macroscopic level when photographing samples) with what is happening at a particle (or microscopic) level. What is happening at a microscopic level will be directly accessible with the availability of the Light Microscopy Module (LMM) on ISS. To meet these goals, the ACE experiment is being built-up in stages, with the availability of confocal microscopy being the ultimate objective. Supported by NASAs Physical Sciences Research Program, ESAESTEC, and the authors respective governments

Correlated rearrangements of disordered colloidal suspensions in the vicinity of the reentrant glass transition

We experimentally investigate correlated rearrangements (dynamic heterogeneity) in disordered colloidal suspensions as a function of increasing inter-particle attraction strength across the reentrant glass transition. Attractive interactions between constituent spheres are induced by polymer depletion forces at fixed particle volume fraction. We vary sample inter-particle attraction strength and concurrently measure particle trajectories by confocal microscopy at each attraction strength. The reentrant transition from repulsive glass to ergodic fluid and from ergodic fluid to attractive glass is readily observed. As the inter-particle attraction increases, we find that inter-particle bonding causes an increasing number of particles to undergo cooperative or correlated displacements; the length scale associated with these correlated rearrangements exhibits reentrant behavior. Other dynamical quantities such as the mean square displacement, the long-time diffusion constant, and the non-Gaussian parameter also exhibit changes as a function of attraction strength. Notably, the arrested (glass) states show small particle displacements at long lag times, whereas the fluid states exhibit fast dynamics over large length scales