Ahmed Alsayed

Thermal vestige of the zero-temperature jamming transition

When the packing fraction is increased sufficiently, loose particulates jam to form a rigid solid in which the constituents are no longer free to move. In typical granular materials and foams, the thermal energy is too small to produce structural rearrangements. In this zero-temperature (T = 0) limit, multiple diverging and vanishing length scales characterize the approach to a sharp jamming transition. However, because thermal motion becomes relevant when the particles are small enough, it is imperative to understand how these length scales evolve as the temperature is increased. Here we used both colloidal experiments and computer simulations to progress beyond the zero-temperature limit to track one of the key parameters—the overlap distance between neighbouring particles—which vanishes at the T = 0 jamming transition. We find that this structural feature retains a vestige of its T = 0 behaviour and evolves in an unusual manner, which has masked its appearance until now. It is evident as a function of packing fraction at fixed temperature, but not as a function of temperature at fixed packing fraction or pressure. Our results conclusively demonstrate that length scales associated with the T = 0 jamming transition persist in thermal systems, not only in simulations but also in laboratory experiments.

Two-step nucleation mechanism in solid–solid phase transitions

The microscopic kinetics of ubiquitous solid-solid phase transitions remain poorly understood. Here, by using single-particle-resolution video microscopy of colloidal films of diameter-tunable microspheres, we show that transitions between square and triangular lattices occur via a two-step diffusive nucleation pathway involving liquid nuclei. The nucleation pathway is favoured over the direct one-step nucleation because the energy of the solid/liquid interface is lower than that between solid phases. We also observed that nucleation precursors are particle-swapping loops rather than newly generated structural defects, and that coherent and incoherent facets of the evolving nuclei exhibit different energies and growth rates that can markedly alter the nucleation kinetics. Our findings suggest that an intermediate liquid should exist in the nucleation processes of solid-solid transitions of most metals and alloys, and provide guidance for better control of the kinetics of the transition and for future refinements of solid-solid transition theory.

Geometric frustration in buckled colloidal monolayers

Geometric frustration arises when lattice structure prevents simultaneous minimization of local interaction energies. It leads to highly degenerate ground states and, subsequently, to complex phases of matter, such as water ice, spin ice, and frustrated magnetic materials. Here we report a simple geometrically frustrated system composed of closely packed colloidal spheres confined between parallel walls. Diameter-tunable microgel spheres are self-assembled into a buckled triangular lattice with either up or down displacements, analogous to an antiferromagnetic Ising model on a triangular lattice. Experiment and theory reveal single-particle dynamics governed by in-plane lattice distortions that partially relieve frustration and produce ground states with zigzagging stripes and subextensive entropy, rather than the more random configurations and extensive entropy of the antiferromagnetic Ising model. This tunable soft-matter system provides a means to directly visualize the dynamics of frustration, thermal excitations and defects.

Synthesis of micrometer-size poly(N-isopropylacrylamide) microgel particles with homogeneous crosslinker density and diameter control

Poly(N-isopropylacrylamide) microgel particles are synthesized using a semi-batch surfactant-free emulsion polymerization method. Particle diameter can be precisely adjusted by controlling the initial conditions, the electrolyte concentration, and the monomer feeding rate and duration. Larger particles are obtained in the presence of small amounts of co-monomer with cationic amino groups that compete against the negative charges arising from the initiator. Monodisperse particles with uniform cross-linker density, homogeneous optical properties, and pronounced thermoresponsivity are readily produced with a wide variety of diameters ranging from several hundred nanometers to a few micrometers. The charge stabilization mechanisms that control particle growth are discussed.

Template-directed convective assembly of three-dimensional face-centered-cubic colloidal crystals

We demonstrate that square two-dimensional grating templates can drive the growth of three-dimensional, face-centered-cubic (fcc) colloidal crystals by convective assembly. The square symmetry [i.e., (100) planes parallel to the substrate] of the underlying template was transferred to the colloidal crystal and maintained throughout its growth of ∼50 layers. We characterized crystals grown on flat and on templated substrates using electron microscopy and small-angle x-ray scattering (SAXS). SAXS measurements of the templated samples clearly show fourfold diffraction patterns that arise from fcc domains without stacking faults.

Helical Packings and Phase Transformations of Soft Spheres in Cylinders

The phase behavior of helical packings of thermoresponsive microspheres inside glass capillaries is studied as a function of the volume fraction. Stable packings with long-range orientational order appear to evolve abruptly to disordered states as the particle volume fraction is reduced, consistent with recent hard-sphere simulations. We quantify this transition using correlations and susceptibilities of the orientational order parameter psi6. The emergence of coexisting metastable packings, as well as coexisting ordered and disordered states, is also observed. These findings support the notion of phase-transition-like behavior in quasi-one-dimensional systems.

Two-dimensional freezing criteria for crystallizing colloidal monolayers

Video microscopy was employed to explore crystallization of colloidal monolayers composed of diameter-tunable microgel spheres. Two-dimensional (2D) colloidal liquids were frozen homogenously into polycrystalline solids, and four 2D criteria for freezing were experimentally tested in thermal systems for the first time: the Hansen-Verlet freezing rule, the Lowen-Palberg-Simon dynamical freezing criterion, and two other rules based, respectively, on the split shoulder of the radial distribution function and on the distribution of the shape factor of Voronoi polygons. Importantly, these freezing criteria, usually applied in the context of single crystals, were demonstrated to apply to the formation of polycrystalline solids. At the freezing point, we also observed a peak in the fluctuations of the orientational order parameter and a percolation transition associated with caged particles. Speculation about these percolated clusters of caged particles casts light on solidification mechanisms and dynamic heterogeneity in freezing.

Two features at the two-dimensional freezing transitions.

We studied the two-dimensional freezing transitions in monolayers of microgel colloidal spheres with short-ranged repulsions in video-microscopy experiments, and monolayers of hard disks, and Yukawa particles in simulations. These systems share two common features at the freezing points: (1) the bimodal distribution profile of the local orientational order parameter; (2) the two-body excess entropy, s(2), reaches -4.5±0.5 k(B). Both features are robust and sensitive to the freezing points, so that they can potentially serve as empirical freezing criteria in two dimensions. Compared with the conventional freezing criteria, the first feature has no finite-size ambiguities and can be resolved adequately with much less statistics; and the second feature can be directly measured in macroscopic experiments without the need for microscopic information.

Particle dynamics in colloidal suspensions above and below the glass-liquid re-entrance transition

We study colloidal particle dynamics of a model glass system using confocal and fluorescence microscopy as the sample evolves from a hard-sphere glass to a liquid with attractive interparticle interactions. The transition from hard-sphere glass to attractive liquid is induced by short-range depletion forces. The development of liquid-like structure is indicated by particle dynamics. We identify particles which exhibit substantial motional events and characterize the transition using the properties of these motional events. As samples enter the attractive liquid region, particle speed during these motional events increases by about one order of magnitude, and the particles move more cooperatively. Interestingly, colloidal particles in the attractive liquid phase do not exhibit significantly larger displacements than particles in the hard-sphere glass.

Plasmonic-Based Mechanochromic Microcapsules as Strain Sensors

Efficiently detecting mechanical deformations within materials is critical in a wide range of devices, from micro-electromechanical systems to larger structures in the aerospace industry. This communication reports the fabrication of new mechanochromic micrometer-size capsules enabling the detection of strains. These microcapsules are synthesized using an emulsification approach. They are made of densely packed gold nanoparticles embedded in a spherical silica crust. Billions of these composite spherical microcapsules are fabricated in a single batch. Each microcapsule is an opto-mechanosensor by itself, and can easily be recovered and incorporated into polymer films. When the films are stretched, the microcapsules are deformed into elongated ellipsoidal shapes and the distance between the Au NPs embedded in their shells concomitantly increases. As the extinction of Au NPs depends on the separation between the Au NPs, microcapsules exhibit different colors when they are elongated. These novel sensitive microcapsules can be used to detect and measure strain in polymer films by outputting color information.