Colloidal aggregation in microgravity by critical Casimir forces.

By using the critical Casimir force, we study the attractive strength dependent aggregation of colloids with and without gravity by means of near field scattering. Significant differences were seen between microgravity and ground experiments, both in the structure of the formed fractal aggregates as well as in the kinetics of growth. In microgravity purely diffusive aggregation is observed. By using the continuously variable particle interaction potential we can for the first time experimentally relate the strength of attraction between the particles and the structure of the aggregates.

Revealing Driving Forces in Quantum Dot Supercrystal Assembly.

The assembly of semiconductor nanoparticles, quantum dots (QDs), into dense crystalline nanostructures holds great promise for future optoelectronic devices. However, knowledge of the sub-nanometer scale driving forces underlying the kinetic processes of nucleation, growth, and final densification during QD assembly remains poor. Emulsion-templated assembly has recently been shown to provide good control over the bulk condensation of QDs into highly ordered 3D supercrystals. Here, emulsion-templated assembly is combined with in situ small-angle X-ray scattering to obtain direct insight into the nanoscale interactions underlying the nucleation, growth, and densification of QD supercrystals. At the point of supercrystal nucleation, nanoparticles undergo a hard-sphere-like crystallization into a hexagonal-close-packed lattice, slowly transforming into a face-centered-cubic lattice. The ligands play a crucial role in balancing steric repulsion against attractive van der Waals forces to mediate the initial equilibrium assembly, but cause the QDs to be progressively destabilized upon densification. The rich detail of this kinetic study elucidates the assembly and thermodynamic properties that define QD supercrystal fabrication approaching single-crystal quality, paving the way toward their use in optoelectronic devices.

Confinement-induced liquid ordering investigated by x-ray phase retrieval.

Using synchrotron x-ray diffraction, we have determined the ensemble-averaged density profile of colloidal fluids within confining channels of different widths. We observe an oscillatory ordering-disordering behavior of the colloidal particles as a function of the channel width, while the colloidal solution remains in the liquid state. This phenomenon has been suggested by surface force studies of hard-sphere fluids and also theoretically predicted, but here we see it by direct measurements of the structure for comparable systems.

Sharp symmetry-change marks the mechanical failure transition of glasses.

Glasses acquire their solid-like properties by cooling from the supercooled liquid via a continuous transition known as the glass transition. Recent research on soft glasses indicates that besides temperature, another route to liquify glasses is by application of stress that drives relaxation and flow. Here, we show that unlike the continuous glass transition, the failure of glasses to applied stress occurs by a sharp symmetry change that reminds of first-order equilibrium transitions. Using simultaneous x-ray scattering during the oscillatory rheology of a colloidal glass, we identify a sharp symmetry change from anisotropic solid to isotropic liquid structure at the crossing of the storage and loss moduli. Concomitantly, intensity fluctuations sharply acquire Gaussian distributions characteristic of liquids. Our observations and theoretical framework identify mechanical failure as a sharp atomic affine-to-nonaffine transition, providing a new conceptual paradigm of the oscillatory yielding of this technologically important class of materials, and offering new perspectives on the glass transition.

Controlling colloidal phase transitions with critical Casimir forces.

The critical Casimir force provides a thermodynamic analogue of the quantum mechanical Casimir force that arises from the confinement of electromagnetic field fluctuations. In its thermodynamic analogue, two surfaces immersed in a critical solvent mixture attract each other due to confinement of solvent concentration fluctuations. Here, we demonstrate the active assembly control of colloidal equilibrium phases using critical Casimir forces. We guide colloidal particles into analogues of molecular liquid and solid phases via exquisite control over their interactions. By measuring the critical Casimir pair potential directly from density fluctuations in the colloidal gas, we obtain insight into liquefaction at small scales. We apply the van der Waals model of molecular liquefaction and show that the colloidal gas-liquid condensation is accurately described by the van der Waals theory, even on the scale of a few particles. These results open up new possibilities in the active assembly control of micro and nanostructures.

Reversible phase transition of colloids in a binary liquid solvent.

We report fluid-fluid and fluid-solid phase transitions of charge-stabilized polystyrene particles suspended in a binary liquid mixture of 3-methylpyridine and water. These thermally reversible phase transitions occur in the homogeneous phase of the binary liquid mixture below the coexistence temperature of the two liquids. Close density matching of the particles and the solvent allows us to follow the phase behavior until complete coexistence of macroscopic phases with temperature as the control parameter. We use small angle x-ray scattering to characterize these phases as colloidal gas, liquid, fcc crystal, and glass.

Gels and glasses in a single system: evidence for an intricate free-energy landscape of glassy materials.

In the free-energy landscape picture of glassy systems, their slow dynamics is due to a complicated free-energy landscape with many local minima. We show that for a colloidal glassy material multiple paths can be taken through the free-energy landscape. The evolution of the nonergodicity parameter shows two distinct master curves that we identify as gels and glasses. We show that for a range of colloid concentrations, the transition to nonergodicity can occur in either direction (gel or glass), accompanied by "hesitations" between the two. Thus, colloidal gels and glasses are merely global free-energy minima in the same free-energy landscape, and the paths leading to these minima can be complicated.

Fluctuation-dissipation theorem in an aging colloidal glass.

We provide a direct experimental test of the fluctuation-dissipation theorem (FDT) in an aging colloidal glass. The use of combined active and passive microrheology allows us to independently measure both the correlation and response functions in this nonequilibrium situation. Contrary to previous reports, we find no deviations from the FDT over several decades in frequency (1 Hz-10 kHz) and for all aging times. In addition, we find two distinct viscoelastic contributions in the aging glass, including a nearly elastic response at low frequencies that grows during aging.

Surface response functions for a thin-film between fluids with infinite boundaries and for a fluid-fluid interface between finite boundaries.

Measuring the surface response function of a fluid allows us to ascertain many of its properties. Simplified surface response functions are presented for several interface conditions, including (a) a thin-film between two fluids of infinite extent, (b) the newly derived fluid-fluid interface between finite boundaries, and (c) the traditional fluid-fluid interface between infinite boundaries. The finite-boundary derivation indicates that wall effects are very short range. This portends that the effects of external vibrations, which traditionally make this measurement challenging, can be mitigated by scattering from thin fluid layers.

Photon correlation and scattering: introduction to the feature issue.

This special issue of Applied Optics contains research papers on photon correlation and scattering, many of which were presented at the OSA Topical Meeting that was held 16-18 August 2004.

Hydrodynamics of droplet coalescence.

We study droplet coalescence in a molecular system with a variable viscosity and a colloid-polymer mixture with an ultralow surface tension. When either the viscosity is large or the surface tension is small enough, we observe that the opening of the liquid bridge initially proceeds at a constant speed set by the capillary velocity. In the first system we show that inertial effects become dominant at a Reynolds number of about 1.5+/- 0.5 and the neck then grows as the square root of time. In the second system we show that decreasing the surface tension by a factor of 10(5) opens the way to a more complete understanding of the hydrodynamics involved.

What controls the thickness of wetting layers near bulk criticality?

We study the thickness of wetting layers in the binary-liquid mixture cyclohexane methanol. Far from the bulk critical point, the wetting layer thickness is independent of temperature, resulting from the competition between van der Waals and gravitational forces. Upon approaching the bulk critical temperature [t=(T(c)-T)/T(c)-->0], we observe that the wetting layer thickness diverges as t(-beta) with effective critical exponent beta=0.23+/-0.06. This is characteristic of a broad, intermediate scaling regime for the crossover from van der Waals wetting to critical scaling. We predict beta=beta/3 approximately 0.11, with beta the usual bulk-order parameter critical exponent, showing a small but significant difference with experiment.