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.
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.
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.
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.
We conduct experiments on two-dimensional packings of colloidal thermosensitive hydrogel particles whose packing fraction can be tuned above the jamming transition by varying the temperature. By measuring displacement correlations between particles, we extract the vibrational properties of a corresponding "shadow" system with the same configuration and interactions, but for which the dynamics of the particles are undamped. The vibrational spectrum and the nature of the modes are very similar to those predicted for zero-temperature idealized sphere models and found in atomic and molecular glasses; there is a boson peak at low frequency that shifts to higher frequency as the system is compressed above the jamming transition.PACS numbers: 63. 63.50 Lm, 82.70 Dd Crystalline solids are all alike in their vibrational properties at low frequencies; every disordered solid is disordered in its own way. Disordered solids nonetheless exhibit common low-frequency vibrational properties that are completely unlike those of crystals, which are dominated by sound modes. Disordered atomic or molecular solids generically exhibit a "boson peak," where many more modes appear than expected for sound. The excess modes of the boson peak are believed to be responsible for the unusual behavior of the heat capacity and thermal conductivity at low-to-intermediate temperatures in disordered solids [2].It has been proposed that a zero-temperature jamming transition may provide a framework for understanding this unexpected commonality [3]. For frictionless, idealized spheres this jamming transition lies at the threshold of mechanical stability, known as the isostatic point [3,4]. As a result of this coincidence, the vibrational behavior of the marginally jammed solid at densities just above the jamming transition is fundamentally different from that of ordinary elastic solids [5][6][7][8]. A new class of lowfrequency vibrational modes arises because the system is at the threshold of mechanical stability [10]; these modes give rise to a divergent boson peak at zero frequency [5]. As the system is compressed beyond the jamming transition, the boson peak shrinks in height and shifts upwards in frequency [5]. Generalizations of the idealized sphere model suggest that the boson peaks of a wide class of disordered solids may arise from proximity to the jamming transition [9][10][11][12]. Moreover, the jamming scenario predicts that systems with larger constituents such as colloids should also have boson peaks.Colloidal glasses offer signal advantages over atomic or molecular disordered solids because colloids can be tracked by video microscopy. Vibrational behavior has been explored in hard-sphere colloids [13] and vibrated granular packings [14], but difficulties with statistics [13] or micro-cracks [14] were encountered. In contrast, we use deformable, thermosensitive hydrogel particles to tune the packing fraction in situ. Our experiments show unambiguously that the commonality in vibrational properties observed in atomic and molecular glas...
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