A revolution in novel nanoparticles and colloidal building blocks has been enabled by recent breakthroughs in particle synthesis. These new particles are poised to become the 'atoms' and 'molecules' of tomorrow's materials if they can be successfully assembled into useful structures. Here, we discuss the recent progress made in the synthesis of nanocrystals and colloidal particles and draw analogies between these new particulate building blocks and better-studied molecules and supramolecular objects. We argue for a conceptual framework for these new building blocks based on anisotropy attributes and discuss the prognosis for future progress in exploiting anisotropy for materials design and assembly.
The melt-state linear and nonlinear shear rheological properties of hybrid materials of polypropylene and amine-exchanged montmorillonite were studied. The materials were prepared by melt mixing with maleic anhydride functionalized polypropylene as the compatibilizer. The clay interlayer spacing (as determined by wide-angle X-ray scattering) increased upon melt mixing; however, the short-range ordering of the clay layers was preserved. Above inorganic loadings of 2.0 wt % the hybrid materials exhibited apparent low-frequency plateaus in the linear viscoelastic moduli. The hybrid storage modulus was sensitive to the chemistry of the amine exchanged into the clay. The amount of stress overshoot observed in flow reversal experiments was found to be a function of the rest time allowed between the reversal. The transient stress in start-up of steady shear scaled with the applied strain. These observations allow features of the polypropylene/montmorillonite hybrid structure to be deduced. The transient nonlinear rheology is consistent with an anisometric, non-Brownian structure. These anisometric particulate domains are mesoscopic, and internally, they contain multiple, ordered platelets. This mesoscopic structure is itself thermodynamically unstable, because the rheology indicates that quiescent structural evolution whose origin is not Brownian relaxation is observed. The demonstration of the sensitivity of melt-state rheological measurements to interparticle structure and chemistry of the hybrid materials indicates the potential usefulness of such studies for the development of new nanocomposite materials.
We review the sequences of structural states that can be induced in colloidal suspensions by the application of flow. Structure formation during flow is strongly affected by the delicate balance among interparticle forces, Brownian motion and hydrodynamic interactions. The resulting nonequilibrium microstructure is in turn a principal determinant of the suspension rheology. Colloidal suspensions with near hard-sphere interactions develop an anisotropic, amorphous structure at low dimensionless shear rates. At high rates, clustering due to strong hydrodynamic forces leads to shear thickening rheology. Application of steady-shear flow to suspensions with repulsive interactions induces a rich sequence of transitions to one-, two-and threedimensional order. Oscillatory-shear flow generates metastable ordering in suspensions with equilibrium liquid structure. On the other hand, shortrange attractive interactions can lead to a fluid-to-gel transition under quiescent suspensions. Application of flow leads to orientation, breakup, densification and spatial reorganization of aggregates. Using a non-Newtonian suspending medium leads to additional possibilities for organization. We examine the extent to which theory and simulation have yielded mechanistic understanding of the microstructural transitions that have been observed.
The development of model materials and image processing methods to directly visualize and quantify colloidal rod assembly by means of confocal laser scanning microscopy (CLSM) is reported. Monodisperse fluorescent colloidal rods are prepared by the uniaxial extensional deformation of sterically stabilized microspheres at elevated temperatures. The particles are stably dispersed in refractive index matching mixed organic solvents for CLSM. An image processing algorithm is developed to detect rod backbones and extract particle centroids and orientation angles from the CLSM image volumes. By means of these methods we quantify the distribution of rod orientation angles in self-assembled structures of rods formed by sedimentation. We find the observations to be consistent with aspect-ratio-dependent jamming and orientational order/disorder transition in the rod sediments.
Transitions in structural heterogeneity of colloidal depletion gels formed through short-range attractive interactions are correlated with their dynamical arrest. The system is a density and refractive index matched suspension of 0.20 volume fraction poly(methyl methacyrlate) colloids with the non-adsorbing depletant polystyrene added at a size ratio of depletant to colloid of 0.043. As the strength of the short-range attractive interaction is increased, clusters become increasingly structurally heterogeneous, as characterized by number-density fluctuations, and dynamically immobilized, as characterized by the single-particle mean-squared displacement. The number of free colloids in the suspension also progressively declines. As an immobile cluster to gel transition is traversed, structural heterogeneity abruptly decreases. Simultaneously, the mean single-particle dynamics saturates at a localization length on the order of the short-range attractive potential range. Both immobile cluster and gel regimes show dynamical heterogeneity. Non-Gaussian distributions of single particle displacements reveal enhanced populations of dynamical trajectories localized on two different length scales. Similar dependencies of number density fluctuations, free particle number and dynamical length scales on the order of the range of short-range attraction suggests a collective structural origin of dynamic heterogeneity in colloidal gels.
We systematically investigate droplet movement, coalescence, and splitting on an open hydrophobic surface. These processes are actuated by magnetic beads internalized in an oil-coated aqueous droplet using an external magnet. Results are organized into an 'operating diagram' that describes regions of droplet stable motion, breakage, and release from the magnet. The results are explained theoretically with a simple model that balances magnetic, friction, and capillary-induced drag forces and includes the effects of particle type, droplet size, surrounding oil layer, surface tension, and viscosity. Finally, we discuss the implications of the results for the design of magnet-actuated droplet systems for applications such as nucleic acid purification, immunoassay and drug delivery.
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