Spontaneous emulsification induced by nanoparticle surfactants.

Microemulsions, mixtures of oil, water, and surfactant, are thermodynamically stable. Unlike conventional emulsions, microemulsions form spontaneously, have a monodisperse droplet size that can be controlled by adjusting the surfactant concentration, and do not degrade with time. To make microemulsions, a judicious choice of surfactant molecules must be made, which significantly limits their potential use. Nanoparticle surfactants, on the other hand, are a promising alternative because the surface chemistry needed to make them bind to a liquid-liquid interface is both well flexible and understood. Here, we derive a thermodynamic model predicting the conditions in which nanoparticle surfactants drive spontaneous emulsification that agrees quantitatively with experiments using Noria nanoparticles. This new class of microemulsions inherits the mechanical, chemical, and optical properties of the nanoparticles used to form them, leading to novel applications.

Capillary deformations of bendable films.

We address the partial wetting of liquid drops on ultrathin solid sheets resting on a deformable foundation. Considering the membrane limit of sheets that can relax compression through wrinkling at negligible energetic cost, we revisit the classical theory for the contact of liquid drops on solids. Our calculations and experiments show that the liquid-solid-vapor contact angle is modified from the Young angle, even though the elastic bulk modulus (E) of the sheet is so large that the ratio between the surface tension γ and E is of molecular size. This finding indicates a new elastocapillary phenomenon that stems from the high bendability of very thin elastic sheets rather than from material softness. We also show that the size of the wrinkle pattern that emerges in the sheet is fully predictable, thus resolving a puzzle in modeling "drop-on-a-floating-sheet" experiments and enabling a quantitative, calibration-free use of this setup for the metrology of ultrathin films.

Curie transitions for attograms of ferroelectric polymers.

Polymer systems having one, two, or three dimensions on the nanometer length scale can exhibit physical properties different from the bulk. The degree of disorder characteristic for large amounts of matter is strongly reduced and changes in symmetry are imposed by means of geometrical confinement. This could be used to induce-through orientation and order-enhancement in the material properties. Experiments on extremely small amounts of matter, however, are naturally characterized by large fluctuations in the measured signals, especially in the case of polymer objects having three dimensions on the nanometer length scale. This imposes the necessity of repeating the measurements until a statistical distribution is obtained. Here we show that investigations on statistical ensembles of attograms of material (1 ag = 10(-18) g) are possible in a single experiment by employing highly ordered arrays of identical, independent, additive nanocontainers. Phase transitions corresponding to attograms of a ferroelectric polymer are measured by this approach. As compared to one- or two-dimensional confinement, significant changes in the Curie transitions are found.

On the kinetics of nanoparticle self-assembly at liquid/liquid interfaces.

We investigate the concentration and size dependent self-assembly of cadmium selenide nanoparticles at an oil/water interface. Using a pendant drop tensiometer, we monitor the assembly kinetics and evaluate the effective diffusion coefficients following changes in the interfacial tension for the early and late stages of nanoparticle adsorption. Comparison with the coefficients for free diffusion reveals the energy barrier for particle segregation to the interface. The formation of a nanoparticle monolayer at the oil/water interface is characterised by transmission electron microscopy.

Symmetric-to-asymmetric transition in triblock copolymer-homopolymer blends.

In blends of a symmetric poly(styrene-ethylene/butylene-styrene) tri-block-copolymer with a polystyrene homopolymer, small-angle x-ray scattering and cryotransmission electron microscopy measurements reveal a microstructure consisting of a disordered arrangement of poly(ethylene/butylene) membranes suspended in polystyrene. For triblock volume fractions less than 0.22, the membranes form an asymmetric sponge or L4 phase, consisting predominantly of equilibrium vesicles. For volume fractions greater than 0.22, they form a symmetric sponge-phase (L3 phase), separated from the L4 phase by a first-order transition.

Nanoparticle assembly and transport at liquid-liquid interfaces.

The self-assembly of particles at fluid interfaces, driven by the reduction in interfacial energy, is well established. However, for nanoscopic particles, thermal fluctuations compete with interfacial energy and give rise to a particle-size-dependent self-assembly. Ligand-stabilized nanoparticles assembled into three-dimensional constructs at fluid-fluid interfaces, where the properties unique to the nanoparticles were preserved. The small size of the nanoparticles led to a weak confinement of the nanoparticles at the fluid interface that opens avenues to size-selective particle assembly, two-dimensional phase behavior, and functionalization. Fluid interfaces afford a rapid approach to equilibrium and easy access to nanoparticles for subsequent modification. A photoinduced transformation is described in which nanoparticles, initially soluble only in toluene, were transported across an interface into water and were dispersed in the water phase. The characteristic fluorescence emission of the nanoparticles provided a direct probe of their spatial distribution.

Surface-responsive materials.

Synthetic polymers offer a wealth of opportunities to design responsive materials triggered by external stimuli. Changing the length, chemical composition, architecture, and topology of the chains allows response mechanisms and rates to be easily manipulated; and devices based on the entropy of the chains, surface energies, and specific segmental interactions can readily be made. Although numerous applications exist, intriguing possibilities are emerging that have tremendous potential to further developments in surface-responsive materials.

Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates.

We show a simple, robust, chemical route to the fabrication of ultrahigh-density arrays of nanopores with high aspect ratios using the equilibrium self-assembled morphology of asymmetric diblock copolymers. The dimensions and lateral density of the array are determined by segmental interactions and the copolymer molecular weight. Through direct current electrodeposition, we fabricated vertical arrays of nanowires with densities in excess of 1.9 x 10(11) wires per square centimeter. We found markedly enhanced coercivities with ferromagnetic cobalt nanowires that point toward a route to ultrahigh-density storage media. The copolymer approach described is practical, parallel, compatible with current lithographic processes, and amenable to multilayered device fabrication.