Stimuli-responsive (active) materials undergo large-scale shape or property changes in response to an external stimulus such as stress, temperature, light or pH. Technological uses range from durable, shape-recovery eye-glass frames, to temperature-sensitive switches, to the generation of stress to induce mechanical motion. Here, we demonstrate that the uniform dispersion of 1-5 vol.% of carbon nanotubes in a thermoplastic elastomer yields nanocomposites that can store and subsequently release, through remote means, up to 50% more recovery stress than the pristine resin. The anisotropic nanotubes increase the rubbery modulus by a factor of 2 to 5 (for 1-5 vol.%) and improve shape fixity by enhancing strain-induced crystallization. Non-radiative decay of infrared photons absorbed by the nanotubes raises the internal temperature, melting strain-induced polymer crystallites (which act as physical crosslinks that secure the deformed shape) and remotely trigger the release of the stored strain energy. Comparable effects occur for electrically induced actuation associated with Joule heating of the matrix when a current is passed through the conductive percolative network of the nanotubes within the resin. This unique combination of properties, directly arising from the nanocomposite morphology, demonstrates new opportunities for the design and fabrication of stimuli-responsive polymers, which are otherwise not available in one material system.

Layered silicates are widely used in nanotechnology and composite materials. We describe a force field for phyllosilicates (mica, montmorillonite, and pyrophyllite) on the basis of physically justified atomic charges, van der Waals parameters, vibrational constants, and distributions of charge defects in agreement with solid state 29 Si NMR data. Unit cell parameters deviate only ∼0.5% relative to experimental X-ray measurements and surface (respectively cleavage) energies deviate less than 10% from experimental data, including the partition between Coulomb and van der Waals contributions. Reproduction of surface energies facilitates quantitative simulations of hybrid interfaces with water, organics, and biomolecules for which accurate force fields are available. Parameters are consistent with the force fields PCFF (polymer consistent force field), CVFF (consistent valence force field), CHARMM (chemistry at Harvard macromolecular mechanics), and GROMACS (Groningen machine for chemical simulations). As an example of interest, we investigate the structure and dynamics of octadecylammonium montmorillonite ("C 18 "-montmorillonite, cation exchange capacity ) 91 mmol/100 g) by molecular dynamics simulation. The surfactant chains assemble essentially as a bilayer with minimal interpenetration within the gallery while the ammonium headgroups are hydrogen-bonded to cavities in the montmorillonite surface. In contrast to quaternary ammonium ions, no rearrangements on the surface have been observed (cavity crossing barrier >5 kcal/mol). The alkyl chains are in a liquidlike state with approximately 30% gauche conformations, in agreement with previous Fourier-transform infrared and solid-state NMR measurements. Computed X-ray diffraction patterns of sodium and C 18 -montmorillonite agree very well with X-ray patterns from experiment, and the computational model can assist in the assignment of complex reflections.

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For nanoparticle-based technologies, efficient and rapid approaches that yield particles of high purity with a specific shape and size are critical to optimize the nanostructure-dependent optical, electrical, and magnetic properties, and not bias conclusions due to the existence of impurities. Notwithstanding the continual improvement of chemical methods for shaped nanoparticle synthesis, byproducts are inevitable. Separation of these impurities may be achieved, albeit inefficiently, through repeated centrifugation steps only when the sedimentation coefficient of the species shows sufficient contrast. We demonstrate a robust and efficient procedure of shape and size selection of Au nanoparticles (NPs) through the formation of reversible flocculates by surfactant micelle induced depletion interaction. Au NP flocculates form at a critical surfactant micelle molar concentration, C(m)* where the number of surfactant micelles is sufficient to induce an attractive potential energy between the Au NPs. Since the magnitude of this potential depends on the interparticle contact area of Au NPs, separation is achieved even for the NPs of the same mass with different shape by tuning the surfactant concentration and extracting flocculates from the sediment by centrifugation or gravitational sedimentation. The refined NPs are redispersed by subsequently decreasing the surfactant concentration to reduce the effective attractive potential. These concepts provide a robust method to improve the quality of large scale synthetic approaches of a diverse array of NPs, as well as fine-tune interparticle interactions for directed assembly, both crucial challenges to the continual realization of the broad technological potential of monodispersed NPs.

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Gold nanorods (Au NRs) are the archetype of a nanoantenna, enabling the directional capture, routing, and concentration of electromagnetic fields at the nanoscale. Solution-based synthesis methods afford advantages relative to top-down fabrication but are challenged by insufficient precision of structure, presence of byproducts, limited tunability of architecture, and device integration. This is due in part to an inadequate understanding of the early stages of Au NR growth. Here, using phase transfer via ligand exchange with monothiolated polystyrene, we experimentally demonstrate the complete evolution of seed-mediated Au NR growth in hexadecyltrimethylammonium bromide (CTAB) solution. Au NR size and shape progress from slender spherocylinders at short reaction times to rods with a dumbbell profile, flattened end facets, and octagonal prismatic structures at later stages. These evolve from a single mechanism and reflect the majority of reported Au NR morphologies, albeit reflecting different stages. Additionally, the fraction of nonrod impurities in a reaction is related to the initial distribution of the structure of the seed particles. Overall, the observations of early and intermediate stage growth are consistent with the formation of a surfactant bilayer on different crystal facets at different growth stages due to a fine balance between kinetic and thermodynamic factors.

Over the past three decades, the combination of inorganic-nanoparticles and organic-polymers has led to a wide variety of advanced materials, including polymer nanocomposites (PNCs). Recently, synthetic innovations for attaching polymers to nanoparticles to create "hairy nanoparticles" (HNPs) has expanded opportunities in this field. In addition to nanoparticle compatibilization for traditional particle-matrix blending, neat-HNPs afford one-component hybrids, both in composition and properties, which avoids issues of mixing that plague traditional PNCs. Continuous improvements in purity, scalability, and theoretical foundations of structure-performance relationships are critical to achieving design control of neat-HNPs necessary for future applications, ranging from optical, energy, and sensor devices to lubricants, green-bodies, and structures.

Cantilevers composed of glassy, photoresponsive liquid crystalline polymer networks (LCNs) are shown to oscillate at high frequency ( ∼ 50 Hz) and large amplitude when exposed to light from a 442 nm coherent wave (CW) laser. Added dimensionality to previously reported in-plane oscillations is enabled by adjusting the orientation of the nematic director to the long axis of the cantilever yielding in-plane bending accompanied by out-of-plane twisting (fl exural-torsional oscillation). The fundamental photoresponse of this class of glassy azobenzene liquid crystal polymer networks (azo-LCN) is further probed by examining the infl uence of cantilever aspect ratio, laser intensity, and temperature. The frequency of photodirected oscillations is strongly correlated to the length of the cantilever while the amplitude and threshold laser intensity for oscillation is strongly correlated to temperature.