Friedel-Crafts Addition of Indoles to Nitrones Promoted by Trimethylsilyl Trifluoromethanesulfonate.

N-Alkylindoles undergo Friedel-Crafts addition to aryl and secondary alkyl nitrones in the presence of trimethylsilyl trifluoromethanesulfonate and trialkylamine to produce 3-(1-(silyloxyamino)alkyl)indoles. Spontaneous conversion to bisindolyl(aryl)methanes, which is thermodynamically favored for nitrones derived from aromatic aldehydes, is suppressed under the reaction conditions. The silyloxyamino group can be deprotected with tetrabutylammonium fluoride to yield hydroxylamines.

Using Unentangled Oligomers To Toughen Materials.

Entanglements between polymer chains are responsible for the strength and toughness of polymeric materials. When the chains are too short to form entanglements, the polymer becomes weak and brittle. Here we show that molecular bridging of oligomers in molecular-scale confinement can dramatically toughen materials even when intermolecular entanglements are completely absent. We describe the fabrication of nanocomposite materials that confine oligomer chains to molecular-scale dimensions and demonstrate that partially confined unentangled oligomers can toughen materials far beyond rule-of-mixtures estimates. We also characterize how partially confined oligomers affect the kinetics of nanocomposite cracking in moist environments and show that the presence of a backfilled oligomeric phase within a nanoporous organosilicate matrix leads to atomistic crack path meandering in which the failure path is preferentially located within the matrix phase.

Dense Vertically Aligned Copper Nanowire Composites as High Performance Thermal Interface Materials.

Thermal interface materials (TIMs) are essential for managing heat in modern electronics, and nanocomposite TIMs can offer critical improvements. Here, we demonstrate thermally conductive, mechanically compliant TIMs based on dense, vertically aligned copper nanowires (CuNWs) embedded into polymer matrices. We evaluate the thermal and mechanical characteristics of 20-25% dense CuNW arrays with and without polydimethylsiloxane infiltration. The thermal resistance achieved is below 5 mm2 K W-1, over an order of magnitude lower than commercial heat sink compounds. Nanoindentation reveals that the nonlinear deformation mechanics of this TIM are influenced by both the CuNW morphology and the polymer matrix. We also implement a flip-chip bonding protocol to directly attach CuNW composites to copper surfaces, as required in many thermal architectures. Thus, we demonstrate a rational design strategy for nanocomposite TIMs that simultaneously retain the high thermal conductivity of aligned CuNWs and the mechanical compliance of a polymer.

Synthesis of Polyimides in Molecular-Scale Confinement for Low-Density Hybrid Nanocomposites.

In this work, we exploit a confinement-induced molecular synthesis and a resulting bridging mechanism to create confined polyimide thermoset nanocomposites that couple molecular confinement-enhanced toughening with an unprecedented combination of high-temperature properties at low density. We describe a synthesis strategy that involves the infiltration of individual polymer chains through a nanoscale porous network while simultaneous imidization reactions increase the molecular backbone stiffness. In the extreme limit where the confinement length scale is much smaller than the polymer's molecular size, confinement-induced molecular mechanisms give rise to exceptional mechanical properties. We find that polyimide oligomers can undergo cross-linking reactions even in such molecular-scale confinement, increasing the molecular weight of the organic phase and toughening the nanocomposite through a confinement-induced energy dissipation mechanism. This work demonstrates that the confinement-induced molecular bridging mechanism can be extended to thermoset polymers with multifunctional properties, such as excellent thermo-oxidative stability and high service temperatures (>350 °C).

Fundamental limits of material toughening in molecularly confined polymers.

The exceptional mechanical properties of polymer nanocomposites are achieved through intimate mixing of the polymer and inorganic phases, which leads to spatial confinement of the polymer phase. In this study we probe the mechanical and fracture properties of polymers in the extreme limits of molecular confinement, where a stiff inorganic phase confines the polymer chains to dimensions far smaller than their bulk radius of gyration. We show that polymers confined at molecular length scales dissipate energy through a confinement-induced molecular bridging mechanism that is distinct from existing entanglement-based theories of polymer deformation and fracture. We demonstrate that the toughening is controlled by the molecular size and the degree of confinement, but is ultimately limited by the strength of individual molecules.

An ultra-sensitive resistive pressure sensor based on hollow-sphere microstructure induced elasticity in conducting polymer film.

Pressure sensing is an important function of electronic skin devices. The development of pressure sensors that can mimic and surpass the subtle pressure sensing properties of natural skin requires the rational design of materials and devices. Here we present an ultra-sensitive resistive pressure sensor based on an elastic, microstructured conducting polymer thin film. The elastic microstructured film is prepared from a polypyrrole hydrogel using a multiphase reaction that produced a hollow-sphere microstructure that endows polypyrrole with structure-derived elasticity and a low effective elastic modulus. The contact area between the microstructured thin film and the electrodes increases with the application of pressure, enabling the device to detect low pressures with ultra-high sensitivity. Our pressure sensor based on an elastic microstructured thin film enables the detection of pressures of less than 1Pa and exhibits a short response time, good reproducibility, excellent cycling stability and temperature-stable sensing.