Roll-to-Roll Continuous Manufacturing Multifunctional Nanocomposites by Electric-Field-Assisted “Z” Direction Alignment of Graphite Flakes in Poly(dimethylsiloxane)

A roll-to-roll continuous process was developed to manufacture large-scale multifunctional poly­(dimethylsiloxane) (PDMS) films embedded with thickness direction (“Z” direction) aligned graphite nanoparticles by application of electric field. The kinetics of particle “Z” alignment and chain formation was studied by tracking the real-time change of optical light transmission through film thickness direction. Benefiting from the anisotropic structure of aligned particle chains, the electrical and thermal properties of the nanocomposites were dramatically enhanced through the thickness direction as compared to those of the nanocomposites containing the same particle loading without electrical field alignment. With 5 vol % graphite loading, 250 times higher electrical conductivity, 43 times higher dielectric permittivity, and 1.5 times higher thermal conductivity was achieved in the film thickness direction after the particles were aligned under electrical field. Moreover, the aligned nanocomposites with merely 2 vol % graphite particles exhibit even higher electric conductivity and dielectric permittivity than those of the nonaligned nanocomposites at random percolation threshold (10 vol % particles), as the “electric-field-directed” percolation threshold concentration is substantially decreased using this process. As the graphite loading increases to 20 vol %, the aligned nanocomposites exhibit thermal conductivity as high as 6.05 W/m·K, which is 35 times the thermal conductivity of pure matrix. This roll-to-roll electric field continuous process provides a simple, low-cost, and commercially viable method to manufacture multifunctional nanocomposites for applications as embedded capacitor, electromagnetic (EM) shielding, and thermal interface materials

Roll to Roll Electric Field “Z” Alignment of Nanoparticles from Polymer Solutions for Manufacturing Multifunctional Capacitor Films

A roll to roll continuous processing method is developed for vertical alignment (“Z” alignment) of barium titanate (BaTiO₃) nanoparticle columns in polystyrene (PS)/toluene solutions. This is accomplished by applying an electric field to a two-layer solution film cast on a carrier: one is the top sacrificial layer contacting the electrode and the second is the polymer solution dispersed with BaTiO₃ particles. Flexible Teflon coated mesh is utilized as the top electrode that allows the evaporation of solvent through the openings. The kinetics of particle alignment and chain buckling is studied by the custom-built instrument measuring the real time optical light transmission during electric field application and drying steps. The nanoparticles dispersed in the composite bottom layer form chains due to dipole–dipole interaction under an applied electric field. In relatively weak electric fields, the particle chain axis tilts away from electric field direction due to bending caused by the shrinkage of the film during drying. The use of strong electric fields leads to maintenance of alignment of particle chains parallel to the electric field direction overcoming the compression effect. At the end of the process, the surface features of the top porous electrodes are imprinted at the top of the top sacrificial layer. By removing this layer a smooth surface film is obtained. The nanocomposite films with “Z” direction alignment of BaTiO₃ particles show substantially increased dielectric permittivity in the thickness direction for enhancing the performance of capacitors

Enhanced Impact Resistance of Three-Dimensional-Printed Parts with Structured Filaments

Net-shape manufacture of customizable objects through three-dimensional (3D) printing offers tremendous promise for personalization to improve the fit, performance, and comfort associated with devices and tools used in our daily lives. However, the application of 3D printing in structural objects has been limited by their poor mechanical performance that manifests from the layer-by-layer process by which the part is produced. Here, this interfacial weakness is overcome using a structured, core–shell polymer filament where a polycarbonate (PC) core solidifies quickly to define the shape, whereas an olefin ionomer shell contains functionality (crystallinity and ionic) that strengthen the interface between the printed layers. This structured filament leads to improved dimensional accuracy and impact resistance in comparison to the individual components. The impact resistance from structured filaments containing 45 vol % shell can exceed 800 J/m. The origins of this improved impact resistance are probed using X-ray microcomputed tomography. Energy is dissipated by delamination of the shell from PC near the crack tip, whereas PC remains intact to provide stability to the part after impact. This structured filament provides tremendous improvements in the critical properties for manufacture and represents a major leap forward in the impact properties obtainable for 3D-printed parts

Role of Hydrogen Bonding on Nonlinear Mechano-Optical Behavior of l‑Phenylalanine-Based Poly(ester urea)s

The uniaxial mechano-optical behavior of a series of amorphous l-phenylalanine-based poly­(ester urea) (PEU) films was studied in the rubbery state. A custom, real-time measurement system was used to capture the true stress, true strain, and birefringence during deformation. When the materials were subjected to deformation at temperatures near the glass transition temperature (<i>T</i>_g), the photoelastic behavior was manifested by a small increase in birefringence with a significant increase in true stress. At temperatures above <i>T</i>_g, PEUs with a shorter diol chain length exhibited a liquid–liquid (<i>T</i>_ll) transition (rubbery–viscous transition) at about 1.06<i>T</i>_g (K) under the tested strain rate of 0.017 s^–1 (stretching speed of 20 mm/min), above which the material transforms from a heterogeneous “liquid of fixed structure” to a “true liquid” state. The initial photoelastic behavior disappears with increasing temperature, as the initial slope of the stress optical curves becomes temperature independent. Fourier transform infrared spectroscopy (FTIR) was used to study the effect of hydrogen bonding on the physical properties of PEUs as a function of temperature. The average strength of hydrogen bonding diminishes with increasing temperature. For PEUs with the longest diol chain length, the area associated with N–H stretching region exhibits a linear temperature dependence. However, a three-stage temperature dependence was observed for PEUs with shorter diol chain length. The presence of hydrogen bonding enhances the “stiff” segmental correlations between adjacent chains in the PEU structure. As a result, the photoelastic constant decreases with increasing hydrogen bonding strength

Large-Scale Roll-to-Roll Fabrication of Vertically Oriented Block Copolymer Thin Films

Large-scale roll-to-roll (R2R) fabrication of vertically oriented nanostructures <i>via</i> directed self-assembly of cylindrical block copolymer (c-BCP) thin films is reported. Nearly 100% vertical orientation of cylinders in sub-100 nm c-BCP films under optimized processing <i>via</i> a dynamic sharp temperature gradient field termed Cold Zone Annealing-Sharp or ‘CZA-S’ is achieved, with successful scale-up on a prototype custom-built 70 ft × 1 ft R2R platform moving at 25 μm/s, with 9 consecutive CZA units. Static thermal annealing of identical films in a conventional vacuum oven fails to produce comparable results. As a potential for applications, we fabricate high-density silicon oxide nanodot arrays from the CZA-S annealed BCP thin film template

Large-Scale Roll-to-Roll Fabrication of Ordered Mesoporous Materials using Resol-Assisted Cooperative Assembly

Roll-to-roll (R2R) processing enables the rapid fabrication of large-area sheets of cooperatively assembled materials for production of mesoporous materials. Evaporation induced self-assembly of a nonionic surfactant (Pluronic F127) with sol–gel precursors and phenolic resin oligomers (resol) produce highly ordered mesostructures for a variety of chemistries including silica, titania, and tin oxide. The cast thick (>200 μm) film can be easily delaminated from the carrier substrate (polyethylene terephthalate, PET) after cross-linking the resol to produce meter-long self-assembled sheets. The surface areas of these mesoporous materials range from 240 m²/g to >1650 m²/g with these areas for each material comparing favorably with prior reports in the literature. These R2R methods provide a facile route to the scalable production of kilograms of a wide variety of ordered mesoporous materials that have shown potential for a wide variety of applications with small-batch syntheses

Hierarchical Electrospun and Cooperatively Assembled Nanoporous Ni/NiO/MnO_<i>x</i>/Carbon Nanofiber Composites for Lithium Ion Battery Anodes

A facile method to fabricate hierarchically structured fiber composites is described based on the electrospinning of a dope containing nickel and manganese nitrate salts, citric acid, phenolic resin, and an amphiphilic block copolymer. Carbonization of these fiber mats at 800 °C generates metallic Ni-encapsulated NiO/MnO_<i>x</i>/carbon composite fibers with average BET surface area (150 m²/g) almost 3 times higher than those reported for nonporous metal oxide nanofibers. The average diameter (∼900 nm) of these fiber composites is nearly invariant of chemical composition and can be easily tuned by the dope concentration and electrospinning conditions. The metallic Ni nanoparticle encapsulation of NiO/MnO_<i>x</i>/C fibers leads to enhanced electrical conductivity of the fibers, while the block copolymers template an internal nanoporous morphology and the carbon in these composite fibers helps to accommodate volumetric changes during charging. These attributes can lead to lithium ion battery anodes with decent rate performance and long-term cycle stability, but performance strongly depends on the composition of the composite fibers. The composite fibers produced from a dope where the metal nitrate is 66% Ni generates the anode that exhibits the highest reversible specific capacity at high rate for any composition, even when including the mass of the nonactive carbon and Ni⁰ in the calculation of the capacity. On the basis of the active oxides alone, near-theoretical capacity and excellent cycling stability are achieved for this composition. These cooperatively assembled hierarchical composites provide a platform for fundamentally assessing compositional dependencies for electrochemical performance. Moreover, this electrospinning strategy is readily scalable for the fabrication of a wide variety of nanoporous transition metal oxide fibers