Nanoscale viscosity of confined polyethylene oxide.

Complex fluids near interfaces or confined within nanoscale volumes can exhibit substantial shifts in physical properties compared to bulk, including glass transition temperature, phase separation, and crystallization. Because studies of these effects typically use thin film samples with one dimension of confinement, it is generally unclear how more extreme spatial confinement may influence these properties. In this work, we used x-ray photon correlation spectroscopy and gold nanoprobes to characterize polyethylene oxide confined by nanostructured gratings (<100nm width) and measured the viscosity in this nanoconfinement regime to be ∼500 times the bulk viscosity. This enhanced viscosity occurs even when the scale of confinement is several times the polymer's radius of gyration, consistent with previous reports of polymer viscosity near flat interfaces.

Graphene-vertically aligned carbon nanotube hybrid on PDMS as stretchable electrodes.

Stretchable electrodes are a critical component for flexible electronics such as displays, energy devices, and wearable sensors. Carbon nanotubes (CNTs) and graphene have been considered for flexible electrode applications, due to their mechanical strength, high carrier mobility, and excellent thermal conductivity. Vertically aligned carbon nanotubes (VACNTs) provide the possibility to serve as interconnects to graphene sheets as stretchable electrodes that could maintain high electrical conductivity under large tensile strain. In this work, a graphene oxide (GO)-VACNT hybrid on a PDMS substrate was demonstrated. Here, 50 µm long VACNTs were grown on a Si/SiO2 wafer substrate via atmospheric pressure chemical vapor deposition. VACNTs were directly transferred by delamination from the Si/SiO2 to a semi-cured PDMS substrate, ensuring strong adhesion between VACNTs and PDMS upon full curing of the PDMS. GO ink was then printed on the surface of the VACNT carpet and thermally reduced to reduced graphene oxide (rGO). The sheet resistance of the rGO-VACNT hybrid was measured under uniaxial tensile strains up to 300% applied to the substrate. Under applied strain, the rGO-VACNT hybrid maintained a sheet resistant of 386 ± 55 Ω/sq. Cyclic stretching of the rGO-VACNT hybrid was performed with up to 50 cycles at 100% maximum tensile strain, showing no increase in sheet resistance. These results demonstrate promising performance of the rGO-VACNT hybrid for flexible electronics applications.

Nanoporous nanocomposite membranes via hybrid twin-screw extrusion-multijet electrospinning.

Non-woven nanoporous membranes of poly(caprolactone), PCL, incorporated with multi-walled carbon nanotubes, CNTs, could be fabricated via an industrially-scalable hybrid twin screw extrusion and electrospinning process. The utilization of a spinneret with multiple nozzles allowed the increase of the flow rate beyond what is possible with conventional electrospinning using a single nozzle, albeit at the expense of difficulties in the control of the thickness distributions of the nanofibrous membranes. The thickness and orientation distributions and the resulting mechanical properties of the membranes could be modified via changes in voltage, angular velocity of the collector mandrel and separation distance of the collector from the spinneret. The increases in crystallinity due to the presence of the CNTs and the preferential alignment of the nanofibers via rotation of the collecting mandrel led to increases in the tensile properties of the nanoporous membranes. The use of poly(ethylene oxide), PEO, together with PCL, followed by the dissolution of the PEO, rendered the nanofibers themselves nanoporous with typical surface porosity values of around 50% and pore sizes of about 220 nm. The demonstrated versatility of the hybrid twin screw extrusion and electrospinning process and the manipulation of mesh dimensions and properties are indicative of the applicability of the hybrid process for fabrication of nanoporous membranes for myriad diverse industrial applications ranging from water treatment to tissue engineering applications.

Reverse Kebab Structure Formed inside Carbon Nanofibers via Nanochannel Flow.

The morphology of polymers inside a confined space has raised great interest in recent years. However, polymer crystallization within a one-dimensional carbon nanostructure is challenging due to the difficulty of polar solvents carrying polymers to enter a nonpolar graphitic nanotube in bulk solution at normal temperature and pressure. Here we describe a method whereby nylon-11 was crystallized and periodically distributed on the individual graphitic nanocone structure within hollow carbon nanofibers (CNF). Differential scanning calorimetry and X-ray diffraction indicate that the nylon polymer is in the crystalline phase. A mechanism is suggested for the initiation of nanochannel flow in a bulk solvent as a prerequisite condition to achieve interior polymer crystallization. Selective etching of polymer crystals on the outer wall of CNF indicates that both surface tension and viscosity affect the flow within the CNF. This approach provides an opportunity for the interior functionalization of carbon nanotubes and nanofibers for applications in the biomedical, energy, and related fields.

Interfacial load transfer in polymer/carbon nanotube nanocomposites with a nanohybrid shish kebab modification.

Interfacial properties are known to have a critical effect on the mechanical properties of a nanocomposite material system. Here, the interfacial load transfer in a carbon nanotube (CNT)/nylon-11 composite was studied with a CNT/nylon-11 nanohybrid shish kebab (NHSK) structure modification using Raman spectroscopy. Characterization of the polymer crystal in the NHSK using differential scanning calorimetry (DSC) for the first time indicates that the NHSK structure formed a more perfect crystal structure than the bulk polymer. On the basis of transmission electron microscopy and DSC results, a new growth model for the NHSK crystal is hypothesized, indicating the formation of an initial uniform crystal layer on the CNT prior to the crystallization of the kebabs. Characterization of the nanocomposites using Raman spectroscopy, with the samples heated to introduce interfacial shear stress caused by thermal expansion mismatch, found that the D* band of the CNT in the NHSK/nylon-11 composite displayed a more pronounced shift with an increase in temperature, which is attributed to the NHSK structure being more effective at transferring load from the nylon matrix to the nanotube inclusions. The NHSK structure was also used to fabricate composites with two amorphous polymers, polycarbonate and poly(methyl methacrylate), to investigate the load transfer mechanism. It was found that when the compatibility between the polymer in the NHSK structure and the bulk polymer matrix at the molecular level is sufficiently high, the ensuing mechanical interlocking effect further enhances the interfacial load transfer for polymer nanocomposites. Additional mechanical characterization of polymer nanocomposites with 0.1 wt % NHSK reinforcement demonstrates how the moduli and ultimate tensile strength of the nanocomposites can be improved via this NHSK structure.

Out-of-plane growth of CNTs on graphene for supercapacitor applications.

This paper describes the fabrication and characterization of a hybrid nanostructure comprised of carbon nanotubes (CNTs) grown on graphene layers for supercapacitor applications. The entire nanostructure (CNTs and graphene) was fabricated via atmospheric pressure chemical vapor deposition (APCVD) and designed to minimize self-aggregation of the graphene and CNTs. Growth parameters of the CNTs were optimized by adjusting the gas flow rates of hydrogen and methane to control the simultaneous, competing reactions of carbon formation toward CNT growth and hydrogenation which suppresses CNT growth via hydrogen etching of carbon. Characterization of the supercapacitor performance of the CNT-graphene hybrid nanostructure indicated that the average measured capacitance of a fabricated graphene-CNT structure was 653.7 µF cm(-2) at 10 mV s(-1) with a standard rectangular cyclic voltammetry curve. Rapid charging-discharging characteristics (mV s(-1)) were exhibited with a capacitance of approximately 75% (490.3 µF cm(-2)). These experimental results indicate that this CNT-graphene structure has the potential towards three-dimensional (3D) graphene-CNT multi-stack structures for high-performance supercapacitors.

Deformation-induced crystallization and associated morphology development of carbon nanotube-PVDF nanocomposites.

Poly(vinylidene fluoride) (PVDF) is a semicrystalline thermoplastic polymer that is of interest for sensor, actuator and biomedical applications because of its piezoelectric and pyroelectric properties, as well as outstanding mechanical and chemical properties. Although it is known that the shear-induced crystallization behavior of nanocomposites can be significantly affected by the presence of nanoparticles, the effects of the incorporation of carbon nanotubes on the deformation-induced crystallization and associated morphology development of PVDF have not been previously investigated. Here the dynamics of the shear-induced crystallization of carbon nanotubes incorporated in PVDF were investigated using simple shear flow. The shear-induced crystallization behavior was affected by the deformation rate, temperature, and the concentration of the carbon nanotubes. Time-dependence of linear viscoelastic properties indicated that the presence of multi-walled carbon nanotubes (MWNTs) in PVDF greatly altered the shear-induced crystallization kinetics of PVDF, while no significant changes in crystallization behavior were observed for pure PVDF samples sheared under similar conditions. Upon increase of the concentration of the MWNTs the crystal size of PVDF decreased while its rate of crystallization increased in conjunction with an increase of the beta phase crystallization. Overall, these findings suggest that the shear-induced crystallization of PVDF nanocomposites (and in general flow-induced crystallization effects associated with the thermo-mechanical history experienced by the nanocomposite during processing) should be integral parts of attempts to generate a comprehensive understanding of the development of the microstructural distributions and the coupled ultimate properties of polymer nanocomposites.