Gas-to-nanotextile: high-performance materials from floating 1D nanoparticles.

Suspended in the gas phase, 1D inorganic nanoparticles (nanotubes and nanowires) grow to hundreds of microns in a second and can be thus directly assembled into freestanding network materials. The corresponding process continuously transforms gas precursors into aerosols into aerogels into macroscopic nanotextiles. By enabling the assembly of very high aspect ratio nanoparticles, this processing route has translated into high-performance structural materials, transparent conductors and battery anodes, amongst other embodiments. This paper reviews progress in the application of such manufacturing process to nanotubes and nanowires. It analyses 1D nanoparticle growth through floating catalyst chemical vapour deposition (FCCVD), in terms of reaction selectivity, scalability and its inherently ultra-fast growth rates (107-108 atoms per second) up to 1000 times faster than for substrate CVD. We summarise emerging descriptions of the formation of aerogels through percolation theory and multi-scale models for the collision and aggregation of 1D nanoparticles. The paper shows that macroscopic ensembles of 1D nanoparticles resemble textiles in their porous network structure, high flexibility and damage-tolerance. Their bulk properties depend strongly on inter-particle properties and are dominated by alignment and volume fraction. Selected examples of nanotextiles that surpass granular and monolithic materials include structural fibres with polymer-like toughness, transparent conductors, and slurry-free composite electrodes for energy storage.

Ultrafast synthesis of SiC nanowire webs by floating catalysts rationalised through in situ measurements and thermodynamic calculations.

This work presents the synthesis of SiC nanowires floating in a gas stream through the vapour-liquid-solid (VLS) mechanism using an aerosol of catalyst nanoparticles. These conditions lead to ultrafast growth at 8.5 µm s-1 (maximum of 50 µm s-1), which is up to 3 orders of magnitude above conventional substrate-based chemical vapour deposition. The high aspect ratio of the nanowires (up to 2200) favours their entanglement and the formation of freestanding network materials consisting entirely of SiCNWs. The floating catalyst chemical vapour deposition growth process is rationalised through in situ sampling of reaction products and catalyst aerosol from the gas phase, and thermodynamic calculations of the bulk ternary Si-C-Fe phase diagram. The phase diagram suggests a description of the mechanistic path for the selective growth of SiCNWs, consistent with the observation that no other types of nanowires (Si or C) are grown by the catalyst. SiCNW growth occurs at 1130 °C, close to the calculated eutectic. According to the calculated phase diagram, upon addition of Si and C, the Fe-rich liquid segregates a carbon shell, and later enrichment of the liquid in Si leads to the formation of SiC. The exceptionally fast growth rate relative to substrate-based processes is attributed to the increased availability of precursors for incorporation into the catalyst due to the high collision rate inherent to this new synthesis mode.

Optimization of Processing Conditions and Mechanical Properties for PEEK/PEI Multilayered Blends.

The goal of producing polyetheretherketone/polyetherimide (PEEK/PEI) blends is to combine the outstanding properties that both polymers present separately. Despite being miscible polymers, it is possible to achieve PEEK/PEI multilayered blends in which PEEK crystallinity is not significantly inhibited, as opposed to conventional extruding processes that lead to homogeneous mixtures with total polymer chain interpenetration. This study investigated a 50/50 (volume fraction) PEEK/PEI multilayered polymer blend in which manufacturing parameters were tailored to simultaneously achieve PEEK-PEI adhesion while keeping PEEK crystallinity in order to optimize the mechanical properties of this heterogeneous polymer blend. The interface adhesion was characterized with the use of three-point bending tests, which proved that a processing temperature below the melting point of PEEK produced weak PEEK-PEI interfaces. Results from differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and X-ray diffraction analysis (XRD) showed that under a 350 °C consolidation temperature, there is a partial mixing of PEEK and PEI layers in the interface that provides good adhesion. The thickness of the mixed homogeneous region at this temperature exhibits reduced sensitivity to processing time, which ensures that both polymers essentially remain separate phases. This also entails that multilayered blends with good mechanical properties can be reliably produced with short manufacturing cycles. The combination of mechanical performance and potential joining capability supports their use in a wide range of applications in the automotive, marine, and aerospace industries.

Effect of Fiber-Matrix Interface on the Mechanical Response of a Woven Carbon Fiber/PEEK Composite Material.

This work studies the relationship between the interface shear strength (IFSS) and the mechanical response of a carbon fiber-reinforced composite with a polyether-ether-ketone (PEEK) thermoplastic matrix. Two types of laminates were studied: the first kind was manufactured with as-received fiber fabrics, while specimens belonging to the second one were fabricated with thermally treated fibers where the original sizing agent was removed. IFSS values were measured with the push-in test, showing that treated fibers exhibit a 25% higher critical shear stress. Microscopic inspection of the laminates revealed that untreated specimens were prone to debonding, generating a much higher crack density. This difference was detected by the C-Scan technique and triggered in the response of both laminates under tensile tests at ±45∘ fiber orientation, where maximum stress and strain at break values of desized specimens showed an increase of 37% and 190%, respectively. Results confirmed that the original fiber sizing weakened the fiber-matrix interface. Lastly, the tensile response of the composite is analyzed in light of interface quality.

Fabrication and Characterization of PEEK/PEI Multilayer Composites.

Polyetheretherketone (PEEK)/polyetherimide (PEI) blends (50/50, v/v) keeping the crystal phase of PEEK have been manufactured by alternate PEEK/PEI layer stacking. This strategy avoided the complete miscibility of both polymers, keeping layers of PEEK and PEI unmixed along the sample thickness, as well as promoting the formation of a smooth interfacial layer where PEEK and PEI were mixed. The properties of this interface after processing at molten state and different times was studied by DSC, DMA, and X-Ray synchrotron. These techniques allowed monitoring the evolution of glass transition, where isolated Tg's for both pristine polymers were observed even after long processing time. PEEK crystallinity slightly decreased during manufacturing, whereas PEEK crystal parameters did not vary. These observations show that, although the interface-the zone where both polymers are mixed-grew, layers with pristine polymers remained even after prolonged processing time. The preservation of the PEEK crystallinity was also observed in the mechanical properties of the multilayer PEEK/PEI films, which were compared with pristine PEEK and PEI films. Multilayer samples processed for shorter times rendered higher young modulus, tensile strength, and strain at break.

Hydrogen in α-iron: role of phonons in the diffusion of interstitials at high temperature.

Ab-initio Density Functional Theory has been used to compute phonons for interstitial hydrogen in α-iron. In the harmonic approximation, these phonons yield Helmholtz's free energy as a function of temperature, which can be used to obtain diffusion barriers from an Arrhenius plot. By comparing with the experimental database compiled by Kiuchi and McLellan, we show that the role of phonons is crucial to understand the diffusion of interstitial hydrogen at T > 300 K. The computed specific heat for Fe16H and Fe behaves quite differently due to the appearance of optical modes and could be used to calibrate the amount of interstitials in the iron matrix.

Preparation and characterization of Nephila clavipes tubuliform silk gut.

Tubuliform silk glands were dissected from Nephila clavipes spiders, and silk gut fibers were produced by immersing the glands in a mild acid solution and subsequent stretching. The tensile properties of the as produced fibers were obtained through tensile tests, and the stress-strain curves were compared with those of naturally spun tubuliform silk fibers. The influence on the mechanical properties of the fibers after immersion in water and drying was also discerned. The microstructure of the silk guts was obtained by X-ray diffraction (XRD) and infrared spectroscopy (FTIR). It was found that the stress-strain curves of the stretched tubuliform silk guts concur with those of their natural counterparts (tubuliform silk fibers).