Examining the Quasi-Static Uniaxial Compressive Behaviour of Commercial High-Performance Epoxy Matrices.

Four commercial high-performance aerospace aromatic epoxy matrices, CYCOM®890, CYCOM®977-2, PR520, and PRISM EP2400, were cured to a standardised 2 h, 180 °C cure cycle and evaluated in quasi-static uniaxial compression, as well as by dynamic scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The thermoplastic toughened CYCOM®977-2 formulation displayed an overall increase in true axial stress values across the entire stress-strain curve relative to the baseline CYCOM®890 sample. The particle-toughened PR520 sample exhibited an overall decrease in true axial stress values past the yield point of the material. The PRISM EP2400 resin, with combined toughening agents, led to true axial stress values across the entire plastic region of the stress-strain curve, which were in line with the stress values observed with the CYCOM®890 material. Interestingly, for all formulations, the dilation angles (associated with the volume change during plastic deformation), recorded at 0.3 plastic strain, were close to 0°, with the variations reflecting the polymer structure. Compression data collected for this series of commercial epoxy resins are in broad agreement with a selection of model epoxy resins based on di- and tetra-functional monomers, cured with polyamines or dicarboxylic anhydrides. However, the fully formulated resins demonstrate a significantly higher compressive modulus than the model resins, albeit at the expense of yield stress.

Vapour-liquid-solid growth of ZnO-ZnMgO core-shell nanowires by gold-catalysed molecular beam epitaxy.

Nanowire heterostructures, combining multiple phases within a single nanowire, modify functional properties and offer a platform for novel device development. Here, ZnO/ZnMgO core-shell nanowires are grown by molecular beam epitaxy. At growth temperatures above 750 °C, Mg diffuses into ZnO making heterostructure growth impossible; at lower shell-growth temperatures (500 °C), the core-shell structure is retained. Even very thin ZnMgO shells show increased intensity photoluminescence (PL) across the ZnO band-gap and a suppression in defect-related PL intensity, relative to plain ZnO nanowires. EDX measurements on shell thickness show a correlation between shell thickness and core diameter which is explained by a simple growth model.

Reductive dissolution of supergrowth carbon nanotubes for tougher nanocomposites by reactive coagulation spinning.

Long single-walled carbon nanotubes, with lengths >10 µm, can be spontaneously dissolved by stirring in a sodium naphthalide N,N-dimethylacetamide solution, yielding solutions of individualised nanotubide ions at concentrations up to 0.74 mg mL-1. This process was directly compared to ultrasonication and found to be less damaging while maintaining greater intrinsic length, with increased individualisation, yield, and concentration. Nanotubide solutions were spun into fibres using a new reactive coagulation process, which covalently grafts a poly(vinyl chloride) matrix to the nanotubes directly at the point of fibre formation. The grafting process insulated the nanotubes electrically, significantly enhancing the dielectric constant to 340% of the bulk polymer. For comparison, samples were prepared using both Supergrowth nanotubes and conventional shorter commercial single-walled carbon nanotubes. The resulting nanocomposites showed similar, high loadings (ca. 20 wt%), but the fibres formed with Supergrowth nanotubes showed significantly greater failure strain (up to ∼25%), and hence more than double the toughness (30.8 MJ m-3), compared to composites containing typical ∼1 µm SWCNTs.

Avoiding artefacts during electron microscopy of silver nanomaterials exposed to biological environments.

Electron microscopy has been applied widely to study the interaction of nanomaterials with proteins, cells and tissues at nanometre scale. Biological material is most commonly embedded in thermoset resins to make it compatible with the high vacuum in the electron microscope. Room temperature sample preparation protocols developed over decades provide contrast by staining cell organelles, and aim to preserve the native cell structure. However, the effect of these complex protocols on the nanomaterials in the system is seldom considered. Any artefacts generated during sample preparation may ultimately interfere with the accurate prediction of the stability and reactivity of the nanomaterials. As a case study, we review steps in the room temperature preparation of cells exposed to silver nanomaterials (AgNMs) for transmission electron microscopy imaging and analysis. In particular, embedding and staining protocols, which can alter the physicochemical properties of AgNMs and introduce artefacts thereby leading to a misinterpretation of silver bioreactivity, are scrutinized. Recommendations are given for the application of cryogenic sample preparation protocols, which simultaneously fix both particles and diffusible ions. By being aware of the advantages and limitations of different sample preparation methods, compromises or selection of different correlative techniques can be made to draw more accurate conclusions about the data.

A one-step route to solubilised, purified or functionalised single-walled carbon nanotubes.

Reductive dissolution is a promising processing route for single walled carbon nanotubes (SWCNTs) that avoids the damage caused by ultrasonication and aggressive oxidation whilst simultaneously allowing access to a wealth of SWCNT functionalisation reactions. Here, reductive dissolution has been simplified to a single one-pot reaction through the use of sodium naphthalide in dimethylacetamide allowing direct synthesis of SWCNT Na+ solutions. Gram quantities of SWCNTs can be dissolved at concentrations over 2 mg mL-1. These reduced SWCNT solutions can easily be functionalised through the addition of alkyl halides; reducing steric bulk of the grafting moiety and increasing polarisability of the leaving group increases the extent of functionalisation. An optimised absolute sodium concentration of 25 mM is shown to be more important than carbon to metal ratio in determining the maximum degree of functionalisation. This novel dissolution system can be modified for use as a non-destructive purification route for raw SWCNT powder by adjusting the degree of charging to dissolve carbonaceous impurities, catalyst particles and defective material, before processing the remaining SWCNTs.

Mapping functional groups on oxidised multi-walled carbon nanotubes at the nanometre scale.

Despite voluminous research on the acid oxidation of carbon nanotubes (CNTs), there is a distinct lack of experimental results showing distributions of functional groups at the nanometre length scale. Here, functional peaks have been mapped across individual multi-walled CNTs with low-dose, monochromated electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM). Density functional theory simulations show that the EELS features are consistent with oxygenated functional groups, most likely carboxyl moieties.

Phosphinate stabilised ZnO and Cu colloidal nanocatalysts for CO2 hydrogenation to methanol.

Colloidal solutions of ZnO-Cu nanoparticles can be used as catalysts for the reduction of carbon dioxide with hydrogen. The use of phosphinate ligands for the synthesis of the nanoparticles from organometallic precursors improves the reductive stability and catalytic activity of the system.

Applications of graphene electrophoretic deposition. A review.

This Review summarizes research progress employing electrophoretic deposition (EPD) to fabricate graphene and graphene-based nanostructures for a wide range of applications, including energy storage materials, field emission devices, supports for fuel cells, dye-sensitized solar cells, supercapacitors and sensors, among others. These carbonaceous nanomaterials can be dispersed in organic solvents, or more commonly in water, using a variety of techniques compatible with EPD. Most deposits are produced under constant voltage conditions with deposition time also playing an important role in determining the morphology of the resulting graphene structures. In addition to simple planar substrates, it has been shown that uniform graphene-based layers can be deposited on three-dimensional, porous, and even flexible substrates. In general, electrophoretically deposited graphene layers show excellent properties, e.g., high electrical conductivity, large surface area, good thermal stability, high optical transparency, and robust mechanical strength. EPD also enables the fabrication of functional composite materials, e.g., graphene combined with metallic nanoparticles, with other carbonaceous materials (e.g., carbon nanotubes) or polymers, leading to novel nanomaterials with enhanced optical and electrical properties. In summary, the analysis of the available literature reveals that EPD is a simple and convenient processing method for graphene and graphene-based materials, which is easy to apply and versatile. EPD has, therefore, a promising future for applications in the field of advanced nanomaterials, which depend on the reliable manipulation of graphene and graphene-containing systems.

Carbon nanotube-nanocrystal heterostructures fabricated by electrophoretic deposition.

Alternating layer, carbon nanotubes-nanocrystal composite films, comprising multi-walled carbon nanotubes (MWCNTs) and iron oxide (Fe(3)O(4)) nanocrystals, have been fabricated via electrophoretic deposition (EPD) on stainless steel and gold substrates. Low field-high current and high field-low current EPD schemes were integrated to produce the composite films. The low field-high current EPD approach produced porous mats from an aqueous suspension of the MWCNTs, while the high field-low current EPD approach produced tightly packed nanocrystal films from a dispersion of the nanocrystals in hexane. Large electric fields applied during the nanocrystal EPD and strong van der Waals interactions among the nanocrystals facilitated the formation of tightly packed nanocrystal films atop the MWCNT mats to create CNT mat-nanocrystal film composites. The surface coverage and homogeneity of the nanocrystal films improved with repeated deposition of the nanocrystals on the same mat. The assembly of nanotube mats on top of the CNT mat-nanocrystal film composite confirmed the feasibility of multilayered CNT mat-nanocrystal film heterostructures suitable for a range of devices. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques were employed to characterize the surface coverage, homogeneity, and topology of these composite films.

Polystyrene grafted multi-walled carbon nanotubes.

Oxidised, multi-walled, carbon nanotubes can be grafted with polystyrene molecules using an situ radical polymerisation reaction, thereby dramatically modifying their solubility and their suitability for nanocomposite applications.