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This paper examines the effect on interfacial shear strength (IFSS) when grafting polyethyleneoxide (PEO) polymers of various molecular weights to a carbon fiber surface. Using copper-azide-alkyne cycloaddition click chemistry, PEO polymers of 1 kDa, 2 kDa, 5 kDa, and 10 kDa were tethered to the fiber surface without causing degradation of the fiber surface. The resulting IFSS increases were maximised (130% and 160%) for the 1 kDa and 10 kDa surface modified fibers, respectively. These data suggest that increases in IFSS are the result of an interplay between the density of surface modification versus the penetration of the grafted polymer into the matrix interphase. The trade-off between interphase penetration and surface grafting density is highlighted for the 2 and 5 kDa PEO chains on the fiber surface which display smaller IFSS increases (85% and 117%, respectively). Measuring the mobility of the PEO polymers by 1H NMR found an order of magnitude decrease in diffusion coefficient for each successive increase in molecular weight, supporting the hypothesis that grafting density decreases with molecular weight. Molecular dynamics simulations of the carbon fiber-matrix interface further supports these observations. These results will inform the design of complementary interfaces for various materials in a range of supporting media.

The surface of carbon fibre was rapidly modified by reductive electrochemical deposition employing a range of diazonium salts. Three sets of fibre were generated possessing pendant amine, carboxylic acid, and lipophilic amide (N-hexyl amide) groups and the effect of these surface chemistries on interfacial shear strength (IFSS) was examined in epoxy resins. Surface grafting of the fibres was studied by X-ray photoelectron spectroscopy, and physical characterisation of the modified fibres showed that our treatments had no detrimental effects on Young's modulus and tensile strength. IFSS increases of 172% and 30% (relative to control fibres) were observed for the amine and lipophilic amide functionalised, respectively. Molecular dynamics simulations of the lipophilic amide suggests IFSS enhancement via soft-soft interactions. Surprisingly, the IFSS of fibres that exhibited carboxylic acid groups at the surface were indistinguishable from that of the untreated control fibres. When applied to polypropylene grafted with maleic anhydride, the amine grafted fibres showed a 67% increase relative to control fibres, attributed to covalent cross-linking between the fibre and maleic anhydride co-monomer.

Reproducible and in-depth studies of the electrochemical graphite intercalation and oxidation processes were carried out with the use of an electrochemical Tee-cell setup. The electrochemical method allowed simpler and greater controllability over the level of oxidation/functionalization, relative to the commonly employed chemical oxidation approach (e.g. the modified Hummers method). Extensive characterization was carried out to understand the properties of the electrochemically-derived graphite oxide (EGrO), and it was found that the abundance of each functionality was highly dependent on the electrochemical reaction time or the concentration of the electrolyte (perchloric acid) employed. Notably, the amount of oxygen functional groups on EGrO could be as high as 30 wt%, but the degree of oxidation did not proceed beyond the generation of carbonyl species. The controllable oxidation level of the EGrO makes it an attractive precursor for many applications, such as electronics and nanocomposites.

Carbon nanotubes (CNTs), particularly of the substrate-grown directly spinnable variety, have a vast number of potential applications. We have devised a recycling methodology to enable the evolution of catalyst morphology and activity and its effect on CNT growth quality and failure to be studied incrementally. Direct spinnability is particularly sensitive to many variables and so provides verification that each cycle is essentially identical. Two processes, utilising acetylene with and without hydrogen, are studied. Acetylene alone gives four cycles of spinnable CNTs before failing abruptly at the fifth at which point catalyst particle (and CNT) areal density increase while CNT diameter and length fall sharply. In contrast, addition of hydrogen doubles the initial growth rate but spinnability declines on the third cycle and fails on the fourth as catalyst (and CNT) areal density decreases sharply. CNT length also falls although diameter increases. Our observations support a proposed ‘sinking plateau’ model of catalyst behaviour where growth rate is driven by the essentially flat accumulation area or ‘plateau plain’ surrounding a local high spot (active catalyst particle). The growth rate remains stable until the plateau plain drops below the substrate surface through diffusion at the base, at which point it falls sharply.

The surface of both oxidized and unoxidized unsized carbon fiber was functionalized using an aziridine linking group derived from reactive nitrenes. The aziridine functionality arose from the cyclization of a reactive nitrene species onto the highly electron rich graphitic surface of the carbon fibers; the nitrene species evolved from thermal N2 elimination from the corresponding (room temperature stable) azide. Surface functionalization using the nitrene approach was supported by X-ray Photoelectron Spectroscopy, in both oxidized and unoxidized carbon fiber. Attempts were also made to functionalize using amide chemistry, the two-step acid chloride coupling being successful for oxidized fibers by utilizing the carboxylic acid rich defect sites on the carbon fiber. None of the chemical treatment pathways had a significant impact on the tensile strength of the individual fibers, and atomic force microscopy revealed that fibers undergoing these treatment methodologies remained intact, without creating additional surface defects.

We report a new method to create covalent crosslinks between carbon nanotubes (CNTs) with reduced intertube and interbundle spaces, for improving the mechanical properties of CNT spun yarns. This is achieved through the pretreatment of a CNT yarn with 4-carboxybenzenediazonium tetrafluoroborate to form reactive carboxyphenyl groups on the CNT sidewalls. These carboxyphenyl groups are then reacted with a multifunctional crosslinker hexa(methoxymethyl) melamine, leading to a highly crosslinked network within the yarn. The CNT yarns were characterized by X-ray photoelectron spectroscopy, focused ion beam scanning electron microscope, and also assessed for their mechanical properties. The results showed that the method developed effectively improved mechanical properties of CNT yarns: we are able to produce CNT yarns with a tensile strength up to 2.5 GPa and Young’s modulus 121 GPa.

Gamma-irradiation of carbon nanotube yarns in air has significantly improved the tensile strength and modulus of the yarns, presumably because of an increased interaction between the individual nanotubes. The improvement has been much greater for tightly structured yarns than for loosely structured yarns. Sonic pulse tests have also shown increased sound velocity and dynamic modulus in the carbon nanotube yarns as a result of gamma-irradiation treatment. X-ray photoelectron spectroscopic analyses on progenitor carbon nanotube forests show that gamma-irradiation treatment in air has dramatically increased the concentration of oxygen, for example as carboxyl groups, in the carbon nanotube assemblies in proportion to radiation dose, indicating that carbon nanotubes were oxidized under the ionizing effect of the gamma-irradiation. Such oxygen species are thought to contribute to the interaction between carbon nanotubes and thus to the improvement of carbon nanotube yarn mechanical properties.