High resolution XPS characterization of chemical functionalised MWCNTs and SWCNTs

High resolution XPS analysis of chemical functionalised multi-wall carbon nanotubes (MWCNTs) and single wall carbon nanotubes (SWCNT) was done with ESCA300 (overall instrument resolution of 0.35 eV). Information to the degree of functionalisation was ascertained by argon ion bombardment of the samples followed by XPS analysis to detect the functional groups, the percentage atomic concentration of various elements present and whether or not the detected functional groups imposed a chemical shift on the CNT atoms. The results show that true chemical functionalisation was achieved and by argon ion bombardment these functional groups can be altered relative to the C 1s carbon atoms of the CNT. The choice of chemicals used for functionalisation, the techniques employed and the types of nanotubes treated are important factors in chemical characterisation. The carbon atom on the nanotube ring to which the functional group (atom) is bonded, the chirality of the CNT, the electronegativity of the functional group, the bond type and whether the CNT is single-wall or multi-wall, or cut (short) could play a role in determining the chemical shift on the CNTs atoms. These investigations are relevant to chemical functionalisation of carbon nanotubes for various applications for example DNA sensors and other biomedical sensors.     

Analysis of the oscillatory behavior of double-walled carbon nanotube-based oscillators

Molecular dynamics simulations of oscillatory behaviors of double-walled carbon nanotube-based oscillators are performed. The second-generation empirical bond-order potential is used for the atomic interactions within a wall, and a registry-dependent and four different registry-independent van der Waals potentials are used for the atomic interactions between walls. It is found that the frequencies of the nanotube oscillators are sensitive to the choice of the van der Waals potentials. An almost non-decay oscillation is observed for the registry-dependent potential when there is no rocking motion. However, an apparent decay oscillation is observed when rocking motion occurs. A decay oscillation is observed for all registry-independent potentials even without rocking motion. Mechanisms leading to unstable oscillatory behavior are analyzed.     

Oxidative functionalization of carbon nanotubes in atmospheric pressure filamentary dielectric barrier discharge (APDBD)

The surface compositional and any structural changes that occur on carbon nanotubes using air-atmospheric pressure dielectric barrier discharge (APDBD) for functionalization are investigated employing Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and neutron diffraction techniques. Atmospheric pressure plasmas (APP) are suggested to be particularly suitable for functionalization of aligned nanotubes, where wet chemical manipulation could damage or even destroy the highly desirable vertical alignment. In this work a detailed experimental study elucidating the effects of APDBD plasma treatment parameters (e.g. power density, discharge composition, inter-electrode gap and treatment time) on the electronic structure, physical, and chemical behaviour of carbon nanotubes has been conducted. In an atmospheric air we find an optimal oxidative functionalization of CNTs in our DBD system within few seconds (<5 s) at a discharge power of ∼0.5 kW. This investigation may find useful application as functionalization technique for CNT engineered devices and sensors.     

Processing-structure-multi-functional property relationship in carbon nanotube/epoxy composites

The novel properties of carbon nanotubes have generated scientific and technical interest in the development of nanotube-reinforced polymer composites. In order to utilize nanotubes in multi-functional material systems it is crucial to develop processing techniques that are amenable to scale-up for high volume, high rate production. In this research we investigate a scalable calendering approach for achieving dispersion of CVD-grown multi-walled carbon nanotubes through intense shear mixing. Electron microscopy was utilized to study the micro and nanoscale structure evolution during the manufacturing process and optimize the processing conditions for producing highly-dispersed nanocomposites. After processing protocols were established, nanotube/epoxy composites were processed with varying reinforcement fractions and the fracture toughness and electrical/thermal transport properties were evaluated. The as-processed nanocomposites exhibited significantly enhanced fracture toughness at low nanotube concentrations. The high aspect ratios of the carbon nanotubes in the as-processed composites enabled the formation of a conductive percolating network at concentrations below 0.1% by weight. The thermal conductivity increased linearly with nanotube concentration to a maximum increase of 60% at 5 wt.% carbon nanotubes.     

Spinose carbon nanotubes grown on graphitized DLC film by low frequency r.f. plasma-enhanced chemical vapor deposition

Spinose carbon nanotubes (SCNTs) are grown on silicon substrates covered with diamond-like carbon film and iron catalyst film (Fe/DLC/Si structure) by low frequency r.f. plasma-enhanced chemical vapor deposition (LFRF-PECVD). During the pre-treatment of the Fe/DLC/Si substrate, there are three processes happened, namely, iron film spalled to small islands, the DLC film graphitized, and the iron island reacted partially with the graphitized DLC (GDLC), which can be deduced from the Raman spectroscopy and SEM pictures. SCNTs film grew from C₂H₂---H₂ mixture under low plasma density. The good contact of carbon nanotube with GDLC film was acquired by the accumulation of the graphite sheets and the reaction between the iron particles and GDLC film. The homogeneous spines with the length of approximately 15 nm and the thickness of <5 nm burgeoned from the defects at the wall of carbon nanotube and distributed uniformly, which were in fact thin bent or rolled-up graphite sheets.     

Low-temperature catalytic growth of carbon nanotubes under microwave plasma assistance

Various carbon nanotubes (CNTs) including aligned arrays, Y-branching and some other novel morphologies have been catalytically grown on anodic porous alumina template (APAT) and on the alumina-supported catalysts with methane (or benzene) as carbon source under microwave plasma assistance below 520 °C. The growth process could be simply operated since neither heating nor bias-voltage was applied to the catalysts or APAT. The results presented in this paper not only greatly richened the nanostructures of carbon family but also provided with a new technique path for synthesizing CNTs or some other nanostructures with the characteristics of low-temperature which has some special advantages or applications.     

Solid-state NMR study of N labelled polyaniline upon reaction with DPPH

The quantitative investigation of the radical scavenging properties of polyaniline (PANI) upon reaction with excess of the stable DPPH radical (a 4:1 ratio of DPPH to aniline units in the polymer) was carried out using ¹⁵N and ¹³C solid state NMR spectroscopy. During the process the polyaniline was oxidised so that the imine content increased from 45 to 65%. The extent of oxidation measured by NMR was confirmed by N1s XPS analysis. However, within a 30 min reaction time, about 85% of the DPPH radicals were scavenged as monitored by the decay in its EPR signal. This is about 20 times greater than the fraction of DPPH required to oxidize PANI from an imine content of 45-65%. An identification of further redox processes is required to explain the high degree of radical scavenging. At the same time, there was no evidence of significant chemical binding or trapping of DPPH in the PANI structure.     

Low temperature SCR of NO with NH3 over carbon nanotubes supported vanadium oxides

A novel multiwalled carbon nanotube (CNTs) supported vanadium catalyst was prepared. The structure of catalyst prepared was characterized by TEM, BET, FTIR, XRD and temperature-programmed desorption (TPD) methods. The results indicated that vanadium particles were highly dispersed on the wall of carbon nanotubes. The V₂O₅/CNT catalysts showed good activities in the SCR of NO with a temperature range of 373–523 K. The Lewis acid sites on the surface of V₂O₅/CNT are the active sites for the selective catalytic reduction (SCR) of NO with NH₃ at low temperatures. It was suggested that the reaction path might involve the adsorbed NH₃ species reacted with NO from gaseous phase and as well as the adsorbed NO₂ species. The diameter of CNTs showed positive effect on the activities of the catalysts. Under the reaction conditions of 463 K, 0.1 Mpa, NH₃/NO = 1, GHSV = 35,000 h⁻¹, and V₂O₅ loading of 2.35 wt%, the outer diameter of CNTs of 60–100 nm, the NO conversion was 92%.     

Carbon nanotubes prepared from three-layered copolymer microspheres of acrylonitrile and methylmethacrylate

Carbon nanotubes (CNTs) were synthesized from fine three-layered copolymer microspheres using the polymer blend technique. Diameter of PMMA core/Poly(AN-co-MMA) shell-1/PMMA shell-2 microspheres, prepared by a radical soap-free emulsion polymerization of methylmethacrylate (MMA) and acrylonitrile (AN), was between 400 nm and 500 nm. Microspheres were subjected to melt-spinning at 305 °C, stabilizing in oxygen at 220 °C for 4 h, and finally carbonizing at 1000 °C for 30 min. FE-SEM study of carbonized sample revealed the presence of CNTs arrays on carbon blocks. Similar arrays were observed in a comparative CNTs sample prepared from three-layered microspheres with the pure PAN shells-1 layers. HRTEM showed that the CNTs derived from copolymer microspheres had different structure when compared to the control sample, i.e. CNTs often adhered to each other and contained the internal compartments. The insufficient PMMA shell-2 coating of copolymer microspheres is believed to be a reason for CNTs adhesion. The possible mechanisms of the carbon block formation and the adhesion of CNTs are introduced.     

High quality double wall carbon nanotubes with a defined diameter distribution by chemical vapor deposition from alcohol

We have synthesized double wall carbon nanotubes (DWNTs) with few defects and little amorphous carbon by hot wall chemical vapor deposition (CVD) of alcohol. Catalysts for the DWNT growth were made from cobalt and molybdenum acetates. Scanning electron microscopy, transmission electron microscopy, multi frequency resonance Raman spectroscopy and optical absorption spectroscopy were used for characterization of the product with regard to DWNT yield, the nanotube diameter distribution, defect concentration and amorphous carbon content. Base pressures lower than 1 × 10⁻⁵ mbar in the CVD reactor considerably suppress defects in the DWNTs. Optimized growth conditions for DWNT formation are presented.