Christopher T. Kingston

Large-scale production of single-walled carbon nanotubes by induction thermal plasma

High quality single-walled carbon nanotubes (SWNT) have been synthesized at large scales by the method of direct evaporation of carbon black and metallic catalyst mixtures, using induction thermal plasma technology. The processing system consists mainly of an RF plasma torch, which generates a plasma jet of extremely high temperature (~15 000 K), with a high energy density and abundance of reactive species (ions and neutrals). With the present reactor system, it has been demonstrated that carbon soot product which contains approximately 40 wt% of SWNT can be continuously synthesized at the high production rate of ~100 g h−1. The processing parameters involved have been examined closely in order to evaluate their individual influences on SWNT synthesis. The results have shown that the quality and purity of the SWNT produced are critically affected by the grade of carbon black, the plasma gas composition and the metallic catalyst employed. Theoretical calculations, including thermodynamic and two-dimensional thermal flow analyses, have also been performed to determine the optimal process environment most suitable for SWNT synthesis and to obtain a better understanding of the effects of process parameters. Finally, product comparisons have been made against other reference materials using Raman spectroscopy, which has shown that the quality of thermal plasma-grown SWNT is superior to that of arc discharge-grown SWNT and approaches the quality of laser-grown SWNT. This result confirms that the induction thermal plasma technology developed in this work is one of the most promising methods for the production of high quality SWNT at large scales for commercial uses.

Hydrogen-Catalyzed, Pilot-Scale Production of Small-Diameter Boron Nitride Nanotubes and Their Macroscopic Assemblies

Boron nitride nanotubes (BNNTs) exhibit a range of properties that are as compelling as those of carbon nanotubes (CNTs); however, very low production volumes have prevented the science and technology of BNNTs from evolving at even a fraction of the pace of CNTs. Here we report the high-yield production of small-diameter BNNTs from pure hexagonal boron nitride powder in an induction thermal plasma process. Few-walled, highly crystalline small-diameter BNNTs (∼5 nm) are produced exclusively and at an unprecedentedly high rate approaching 20 g/h, without the need for metal catalysts. An exceptionally high cooling rate (∼10(5) K/s) in the induction plasma provides a strong driving force for the abundant nucleation of small-sized B droplets, which are known as effective precursors for small-diameter BNNTs. It is also found that the addition of hydrogen to the reactant gases is crucial for achieving such high-quality, high-yield growth of BNNTs. In the plasma process, hydrogen inhibits the formation of N2 from N radicals and promotes the creation of B-N-H intermediate species, which provide faster chemical pathways to the re-formation of a h-BN-like phase in comparison to nitridation from N2. We also demonstrate the fabrication of macroscopic BNNT assemblies such as yarns, sheets, buckypapers, and transparent thin films at large scales. These findings represent a seminal milestone toward the exploitation of BNNTs in real-world applications.

Fabrication of Carbon Nanotubes

Abstract The remarkable properties of carbon nanotubes give promise of a diverse array of revolutionary technologies and applications. Synthesis remains the key to their development. This article will review many of the current methods used for nanotube synthesis and the recent results towards achieving the goal of large-scale production with rational control of nanotube structure and properties.

Toughening of epoxy matrices with reduced single-walled carbon nanotubes

Reduced single-walled carbon nanotubes (r-SWCNT) are shown to react readily at room temperature under inert atmosphere conditions with epoxide moieties, such as those in triglycidyl p-amino phenol (TGAP), to produce a soft covalently bonded interface around the SWCNT. The soft interface is compatible with the SWCNT-free cross-linked cured matrix and acts as a toughener for the composite. Incorporation of 0.2 wt % r-SWCNT enhances the ultimate tensile strength, toughness and fracture toughness by 32, 118, and 40%, respectively, without change in modulus. A toughening rate (dK(IC)/dwt(f)) of 200 MPa m(0.5) is obtained. The toughening mechanism is elucidated through dynamic mechanical analyses, Raman spectroscopy and imaging, and stress-strain curve analyses. The method is scalable and applicable to epoxy resins and systems used commercially.

Raman microscopy mapping for the purity assessment of chirality enriched carbon nanotube networks in thin-film transistors

With recent improvements in carbon nanotube separation methods, the accurate determination of residual metallic carbon nanotubes in a purified nanotube sample is important, particularly for those interested in using semiconducting single-walled carbon nanotubes (SWCNTs) in electronic device applications such as thin-film transistors (TFTs). This work demonstrates that Raman microscopy mapping is a powerful characterization tool for quantifying residual metallic carbon nanotubes present in highly enriched semiconducting nanotube networks. Raman mapping correlates well with absorption spectroscopy, yet it provides greater differentiation in purity. Electrical data from TFTs with channel lengths of 2.5 and 5 µm demonstrate the utility of the method. By comparing samples with nominal purities of 99.0% and 99.8%, a clear differentiation can be made when evaluating the current on/off ratio as a function of channel length, and thus the Raman mapping method provides a means to guide device fabrication by correlating SWCNT network density and purity with TFT channel scaling.

Covalent Functionalization of Boron Nitride Nanotubes via Reduction Chemistry

Boron nitride nanotubes (BNNTs) exhibit a range of properties that hold great potential for many fields of science and technology; however, they have inherently low chemical reactivity, making functionalization for specific applications difficult. Here we propose that covalent functionalization of BNNTs via reduction chemistry could be a highly promising and viable strategy. Through density functional theory calculations of the electron affinity of BNNTs and their binding energies with various radicals, we reveal that their chemical reactivity can be significantly enhanced via reducing the nanotubes (i.e., negatively charging). For example, a 5.5-fold enhancement in reactivity of reduced BNNTs toward NH2 radicals was predicted relative to their neutral counterparts. The localization characteristics of the BNNT π electron system lead the excess electrons to fill the empty p orbitals of boron sites, which promote covalent bond formation with an unpaired electron from a radical molecule. In support of our theoretical findings, we also experimentally investigated the covalent alkylation of BNNTs via reduction chemistry using 1-bromohexane. The thermogravimetric measurements showed a considerable weight loss (12-14%) only for samples alkylated using reduced BNNTs, suggesting their significantly improved reactivity over neutral BNNTs. This finding will provide an insight in developing an effective route to chemical functionalization of BNNTs.

Coupled thermogravimetry, mass spectrometry, and infrared spectroscopy for quantification of surface functionality on single-walled carbon nanotubes

AbstractWe have successfully applied coupled thermogravimetry, mass spectrometry, and infrared spectroscopy to the quantification of surface functional groups on single-walled carbon nanotubes. A high-purity single-walled carbon nanotube sample was subjected to a rapid functionalization reaction that attached butyric acid moieties to the nanotube sidewalls. This sample was then subjected to thermal analysis under inert desorption conditions. Resultant infrared and mass spectrometric data were easily utilized to identify the desorption of the butyric acid groups across a narrow temperature range and we were able to calculate the degree of substitution of the attached acid groups within the nanotube backbone as 1.7 carbon atoms per hundred, in very good agreement with independent analytical measurements made by inductively coupled plasma optical emission spectrometry (ICP-OES). The thermal analysis technique was also able to discern the presence of secondary functional moieties on the nanotube samples that were not accessible by ICP-OES. This work demonstrates the potential of this technique for assessing the presence of multiple and diverse functional addends on the nanotube sidewalls, beyond just the principal groups targeted by the specific functionalization reaction. Figure3D contour map of the FTIR spectra of the species desorbed from the GAP-functionalized SWCNT sample as a function of temperature.

About the solubility of reduced SWCNT in DMSO

Single-walled carbon nanotubes (SWCNT) have been reduced with sodium naphthalide in THF. The reduced SWCNT are not only soluble in dimethylsulfoxide (DMSO) to form a stable solution/suspension, but also react spontaneously at room temperature with DMSO to evolve hydrocarbon gases and are converted into functionalized SWCNT. The degree of functionalization is about 2C% and the addends are mainly methyl and small oxygen-containing hydrocarbons. The functionalized SWCNT are apparently more soluble and stable in DMSO solution. It may open a new era for further processing and applications.

NanoRelease: Pilot interlaboratory comparison of a weathering protocol applied to resilient and labile polymers with and without embedded carbon nanotubes

A major use of multi-walled carbon nanotubes (MWCNTs) is as functional fillers embedded in a solid matrix, such as plastics or coatings. Weathering and abrasion of the solid matrix during use can lead to environmental releases of the MWCNTs. Here we focus on a protocol to identify and quantify the primary release induced by weathering, and assess reproducibility, transferability, and sensitivity towards different materials and uses. We prepared 132 specimens of two polymer-MWCNT composites containing the same grade of MWCNTs used in earlier OECD hazard assessments but without UV stabilizer. We report on a pilot inter-laboratory comparison (ILC) with four labs (two US and two EU) aging by UV and rain, then shipping for analysis. Two labs (one US and one EU) conducted the release sampling and analysis by Transmission Electron Microscopy (TEM), Inductively Coupled Plasma- Mass Spectrometry (ICP-MS), UltravioleteVisible Spectroscopy (UVeVis), Analytical Ultracentrifugation (AUC), and Asymmetric Flow Field Flow Fractionation (AF4). We compare results between aging labs, between analysis labs and between materials. Surprisingly, we found quantitative agreement between analysis labs for TEM, ICP-MS, UVeVis; low variation between aging labs by all methods; and consistent rankings of release between TEM, ICP-MS, UVeVis, AUC. Significant disagreement was related primarily to differences in aging, but even these cases remained within a factor of two.

Polymer nanocomposites from free-standing, macroscopic boron nitride nanotube assemblies†

Here we report the fabrication of free-standing boron nitride nanotube (BNNT) sheets by direct deposition and by vacuum filtration methods, including novel hybrid assemblies with BNNT and carbon nanotubes. Such sheets have enabled production of polymer nanocomposites with high nanotube content. Two example cases, BNNT–epoxy nanocomposites (>30 wt% BNNTs) produced by impregnation of dry sheets and BNNT sheets modified by integration of a thermoplastic polyurethane are described. Related methods have proven advantageous for carbon nanotube composites and, enabled by new technology for large scale BNNT production, such composites have now been realized with BNNTs. This represents an important milestone towards the development of BNNT-based multifunctional composites.