Single-walled Carbon Nanotubes Material Research Articles

Comparison of sample digestion techniques for the determination of trace and residual catalyst metal content in single-wall carbon nanotubes by inductively coupled plasma mass spectrometry

A single-wall carbon nanotube material produced by laser ablation of renewable biochar in the presence of Ni and Co catalyst was characterized for residual catalyst (Co and Ni) as well as trace metal impurity content (Fe, Mo, Cr, Pb and Hg) by isotope dilution ICP-MS following sample digestion. Several matrix destruction procedures were evaluated, including a multi-step microwave-assisted acid digestion, dry ashing at 450°C and microwave-induced combustion with oxygen. Results were benchmarked against those derived from neutron activation analysis and also supported by solid sampling continuum source GF-AAS for several of the elements. Although laborious to execute, the multi-step microwave-assisted acid digestion proved to be most reliable for recovery of the majority of the analytes, although content of Cr remained biased low for each approach, likely due to its presence as refractory carbide.

Realizing one-dimensional quantum and high-frequency transport features in aligned single-walled carbon nanotube ropes

The superiority of the electronic transport properties of single-walled carbon nanotube (SWNT) ropes over SWNT mats is verified from low temperature and frequency-dependent transport. The overall change of resistance versus in nanotube mats shows that 3D variable range hopping is the dominant conduction mechanism within the 2–300 K range. The magneto-resistance (MR) is found to be predominantly negative with a parabolic nature, which can also be described by the hopping model. Although the positive upturn of the MR at low temperatures establishes the contribution from quantum interference, the inherent quantum transport in individual tubes is suppressed at elevated temperatures. Therefore, to minimize multi-channel effects from inter-tube interactions and other defects, two-terminal devices were fabricated from aligned SWNT (extracted from a mat) for low temperature transport as well as high-frequency measurements. In contrast to the mat, the aligned ropes exhibit step-like features in the differential conductance within the 80–300 K temperature range. The effects of plasmon propagation, unique to one dimension, were identified in electronic transport as a non-universal power-law dependence of the differential conductance on temperature and source-drain voltage. The complex impedance showed high power transmission capabilities up to 65 GHz as well as oscillations in the frequency range up to 30 GHz. The measurements suggest that aligned SWNT ropes have a realistic potential for high-speed device applications.

Relaxivity enhancement of aquated Tris(β-diketonate)gadolinium(III) chelates by confinement within ultrashort single-walled carbon nanotubes.

Ultrashort single-walled carbon nanotubes loaded with gadolinium ions (gadonanotubes) have been previously shown to exhibit extremely high T1 -weighted relaxivities (>100 mm(-1) s(-1) ). To further examine the effect of nanoconfinement on the relaxivity of gadolinium-based contrast agents for magnetic resonance imaging, a series of ultrashort single-walled carbon nanotube (US-tube) materials internally loaded with gadolinium chelates have been prepared and studied. US-tubes were loaded with Gd(acac)3 · 2H2 O, Gd(hfac)3 · 2H2 O, and Gd(thd)3 (acac = acetylacetone, hfac = hexafluoroacetylacetone, thd = tetramethylheptanedione). The longitudinal relaxivities of the prepared materials determined at 25°C in a 1.5 T field were 103 mm(-1) s(-1) for Gd(acac)3 · 2H2 O@US-tubes, 105 mm(-1) s(-1) for Gd(hfac)3 · 2H2 O@US-tubes and 26 mm(-1) s(-1) for Gd(thd)3 @US-tubes. Compared with the relaxivities obtained for the unloaded chelates (<10 mm(-1) s(-1) ) as well as accounting for the T1 reduction observed for the empty US-tubes, the boost in relaxivity for chelate-loaded US-tubes is attributed to confinement within the nanotube and depends on the number of coordinated water molecules.

Photoenergy Transfer in SWCNT Mesomaterials

Individual single-walled carbon nanotubes (SWCNTs) have interesting optoelectronic properties that have shown potential uses in photovoltaics, transparent conducting films and sensing devices. However, due to the extreme sensitivity of their optoelectronic properties to environmental stimuli, engineering SWCNT materials is complex. The key ingredient is maintaining a relatively interaction-free local environment during the material synthesis. Toward this end, selection of the correct protective wrappings (i.e. surfactants, polymers, DNA, etc) and added materials (i.e. porphyrin, salts, acids, etc) to maintain or tune the tubes optoelectronic properties for a desire application is crucial. We will highlight some of our recent SWCNT mesomaterials and discuss the effects each of the matrixes has on SWCNT optoelectronic properties. We will introduce photoactive molecules and discuss the electronic interactions we observe with SWCNTs and how these various additives can be used to control the final material properties for targeted applications such as sensors and photovoltaics.

Removing Aggregates from Single-Walled Carbon Nanotube Samples by Magnetic Purification

Purification of raw single-walled carbon nanotube (SWCNT) material remains an important challenge in nanotube research and applications. We describe here a simple but effective purification method that uses permanent magnets to remove many nanotube aggregates, as well as residual metallic catalyst, from aqueous suspensions of surfactant-coated SWCNTs. Samples have been characterized by optical absorption, fluorescence, and Raman spectroscopies; atomic force microscopy and near-infrared fluorescence microscopy; and thermogravimetric analysis. It is found that magnetic purification reduces absorption backgrounds and increases average fluorescence efficiencies to levels comparable to those in ultracentrifuged samples. The ratio of individualized SWCNTs to aggregates in magnetically processed HiPco samples is estimated to be approximately 4:1. As compared to ultracentrifugation, magnetic processing promises major advantages in cost, simplicity, energy consumption, and scalability.

Opto-electronic properties of the single-walled carbon nanotube film and melamine formaldehyde resin composite

The single-walled carbon nanotube (SWCNT) can strongly absorb light, particularly in the near infrared region, and can convert it into thermal energy, while the SWCNT also has a great capacity of converting thermal energy into electrical energy. In this paper, by means of vacuum filtering, SWCNT film is prepared by SWCNT arrays generated by the chemical vapor deposition. A simple experimental device of SWCNT is designed and the conversion from the infrared light to voltage output is successfully achieved. The SWCNT/melamine formaldehyde resin composite film is prepared by the functional steps. The experimental results show that the composite material can produce an output voltage of opposite sign, which indicates that the SWCNT and melamine formaldehyde resin composite material have good application prospect in the field of photo-electrical applications.

Counter-current ammonia injection flow during synthesis of single-walled carbon nanotubes by induction thermal plasma

Mass production of single-walled carbon nanotubes (SWCNTs) has been enabled through introduction of solid feedstock into the Ar–He thermal plasma generated by radio-frequency induction torch. The non-reactive nature of Ar–He plasma and solid carbon results in formation of pristine SWCNT final product soot which is insoluble in many solvents and is poorly incorporated in polymers matrix. To better understand the effects of reactive synthesis environment on the SWCNTs material, ammonia (NH3) was counter-currently injected into the main plasma stream with different nozzles and at different positions in the reactor. Raman analysis showed that the quality of SWCNTs was evidently altered upon the ammonia injection. Elemental analysis of nitrogen on the SWCNT samples revealed a maximum of 10-fold increase after NH3 injection. TEM imaging showed the presence of onion-like and planar carbon nanostructures in the SWCNT sample obtained after the highest NH3 injection rate (15vol%). A long-term dispersibility enhancement was observed for the NH3-treatd SWCNT sample in dimethylformamide and isopropanol. Finally, to clarify possible reactions and species at equilibrium state and to better understand the importance of nozzle in the NH3 injection process on the thermo-flow field of the induction thermal plasma reactor, the synthesis system was simulated through a thermodynamic calculation and computational fluid dynamic (CFD) method, respectively.

Additive-Free Assemblies of Ramified Single-Walled Carbon Nanotubes

Carbon nanotubes (CNTs) are difficult to process, and their assembly in macroscopic materials that allow us to benefit from the exceptional properties of the nanotubes is of crucial interest for applications. The developed CNT processing procedures usually involve additives that remain in the final product and are known to diminish the properties of the CNT-based material. Here, we propose a multistep approach to process single-walled carbon nanotubes (SWNTs) and obtain macroscopic additive-free SWNT materials. High-quality dispersion of purified SWNTs is first induced in polar solvent due to their preceding reduction reaction with an alkali metal. The partial debundling process occurring at this stage leads to ramified SWNTs. They can then be self-assembled by attractive intermolecular forces through a controlled destabilization of the dispersions by a simple oxidation. Swollen gels of SWNTs are formed at an air/solvent interface. After freeze-drying, the additive-free SWNT material shows a hierarchical structure with highly interconnected SWNTs. Thanks to the obtained ramification of the SWNTs, these latter are able to well entangle what guarantees the robustness of the obtained additive-free SWNT material. Moreover, this integrated process offers an increase of the accessible surface compared to that of the raw bundled SWNTs. The obtained assembled SWNTs show an improved adsorption capacity.

Statistical sampling of carbon nanotube populations by thermogravimetric analysis

Carbon nanotubes are one of the most promising nanomaterials available with applications in electronics devices, sensing, batteries, composites and medicine. Strict control of the carbon nanotube chemistry and properties is necessary as the applications proceed into more specialized areas. Thermogravimetric analysis (TGA) is one analytical method currently utilized for the characterization of carbon nanotubes. Though TGA can provide quantitative measurements of the composition of a sample, many researchers do not ensure the variance of the sample is properly captured. This research demonstrates for four single-wall carbon nanotube (SWCNT) samples how to statistically evaluate the material with TGA to ensure that the variance within the material is represented. SEM results are used to help reach conclusions about purity of the material by providing a visual means for inspection. This data is used to select the SWCNT material with the lowest variability and highest quality, as evaluated by composition and reproducibility.

STUDY OF THE NEAR INFRARED-MEDIATED HEATING OF DISPERSIONS OF PROTEIN-COATED PRISTINE AND CARBOXYLATED SINGLE-WALLED CARBON NANOTUBES.

Previously, we demonstrated the selective NIR-mediated ablation of tumor cells in vitro using pristine single-walled carbon nanotubes (SWNTs) with adsorbed tumor-targeting ligands and carboxylated SWNTs with covalently-attached ligands. The covalent approach is advantageous in ensuring that protein ligands remain associated with the NIR-absorbing SWNTs in biological matrices and the noncovalent approach has the advantage of enabling SWNT functionalization without perturbation of the SWNT lattice and photothermal properties. Herein, we compare the ability of moderately-carboxylated (~4 at.% carboxylic acid groups) and pristine SWNT materials to absorb 808 nm radiation and convert it to heat. Under conditions of a constant 808 nm laser power density, the approach involved measuring the temperature of aqueous dispersions of protein-coated SWNTs as a function of the irradiation time. Nearly identical temperature profiles were observed for dispersions of moderately-carboxylated and pristine SWNTs possessing matched 808 nm optical densities and equivalent concentrations of carbonaceous species (i.e., SWNTs and amorphous carbon impurities). The results indicate that the amount of carbonaceous species in purified dispersions of protein-coated SWNTs is more important for converting absorbed 808 nm radiation into heat than whether or not the SWNTs were moderately carboxylated, and that moderately-carboxylated SWNTs could be the SWNT-material of choice for the targeted photothermal ablation of tumor cells.

Coaxial cables with single-wall carbon nanotube outer conductors exhibiting attenuation/length within specification

In this Letter, high-purity, KAuBr4-treated single-wall carbon nanotube (SWCNT) materials are utilised as outer conductors in coaxial cables. The attenuation/length is within Mil-C-17 specification and nearly equivalent to traditional copper outer conductors up to 3 GHz. The improved transmission performance is attributed to higher conductivity and density of the SWCNT network which creates enhanced nanoscale coverage to improve screening. The weight/length which can be achieved with SWCNT outer coaxial cables results in greater than 40% savings compared with conventional coaxial cables while maintaining a flexible cable design.

Empirical evaluation of attractive van der Waals potentials for type-purified single-walled carbon nanotubes

van der Waals forces play a critical role in the structure and stability of single-wall carbon nanotube (SWCNT) materials. Thin films assembled from SWCNTs purified by electronic type show particular promise for flexible electronics applications, but mechanical durability remains an unresolved issue. Using transition resonances determined from spectroscopic measurements of type-purified SWCNTs deposited on quartz, coupled with analogous spectroscopic characterization of polydimethylsiloxane (PDMS) substrates, we use the Lifshitz theory of van der Waals dispersion interactions developed by Rajter and co-workers [Rajter et al., Phys. Rev. B 76, 045417 (2007)] to examine the influence of electronic type on van der Waals contact potentials in polymer-supported nanotube networks. Our results suggest a significantly stronger nanotube-nanotube and nanotube-polymer attraction for the semiconducting SWCNT fractions, consistent with recent measurements of the electronic durability of flexible transparent SWCNT coatings.

Brightening of the Lowest Exciton in Carbon Nanotubes via Chemical Functionalization

Using time-dependent density functional theory, we found that chemical functionalization at low concentrations of single-walled carbon nanotubes (SWNTs) locally alters the π-conjugated network of the nanotube surface and leads to a spatial confinement of the electronically excited wave functions. Depending on the adsorbant positions, the chemisorption significantly modifies the optical selection rules. Our modeling suggests that photoluminescent efficiency of semiconducting SWNT materials can be controlled by selective chemical functionalization.

DFT calculations of structures, 13C NMR chemical shifts and Raman RBM mode of simple models of ultra small diameter (4,0) zigzag hydroxylated single wall carbon nanotubes

Selected acenes, cyclic acenes and model zigzag (4,0) single wall carbon nanotubes (SWCNTs) with one hydroxylic group at the open end were fully optimized at the B3LYP/6-31G* level of theory. The impact of molecule size on the B3LYP/pcS-2 calculated 13C NMR chemical shifts was studied to characterize pristine and tip-monofunctionalized ultra narrow SWCNTs. The harmonic frequency of Raman radial breathing mode (RBM) was determined for monohydroxylated cyclic acenes and correlated with their diameter. A regular convergence of selected CC bond lengths, RBM frequency and carbon chemical shifts upon increasing the size of the systems was observed and fitted toward very large systems with two-parameter mathematical formula. The observed values of selected structural, Raman and 13C NMR chemical shifts in the studied models point out toward a feasibility of NMR technique as a tool for characterization of pristine and OH functionalized SWCNT materials.

Cytotoxicity Screening of Single-Walled Carbon Nanotubes: Detection and Removal of Cytotoxic Contaminants from Carboxylated Carbon Nanotubes

This study compares the cytotoxicity to cultured mammalian cells of nine different single-walled carbon nanotube (SWNT) products synthesized by a variety of methods and obtained from a cross section of vendors. A standard procedure involving sonication and centrifugation in buffered bovine serum albumin was developed to disperse all the SWNTs in a biocompatible solution to facilitate comparisons. The effect of the SWNTs on the proliferative ability of a standard cell line was then assessed. Of the nine different SWNT materials tested, only two were significantly toxic, and both were functionalized by carboxylation from different vendors. This was unexpected because carboxylation makes SWNTs more water-soluble, which would presumably correlate with better biocompatibility. However, additional purification work demonstrated that the toxic material in the carboxylated SWNT preparations could be separated from the SWNTs by filtration. The filtrate that contained the toxic activity also contained abundant small carbon fragments that had Raman signatures characteristic of amorphous carbon species, suggesting a correlation between toxicity and oxidized carbon fragments. The removal of a toxic contaminant associated with carboxylated SWNTs is important in the development of carboxylated SWNTs for pharmacological applications.

Use of neutron activation analysis for the characterization of single-wall carbon nanotube materials

Instrumental neutron activation analysis (INAA) and prompt gamma neutron activation analysis (PGAA) were used to characterize a variety of single-wall carbon nanotube (SWCNT) materials from different principal production processes, as well as a material containing SWCNTs together with other carbon species, catalyst residues, and trace element contaminants to be issued by the National Institute of Standards and Technology for characterization and distribution as Standard Reference Material SRM 2483 Carbon Nanotube Soot. INAA proved to be well suited for the direct determination of catalyst and contaminant trace elements requiring only minimal sample preparation. PGAA complemented the INAA data in particular with determinations of the light elements. Carbon and hydrogen results provided information on the materials purity and storage properties. Strategies for the quality assurance of the measurements in these new materials were developed. INAA and PGAA data were provided for the value assignment of mass fractions of catalyst and trace elements in the candidate SRM and a systematic overview was obtained of the catalyst and trace element contaminants associated with each of the major production routes.

Transparent Conductors from Carbon Nanotubes LBL-Assembled with Polymer Dopant with π−π Electron Transfer

Single-walled carbon nanotube (SWNT) and other carbon-based coatings are being considered as replacements for indium tin oxide (ITO). The problems of transparent conductors (TCs) coatings from SWNT and similar materials include poor mechanical properties, high roughness, low temperature resilience, and fast loss of conductivity. The simultaneous realization of these desirable characteristics can be achieved using high structural control of layer-by-layer (LBL) deposition, which is demonstrated by the assembly of hydroethyl cellulose (HOCS) and sulfonated polyetheretherketone (SPEEK)-SWNTs. A new type of SWNT doping based on electron transfer from valence bands of nanotubes to unoccupied levels of SPEEK through π-π interactions was identified for this system. It leads to a conductivity of 1.1 × 10(5) S/m at 66 wt % loadings of SWNT. This is better than other polymer/SWNT composites and translates into surface conductivity of 920 Ω/◻ and transmittance of 86.7% at 550 nm. The prepared LBL films also revealed unusually high temperature resilience up to 500 °C, and low roughness of 3.5 nm (ITO glass -2.4 nm). Tensile modulus, ultimate strength, and toughness of such coatings are 13 ± 2 GPa, 366 ± 35 MPa, and 8 ± 3 kJ/m(3), respectively, and exceed corresponding parameters of all similar TCs. The cumulative figure of merit, ∏(TC), which included the critical failure strain relevant for flexible electronics, was ∏(TC) = 0.022 and should be compared to ∏(TC) = 0.006 for commercial ITO. Further optimization is possible using stratified nanoscale coatings and improved doping from the macromolecular LBL components.

Super-high-frequency shielding properties of excimer-laser-synthesized-single-wall-carbon-nanotubes/polyurethane nanocomposite films

Electromagnetic shielding attenuation (ESA) properties of carbon nanotubes/polymer nanocomposite films, in the super high frequency (SHF) X-band (7–12 GHz) domain are studied. The nanocomposite films consisted of thermoset polyurethane (PU) resin blended with single-walled carbon nanotubes (SWCNTs) mats, and deposited on fused quartz substrates. Two different approaches were used to achieve the nanocomposite films, namely (i) through the on-substrate “all-laser” growth approach of SWCNTs directly onto substrate, followed by their infiltration by the PU resin, and (ii) by appropriately dispersing the chemically-purified SWCNTs (in the soot form) into the PU matrix and their subsequent deposition onto quartz substrates by means of a solvent casting process. Characterizations of the ESA properties of the developed nanocomposite films show that they exhibit systematically a deep shielding band, centered at around 9.5 GHz, with an attenuation as high as |− 30| dB, recorded for SWCNT loads of 2.5 wt. % and above. A direct correlation is established between the electrical conductivity of the nanocomposite films and their electromagnetic shielding capacity. The SWCNTs/PU nanocomposites developed here are highly promising shielding materials as SHF notch filters, as their ESA capacity largely exceeds the target value of |− 20| dB generally requested for commercial applications.

Multifunctional Free-Standing Single-Walled Carbon Nanotube Films

We report a simple and rapid method to prepare multifunctional free-standing single-walled carbon nanotube (SWCNT) films with variable thicknesses ranging from a submonolayer to a few micrometers having outstanding properties for a broad range of exceptionally performing devices. We have fabricated state-of-the-art key components from the same single component multifunctional SWCNT material for several high-impact application areas: high efficiency nanoparticle filters with a figure of merit of 147 Pa(-1), transparent and conductive electrodes with a sheet resistance of 84 Ω/◻ and a transmittance of 90%, electrochemical sensors with extremely low detection limits below 100 nM, and polymer-free saturable absorbers for ultrafast femtosecond lasers. Furthermore, the films are demonstrated as the main components in gas flowmeters, gas heaters, and transparent thermoacoustic loudspeakers.

Single walled carbon nanotubes (SWNTs) as templates for the growth of TiO2: the effect of silicon in coverage and the positive and negative synergies for the photocatalytic degradation of Congo red dye

Single walled carbon nanotubes (SWNTs) are used as scaffolds to grow titania (TiO2) under a range of different growth conditions. It is found that the titania growth occurring on SWNTs is significantly different in the presence of silica; this is contrary to prior reports, the important controlling factor for obtaining good coverage is not “nanoscopic HF bubbles”. The silica is either sourced from the reaction vessel if made from glass or may be added in the form of fumed silica: the greater the silicon content the greater the coverage of the SWNT. The adsorption and photocatalysis of organic Congo red dye on these hybrid titania covered SWNT materials are studied; while the adsorption of the dye onto the catalyst may be high, it is only in certain cases wherein it results in superior catalytic performance. The synergy between TiO2 and SWNTs with regard to photocatalysis is not always positive. The addition of silica promotes the complete coating of SWNT with TiO2, the resulting materials show very high absorption of Congo red but essentially no catalytic activity. In order to promote catalytic activity, it is necessary to have less full coverage of the SWNTs and the smallest average particle size of the grown titania. Intimate contact between the SWNT and the TiO2 is needed (rather than a physical mixture) for any catalysis, and the electronic properties of the SWNTs are clearly important since multiwalled carbon nanotubes appear to have little effect on altering the photocatalytic activity.