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Ultraviolet photoelectron spectra (UPS) are reported for mass-selected negative carbon clusters extracted from a pulsed supersonic beam. In the size range from 48 to 84 atoms, three clusters were found to be closed-shell species with appreciable HOMO–LUMO gaps: C 50 (0.3–0.6 eV), C 60 (1.5–2.0 eV), and C 70 (0.7–1.2 eV). UPS data for all other clusters revealed no appreciable HOMO–LUMO gap, indicating they are either open-shell species, or closed-shell species with small HOMO–LUMO gaps. Buckminsterfullerene (C 60 ) was found to have the lowest electron affinity (2.6–2.8 eV) of any cluster. Agreement between these UPS data and electronic structure calculations strongly support the spheroidal shell model for C 60 .

The present study demonstrates the viability of the reductive attachment step of the single walled carbon nanotube (SWCNT) lengthening process in which long SWCNTs are grown from short nanotube seeds. Aryl sulfonate sidewall-functionalized, carboxylate end-functionalized SWCNTs are attached to an inorganic cluster pro-catalyst (FeMoC) via ligand exchange. The SWCNT–FeMoC complex was electrodeposited onto highly ordered pyrolytic graphite (HOPG), heated and exposed to etching conditions. Pre- and post-treatment AFM imaging shows that controlled reductive etching of the SWCNTs is attainable at a variety of pressures and temperatures in hot surface/cold gas and hot surface/hot gas systems.

Electron beam irradiation with moderate fluences of approximately 10 16 –10 17 electrons per cm 2 is used for controllable, bulk-scale cutting of single-walled carbon nanotubes (SWCNTs). The effectiveness of high energy electron irradiation in cutting SWCNTs is dependent on the nature of the sidewall. While pristine nanotubes are very stable under irradiation conditions, ozonated SWCNTs combined with a moderate fluence of electrons resulted in bulk-scale cutting of nanotubes. The length distribution of the cut SWCNTs could be controlled by adjusting the irradiation fluence. The average length of the cut nanotubes was 65 nm with 85% of the nanotubes shorter than 100 nm.

Single-walled carbon nanotubes (SWNTs) show great promise for use in a wide range of applications. One of the most promising avenues for attaining these applications is the dispersion of SWNTs at high concentrations in superacids, and their processing into macroscopic articles such as fibres or films. Fibres spun from SWNT/superacid dispersions indicate that the morphology of the starting SWNT material is reflected in the final morphology of the as-spun fibre. Here, we describe a method (termed disentanglement) of dispersing SWNTs in superacids and treating them using a high-shear, rotor/stator homogenizer, followed by coagulation to recover the solid SWNT material for use in fibre spinning. Several lines of experimental evidence (rheology and optical microscopy of the SWNTs in solution, scanning electron microscopy (SEM) of the coagulated material, and SEM of fibres spun from the coagulated material) show that this treatment radically improves the degree of alignment in the SWNTs' morphology, which in turn improves the dispersibility and processability. Raman microscopy and thermogravimetric analysis (TGA) before and after homogenization show that the treatment does not damage the SWNTs. Although this technique is particularly useful as a pre-processing step for fibre spinning of neat SWNT fibres, it is also useful for neat SWNT films, SWNT/polymer composites, and surfactant- or polymer-stabilized SWNT dispersions.

BACKGROUND. Single-walled carbon nanotubes (SWNTs) have remarkable physicochemical properties that may have several medical applications. The authors have discovered a novel property of SWNTs—heat release in a radiofrequency (RF) field—that they hypothesized may be used to produce thermal cytotoxicity in malignant cells. METHODS. Functionalized, water-soluble SWNTs were exposed to a noninvasive, 13.56-megahertz RF field, and heating characteristics were measured with infrared thermography. Three human cancer cell lines were incubated with various concentrations of SWNTs and then treated in the RF field. Cytotoxicity was measured by fluorescence-activated cell sorting. Hepatic VX2 tumors in rabbits were injected with SWNTs or with control solutions and were treated in the RF field. Tumors were harvested 48 hours later to assess viability. RESULTS. The RF field induced efficient heating of aqueous suspensions of SWNTs. This phenomenon was used to produce a noninvasive, selective, and SWNT concentration-dependent thermal destruction in vitro of human cancer cells that contained internalized SWNTs. Direct intratumoral injection of SWNTs in vivo followed by immediate RF field treatment was tolerated well by rabbits bearing hepatic VX2 tumors. At 48 hours, all SWNT-treated tumors demonstrated complete necrosis, whereas control tumors that were treated with RF without SWNTs remained completely viable. Tumors that were injected with SWNTs but were not treated with RF also were viable. CONCLUSIONS. The current results suggested that SWNTs targeted to cancer cells may allow noninvasive RF field treatments to produce lethal thermal injury to the malignant cells. Now, the authors are developing SWNTs coupled with cancer cell-targeting agents to enhance SWNT uptake by cancer cells while limiting uptake by normal cells. Cancer 2007. © 2007 American Cancer Society.

Pristine, individualized single-walled carbon nanotubes (SWCNTs) have been noncovalently captured within PEG-terminated block copolymer amphiphiles. Two cross-linkable amphiphiles were evaluated: polyethylene glycol-polyacrylic acid-polystyrene (PEG-PAA-PS) and polyethylene glycol-polybutadiene (PEG-PB). The resulting self-assembled PEG-PAA-PS structures, called PEG-eggs, are freely soluble in water and stable in physiological media. SWCNTs in PEG-eggs retain their intrinsic near-infrared fluorescence, resist exchange with serum proteins, and are non-cytotoxic to mouse macrophage and human renal cells based on in vitro viability assays.

The ability to accurately measure the length of nanotubes is important to understanding nanotube growth and cutting processes. To date, there have been few methods available to obtain a statistically significant length measurement of any nanotube sample due to difficulties in obtaining a complete suspension of individual nanotubes and the tedious nature of measuring 1000+ nanotubes. Here we describe a relatively simple method that functionalizes single-walled carbon nanotubes to achieve a high propensity of individual nanotubes in chloroform as high as 92%. This suspension can be dispersed on mica substrates for AFM analysis. Nanotube lengths and heights can be determined using the Nanotube Length Analysis module of SIMAGIS yielding an accurate measure of length and height distribution of a large population of the nanotube sample.

We describe a fast, reproducible method to accurately measure the length of single-walled carbon nanotubes (SWNTs). The method is based on measuring the viscosity of a macroscopic sample of dilute suspended SWNTs. The average length is determined from the difference between the zero-shear viscosity of the suspension and that of the solvent. Using the relationship between viscosity and length, the average length of HiPco SWNTs is found to range from 400 to 700 nm, in agreement with atomic force microscopy (AFM) measurements. Compared to AFM, length determination by viscosity is faster and appears more reproducible.

Carbon nano-tubes (CNTs) are attracting tremendous interest as the object of fundamental studies in condensed matter and molecular physics as well as possible functional units for future nano-devices. Some of the most striking features of CNTs are related to the symmetry breaking effect of high magnetic fields threading the tube axis. In the present paper we review the results of recent magneto-optical studies of single-walled CNTs in pulsed magnetic fields up to 71 T and at temperatures between 4.2 and 300 K. We present clear evidence for (a) the effect of the Aharonov-Bohm phase on the bandstructure of CNTs, (b) the existence of dark excitons in CNTs due to Coulomb mixing and (c) the effect of magnetic brightening, i.e. the increase of the quantum yield of CNTs under the influence of an external field. Experimental data was derived from large ensembles of individualized tubes in either aligned films or in liquid suspension. A brief discussion of the effect of dynamic magnetic alignment of suspended tubes will be included.

We report on a one-pot, highly selective chemistry to remove residual catalysts from single-walled carbon nanotubes (SWNTs). The impurities, initially present at approximately 35 wt % and mostly as carbon-coated iron nanoparticles, can be driven below 5 wt % with nearly no loss of SWNTs. The carbon-coated iron impurities are dissolved simply by reacting with an aqueous mixture of H2O2 and HCl at 40-70 degrees C for 4-8 h. This purification combines two known reactions involving H2O2 and HCl, respectively; however, by combining these two typically inefficient reactions into a one-pot reaction, the new process is surprisingly selective toward the removal of the metal impurities. This high selectivity derives from the proximity effect of the iron-catalyzed Fenton chemistry. At pH approximately 1-3, iron is dissolved upon exposure, avoiding the otherwise aggressive iron-catalyzed digestion of SWNTs by H2O2. This extremely simple and selective chemistry offers a "green" and scalable process to purify carbon nanotube materials.

Continued growth is a way of growing nanotubes targeted to produce continuous and chirality-controlled single-walled carbon nanotube (SWNT) materials. This growth method strongly depends on efficient preparation of open-ended SWNT substrates. Nanoscopically flat open-ended SWNT substrates have been prepared by cutting the SWNT spun fiber with a focused ion beam cutting technique and followed by etching schemes for cleaning amorphous carbon and opening the ends of the SWNTs. The open ends were effectively characterized through selective etch back of open SWNT ends by carbon dioxide gas at 950 °C. High density continued growth was demonstrated from these nanoscopically flat open-ended substrates.

Individualized, chemically pristine single-walled carbon nanotubes have been intravenously administered to rabbits and monitored through their characteristic near-infrared fluorescence. Spectra indicated that blood proteins displaced the nanotube coating of synthetic surfactant molecules within seconds. The nanotube concentration in the blood serum decreased exponentially with a half-life of 1.0 ± 0.1 h. No adverse effects from low-level nanotube exposure could be detected from behavior or pathological examination. At 24 h after i.v. administration, significant concentrations of nanotubes were found only in the liver. These results demonstrate that debundled single-walled carbon nanotubes are high-contrast near-infrared fluorophores that can be sensitively and selectively tracked in mammalian tissues using optical methods. In addition, the absence of acute toxicity and promising circulation persistence suggest the potential of carbon nanotubes in future pharmaceutical applications.

Room temperature ozonolysis of fluorinated SWNT and phenyl-sulfonated SWNT have been studied in perfluoropolyether (PFPE) solvents. Etching at the end caps (approximately 70 nm/hour for fluorinated SWNT/PFPE suspension with 1 g/l concentration) has been demonstrated to be the dominating effect during the ozonolysis of fluorinated SWNT. Base on characterization by AFM analysis, X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy, fluorination along the SWNT sidewalls protects F-SWNT from extensive functionalization by ozonolysis. An ozone reaction with fluorinated SWNT has been found to improve its solubility in 96% sulfuric acid. This allows oxidative cutting by ammonium peroxydisulfate without defluorination. In comparison to fluorinated SWNT, phenyl-sulfonated SWNT was found to be effectively and homogeneous cut by ozonolysis in a water suspension.

Single-walled carbon nanotubes functionalized by phenyl groups can be sulfonated in oleum (H2SO4, 20% free SO3) to give materials that exhibit high solubility in water as determined by centrifugation in conjunction with UV−vis−near-infrared measurements. Cryo-transmission electron microscopy images show that extensive debundling occurs during the sulfonation step.

Directed assembly of nanoscale building blocks such as single-walled carbon nanotubes (SWNTs) into desired architectures is a major hurdle for a broad range of basic research and technological applications (e.g., electronic devices and sensors). Here we demonstrate a parallel assembly process that allows one to simultaneously position, shape, and link SWNTs with sub-100-nm resolution. Our method is based on the observation that SWNTs are strongly attracted to COOH-terminated self-assembled monolayers (COOH-SAMs) and that SWNTs with lengths greater than the dimensions of a COOH-SAM feature will align along the boundary between the COOH-SAM feature and a passivating CH 3 -terminated SAM. By using nanopatterned affinity templates of 16-mercaptohexadecanonic acid, passivated with 1-octadecanethiol, we have formed SWNT dot, ring, arc, letter, and even more sophisticated structured thin films and continuous ropes. Experiment and theory (Monte Carlo simulations) suggest that the COOH-SAMs localize the solvent carrying the nanotubes on the SAM features, and that van der Waals interactions between the tubes and the COOH-rich feature drive the assembly process. A mathematical relationship describing the geometrically weighted interactions between SWNTs and the two different SAMs required to overcome solvent–SWNT interactions and effect assembly is provided.

The synthetic conditions for the isolation of the iron-molybdenum nanocluster FeMoC [HxPMo12O40 [subset]H4Mo72Fe30(O2CMe)15O254(H2O)98], along with its application as a catalyst precursor for VLS growth of SWNTs have been studied. As-prepared FeMoC is contaminated with the Keplerate cage [H4Mo72Fe30(O2CMe)15O254(H2O)98] without the Keggin [HxPMo12O40]n- template, however, isolation of pure FeMoC may be accomplished by Soxhlet extraction with EtOH. The resulting EtOH solvate is consistent with the replacement of the water ligands coordinated to Fe being substituted by EtOH. FeMoC-EtOH has been characterized by IR, UV-vis spectroscopy, MS, XPS and 31P NMR. The solid-state 31P NMR spectrum for FeMoC-EtOH (delta-5.3 ppm) suggests little effect of the paramagnetic Fe3+ centers in the Keplerate cage on the Keggin ion's phosphorous. The high chemical shift anisotropy, and calculated T1 (35 ms) and T2 (8 ms) values are consistent with a weak magnetic interaction between the Keggin ion's phosphorus symmetrically located within the Keplerate cage. Increasing the FeCl2 concentration and decreasing the pH of the reaction mixture optimizes the yield of FeMoC. The solubility and stability of FeMoC in H2O and MeOH-H2O is investigated. The TGA of FeMoC-EtOH under air, Ar and H2 (in combination with XPS) shows that upon thermolysis the resulting Fe : Mo ratio is highly dependent on the reaction atmosphere: thermolysis in air results in significant loss of volatile molybdenum components. Pure FeMoC-EtOH is found to be essentially inactive as a pre-catalyst for the VLS growth of single-walled carbon nanotubes (SWNTs) irrespective of the substrate or reaction conditions. However, reaction of FeMoC with pyrazine (pyz) results in the formation of aggregates that are found to be active catalysts for the growth of SWNTs. Activation of FeMoC may also be accomplished by the addition of excess iron. The observation of prior work's reported growth of SWNTs from FeMoC is discussed with respect to these results.

We present the first quantitative assessment of the maximum amount of nanotubes that can exist in the isotropic phase () of single-walled carbon nanotubes (SWNTs) in Brønsted-Lowry acids. We employ a centrifugation technique in conjunction with UV-vis-nIR spectroscopy to quantify , which is also the critical concentration of the isotropic-nematic transition of SWNTs in strong acids. Centrifugation of biphasic dispersions of SWNTs, that is, acid dispersions consisting of an isotropic phase in equilibrium with an ordered nematic liquid crystalline phase, results in a clear phase separation, where the isotropic phase is supernatant. Dilution of the isotropic phase with a known amount of acid followed by UV-vis-nIR absorbance measurements yields , that is, the maximum concentration of SWNTs that can exist in the isotropic phase in a given acid for a given SWNTs' length distribution. At low SWNT concentration (below 200 ppm) in superacids, light absorbance in the range from 400 to 1400 nm scales linearly with concentration. This Beer's law behavior yields calibration curves for measuring SWNTs' concentration in acids. We find that the critical concentration of the isotropic-nematic transition increases with acid strength in accordance with the previously proposed sidewall protonation mechanism for dispersing SWNTs in acids.

A two-phase liquid-liquid extraction process is presented which is capable of extracting water-soluble single-walled carbon nanotubes into an organic phase. The extraction utilizes electrostatic interactions between a common phase transfer agent and the sidewall functional groups on the nanotubes. Large length-dependent van der Waals forces for nanotubes allow the ability to control the length of nanotubes extracted into the organic phase as demonstrated by atomic force microscopy.

Single-walled carbon nanotubes (SWNTs) uniquely combine characteristics of polymers (e.g., they are molecules composed of repeat units) as well as nanoscale colloids (e.g., they are extremely stiff); because of these characteristics, they may qualify as the ideal building blocks for the long-sought Staudinger's “continuous crystal.” To this end, neat SWNT fibers have been produced by wet-spinning concentrated dispersions of 6−10 wt % SWNTs in 102% H2SO4. A unique protocol that combined UV−ozone dry chemical etching and cryoultramicrotoming was developed to directly visualize the internal voids, alignment, and composition of these SWNT neat fibers. A substructure of large aligned SWNT ropes, 200−500 nm in diameter, was revealed throughout the fibers. This substructure may be linked to the SWNT spaghetti, threadlike liquid-crystalline domains observed in dispersions of SWNTs in H2SO4.

We review our recent optical experiments on single-walled carbon nanotubes in high magnetic fields. The data revealed magnetic-field-induced optical anisotropy as well as broadening, splittings, and shifts of interband absorption and photoluminescence peaks. Quantitative comparison with theoretical predictions based on the Aharonov–Bohm effect is presented. r 2005 Elsevier B.V. All rights reserved. PACS: 73.22.� f; 78.67.Ch; 75.75.+a

The charge transfer induced lithiation of single-wall carbon nanotubes (SWNTs) was investigated by in situ monitoring by Raman spectroscopy as lithium was added incrementally to a dispersion of SWNTs in liquid ammonia. Charge transfer from liquid ammonia solvated lithium to the SWNTs led to intercalation of lithium into the SWNT ropes, as well as to the semi-covalent lithiation of the SWNTs. Raman spectra of the SWNTs recorded as lithium was added showed a ∼30 wavenumber downshift of the G band (1594 cm −1 ) with the concomitant appearance of a new peak at 1350 cm −1 that was assigned as the signature of the lithiated SWNTs. Addition of 1-iodododecane to the lithiated SWNTs resulted in the covalent attachment of dodecyl groups. The intercalation of lithium throughout the SWNT ropes led to complete dodecylation of all individual SWNTs.

Using the High Pressure carbon monoxide (HiPco) reactor we conducted an experiment on the effects of changing the catalyst concentration. With each catalyst concentration tested the resulting raw HiPco material was characterized for average SWNT lengths, SWNT diameters, residual iron particle size, and large fullerene content. We were able to determine trends in each of these characteristics as the catalyst concentration was changed. As the catalyst concentration was decreased SWNT lengths increased, SWNT diameters increased, the residual iron particle size increased, and the large fullerene content decreased. From these trends we have developed a Competitive Growth model for nucleation and growth of SWNTs via the HiPco process.

Manipulating optical properties of single-walled nanotubes (SWNTs) is necessary for the development of nanoscale optical devices and probes for biomedical research. In life sciences it will make possible the direct observation of SWNTs inside living cells using optical microscopes. In the nanotechnology field it will enable the development of nanosensors with fluorescent reporting. However, the direct fluorescent labeling of SWNTs is obstructed by their strong light quenching qualities. Besides, chemical functionalization of SWNTs needed for the covalent attachment of fluorescent dyes could change favorable properties of nanotubes. Here we report that optical properties of SWNTs can be manipulated without their covalent modification by wrapping them with fluorescently labeled polymer poly(vinylpyrrolidone) (PVP-1300). Fluorescent PVP-1300 forms a monomolecular approximately 2.5 nm thick layer coiling around individual SWNTs and nanotube bundles. PVP casing is fluorescent although it is only several nanometers thick. This makes individual SWNTs observable by a fluorescent microscope. The spare polymer strands left over after wrapping around the relatively shorter nanotubes form junctions between SWNTs tying them together into new configurations, primarily Y- and psi-type junctions. The ability to use a single fluorescent polymer strand to fasten nanotubes together can be useful in assembly of nanotube-made devices. In PVP-covered SWNTs multiple fluorophores are attached to each single nanotube making them unique composite fluorophores attractive as parts of biological fluorescent probes and in the development of the new materials in photonics and nanotechnology.

We demonstrate the continued growth of single-walled carbon nanotubes (SWNTs) from ordered arrays of open-ended SWNTs in a way analogous to epitaxy. Nanometer-sized metal catalysts were docked to the SWNT open ends and subsequently activated to restart growth. SWNTs thus grown inherit the diameters and chirality from the seeded SWNTs, as indicated by the closely matched frequencies of Raman radial breathing modes before and after the growth.

EPR studies of matrix-isolated tar molecules have shown the presence of four different free radicals in the original gaseous tars evolved from coal over the 300–600°C temperature range. The tars are isolated in a carbon dioxide matrix at 77 K. EPR spectra suggest strong similarities to peroxy-type or oxygen-centered radicals for three of the radicals with characteristic g values of g ‖ = 2.0375, 2.0318, and 2.0257, and g ⊥ = 2.0025. The fourth radical, which does not exhibit the large anisotropy of the other three, is tentatively assigned to a carbon-centered radical. Formation of these free radicals is quenched in the presence of coal char and remains unaffected in the presence of metal oxides such as CaO and SiO 2 . The free radical species react as the coal tar is warmed to room temperature.

The effects of applied hydrostatic pressure on the optical transitions in semiconducting single-walled carbon nanotubes with different diameters and chiralities have been studied using optical absorption and photoluminescence spectroscopy. The excitonic transitions associated with the band-gap (the first van Hove transition) energies in the carbon nanotubes are found to shift to lower energy at a rate depending on nanotube structure. The excitonic transitions between the first excited confinement states (the second van Hove transitions) are found to be much less sensitive to the applied hydrostatic pressure. All nanotubes show a dependence on their chirality in terms of pressure coefficient of the band-gap energy, with the larger-diameter nanotubes exhibiting a higher sensitivity of the band-gap energy to hydrostatic pressure.

Well-aligned macroscopic fibers composed solely of single-walled carbon nanotubes (SWNTs) were produced by conventional spinning. Fuming sulfuric acid charges SWNTs and promotes their ordering into an aligned phase of individual mobile SWNTs surrounded by acid anions. This ordered dispersion was extruded via solution spinning into continuous lengths of macroscopic neat SWNT fibers. Such fibers possess interesting structural composition and physical properties.

Strong tube−tube van der Waal attractions that hinder the dissolution of single walled carbon nanotubes (SWNTs) as individuals have been overcome by the direct protonation of the tubes by superacids. The pristine nanotubes disperse as individuals in 100% H2SO4, oleum, trifluromethanesulfonic acid, and chlorosulfonic acid to varying solubility levels. Optically homogeneous solutions with concentration as high as 45 g/L (2.5 wt %) at room temperature have been observed in the case of chlorosulfonic acid, the strongest among the series of superacids investigated. A dissolution model is proposed wherein the solubilized tubes exist as protonated polycarbocations, charge balanced by corresponding conjugate base anions. The removal of electrons from the SWNT, leading to a fractional positive charge on the carbons in the protonated state, is reversible upon deprotonation. With increasing concentration of the solubilized nanotubes, anion-mediated attractions at lower concentrations and spatial constraints at high ...

The growth mechanism of long and aligned single walled carbon nanotubes using a recently reported “fast heating” chemical vapor deposition (CVD) method is discussed. The effect of heating speed at the initial stage of the CVD process has been systematically studied, and a “kite-mechanism” for the nanotube growth is proposed. The understanding of the growth mechanism would enable us to design future experiments to obtain better control of the morphology of the produced nanotubes.

Ultrafast carrier dynamics in individual semiconducting single-walled carbon nanotubes was studied by femtosecond transient absorption and fluorescence measurements. After photoexcitation of the second van Hove singularity of a specific tube structure, the relaxation of electrons and holes to the fundamental band edge occurs to within 100 fs. The fluorescence decay from this band is dependent on the excitation density and can be rationalized by exciton annihilation theory. In contrast to fluorescence, the transient absorption has a distinctly different time and intensity dependence for different tube structures, suggesting a branching to emissive and trap states following photoexcitation.

Fibers of single wall carbon nanotubes extruded from super-acid suspensions exhibit preferred orientation along their axes. We characterize the alignment by x-ray fiber diagrams and polarized Raman scattering, using a model which allows for a completely unaligned fraction. This fraction ranges from 0.17 to 0.05±0.02 for three fibers extruded under different conditions, with corresponding Gaussian full widths at half maximum (FWHM) from 64° to 44°±2°. FWHM, aligned fraction, electrical, and thermal transport all improve with decreasing extrusion orifice diameter. Resistivity, thermoelectric power, and resonant-enhanced Raman scattering indicate that the neat fibers are strongly p doped; the lowest observed ρ is 0.25 mΩ cm at 300 K. High temperature annealing increases ρ by more than 1 order of magnitude and restores the Raman resonance associated with low-energy van Hove transitions, without affecting the nanotube alignment.

Single-walled carbon nanotubes (SWNTs) can be dispersed at high concentration in superacids; the protonation of SWNTs sidewalls eliminates wall-wall van der Waals interactions and promotes the dispersion process. At very low concentration, SWNTs in superacids dissolve as individual tubes which behave as Brownian rods. At higher concentration, SWNTs form a highly unusual nematic phase consisting of spaghetti-like self-assembled supermolecular strands of mobile, solvated tubes in equilibrium with a dilute isotropic phase. At even higher concentration, the spaghetti strands self-assemble into a polydomain nematic liquid crystal. Upon the introduction of small amounts of water, the liquid crystal phase separates into needle-shaped strands (20 Im long) of highly aligned SWNTs, termed alewives. Under anhydrous condition, the liquid crystalline phase can be processed into highly aligned fibers of pure SWNT without the aid of any surfactants or polymers.

Individual single-walled carbon nanotubes (SWNTs) have been suspended in aqueous media using various anionic, cationic, nonionic surfactants and polymers. The surfactants are compared with respect to their ability to suspend individual SWNTs and the quality of the absorption and fluorescence spectra. For the ionic surfactants, sodium dodecylbenzene sulfonate (SDBS) gives the most well resolved spectral features. For the nonionic systems, surfactants with higher molecular weight suspend more SWNT material and have more pronounced spectral features.

We have carried out magneto-absorption and magneto-photoluminescence experiments on micelle-suspended single-walled carbon nanotubes in magnetic fields up to 45 T. Chirality-assigned spectral peaks exhibit significant changes with increasing magnetic field, which can be quantitatively explained in terms of the theoretically predicted splittings and redshifts of the band edge due to the Aharonov–Bohm effect combined with the magnetic-field-induced alignment of the nanotubes.

Poly(vinyl alcohol) (PVA) composite films using poly(vinyl pyrrolidone) (PVP) and sodium dodecyl sulfate (SDS)-covered, well dispersed single wall carbon nanotubes (SWNT) exhibit significant improvement in tensile strength and modulus as compared to the control PVA and PVA/ PVP/SDS films. The evidence of load transfer to the nanotubes in the composite film has been obtained from the shift in the Raman SWNT D* band peak position.

Raman spectroscopy performed between 565 and 627 nm and also between 458- and 514.5-nm laser excitation was used to map the lowest-energy van Hove singularities of metallic single-walled carbon nanotubes suspended in aqueous solution using sodium dodecyl sulfate. The interband transitions of distinct metallic nanotubes were observed directly and assigned using a correlation of the diameter and radial breathing mode (RBM) in the Raman spectrum. The results were extrapolated to all metallic nanotubes using a generalized scaling derived from the tight-binding formalism and were shown to be valid for describing the electronic structure of semiconducting nanotubes as well. The model results are compared using excitation profiles outside of the above-reported scan ranges with excellent agreement between observed and predicted profile widths and transition energies.

In acidic solution between pH 6 and 2.5, protons react reversibly and selectively in the presence of preadsorbed oxygen at the sidewall of aqueous dispersed single-walled carbon nanotubes suspended in sodium dodecyl sulfate. This reactive complex, which protonates the nanotube sidewall, reversibly diminishes absorption intensity, fluorescent emission, and resonant Raman scattering intensity. The results document the first evidence of electronic selectivity with metallic nanotubes reacting initially near neutral pH, followed by successive protonation of nanotubes with increasing band gap as the solution is increasingly acidified. Preadsorption of molecular oxygen is shown to play a critical role in the interaction, and its desorption kinetics is followed using UV irradiation. The role of the charged electric double layer of the surfactant is discussed. This chemistry, which proceeds under relatively mild conditions, holds promise for separating nanotubes by metal and semiconducting types.

Capillary electrophoresis (CE) has been performed on polymer-stabilized bundles and sodium dodecyl sulfate (SDS) suspensions of high-pressure carbon monoxide (HiPco)-produced single-walled carbon nanotubes. Real-time Raman spectroscopy has been used for detection and characterization of the separation process. Radial-breathing-mode vibrational frequencies are sensitive to nanotube diameter. Monitoring of these modes demonstrates the separation of poly(vinylpyrrolidone) (PVP)-stabilized tubes into fractions of differing bundle composition. Separations on SDS suspensions indicate that CE is capable of separating bundled nanotubes from isolated individuals on the basis of differences in nanotube mobility, depending on changes in diameter or bundle size.

Crystallization behavior of melt-blended polypropylene (PP)/single wall carbon nanotube (SWNT) composites has been studied using optical microscopy and differential scanning calorimetry. Polypropylene containing 0.8 wt% SWNT exhibits faster crystallization rate as compared to pure polypropylene. PP/SWNT fibers have been spun using typical polypropylene melt spinning conditions. The PP crystallite orientation and the SWNT alignment in the fibers have been studied using X-ray diffraction and polarized Raman spectroscopy, respectively.

Thick macroscopic membranes of magnetically aligned single-wall carbon nanotubes (SWNT) have been produced via high pressure filtration of aqueous surfactant-suspended SWNT in a magnetic field, resulting in membrane thicknesses of 10 μm and surface areas of 125 cm2. Field strengths of 7 and 25 T were used. Polarized Raman spectroscopy shows an anisotropy of (2.5±0.5), indicating good alignment. A similar degree of alignment was seen at both intensities of magnetic field. Furthermore, the degree of alignment is comparable to that achieved in previous work that produced smaller and thinner membranes at 25 T. The membranes also exhibit uniform anisotropy across their surface and throughout their thickness.

Thick films of single wall carbon nanotubes (SWNT) exhibiting in-plane preferred orientation have been produced by filter deposition from suspension in strong magnetic fields. We characterize the field-induced alignment with x-ray fiber diagrams and polarized Raman scattering, using a model which includes a completely unaligned fraction. We correlate the texture parameters with resistivity and thermal conductivity measured parallel and perpendicular to the alignment direction. Results obtained with 7 and 26 T fields are compared. We find no significant field dependence of the distribution width, while the aligned fraction is slightly greater at the higher field. Anisotropy in both transport properties is modest, with ratios in the range 5–9, consistent with the measured texture parameters assuming a simple model of rigid rod conductors. We suggest that further enhancements in anisotropic properties will require optimizing the filter deposition process rather than larger magnetic fields. We show that both ...

The chemical stability of fluoronanotubes in selected solid inorganic matrixes has been studied by initially mixing and mechanically grinding the components and subsequently heating them at temperatures ranging from 35 to 600 degrees C. The inorganic compounds selected for matrixes included halides (KBr, KI, Lil, LiBr, LiCl, NaCl, Znl2), oxides (Li2O, Fe2O3, PbO, MnO), lithium peroxide (Li2O2), potassium superoxide (KO2), sulfides (Li2S and ZnS), zinc selenide (ZnSe), lithium nitride (Li3N), and aluminum phosphide (AIP). Solid products, resulting from the proceeding chemical reactions, were analyzed by X-ray diffraction, Raman spectroscopy, and SEM/EDX elemental analysis. Gaseous and volatile products were identified with the help of the TGA/MS technique. Experimental data presented in this paper provide clear evidence that fluoronanotubes are not chemically inert toward the solid matrixes studied and exhibit significant oxidative properties in the redox reactions occurring under various temperatures, depending on the nature of the inorganic compound.

Iron-catalyzed, gas-phase disproportionation of carbon monoxide under high pressures is known to produce single-walled carbon nanotubes (SWNT) in high yields. Small amounts of nontubular nanocarbons and iron encapsulated-graphitic shelled nanoparticles are produced concomitantly. Differences in the oxidation kinetics among the SWNT, nontubular carbon, and iron core−graphitic shell nanoparticles have been exploited as a tool for the quantitative determination of high-molecular-weight nontubular, carbon products. The nontubular carbon materials were eliminated by selective oxidation wherein the raw material was subjected to increasing oxidation thresholds followed by acid leaching in an aqueous or gas−solid reaction. Relative concentrations of nontubular nanocarbons in differentially oxidized samples were determined employing laser desorption ionization-mass spectrometry (LDI-MS) with C60 and bismuth triphenyl as internal markers. The identity of the nontubular carbon was examined by nondestructive extracti...

Spectrofluorimetric measurements on single-walled carbon nanotubes (SWNTs) isolated in aqueous surfactant suspensions have revealed distinct electronic absorption and emission transitions for more than 30 different semiconducting nanotube species. By combining these fluorimetric results with resonance Raman data, each optical transition has been mapped to a specific ( n , m ) nanotube structure. Optical spectroscopy can thereby be used to rapidly determine the detailed composition of bulk SWNT samples, providing distributions in both tube diameter and chiral angle. The measured transition frequencies differ substantially from simple theoretical predictions. These deviations may reflect combinations of trigonal warping and excitonic effects.

An optically homogeneous solution/dispersion of single-wall carbon nanotubes (SWNTs) in oleum has been used to form isotropic films exhibiting fibrillar morphology. Tensile modulus, strength, and strain to failure of the film are 8 GPa, 30 MPa, and 0.5%, respectively. The electrical conductivity in the plane of the film is 1 × 105 S/m.

Poly(p-phenylene benzobisoxazole) (PBO) has been synthesized in the presence of single-wall carbon nanotubes (SWNTs) in poly(phosphoric acid) (PPA) using typical PBO polymerization conditions. PBO and PBO/SWNT lyotropic liquid crystalline solutions in PPA have been spun into fibers using dry-jet wet spinning. The tensile strength of the PBO/SWNT fiber containing 10 wt % SWNTs is about 50% higher than that of the control PBO fibers containing no SWNTs. The structure and morphology of these fibers have been studied.

The fluorination of purified HiPco single-wall carbon nanotubes to a stoichiometry CFx (x ⩽ 0.2) followed by pyrolysis of the partially fluorinated nanotubes up to 1000 °C was found to have “cut” the nanotubes to a range of short lengths (average

Molecular dynamics simulations were performed, in the physiological condition (300 K and 1 atm), on nanotube segments of various diameters submerged in water. The results show that water molecules can exist inside the nanotube segments, and, most importantly, the water molecules inside the tubes tend to organize themselves into a highly hydrogen-bonded network, i.e., solid-like wrapped-around ice sheets. The disorder-to-order transition of these ice-sheets can be achieved purely by tuning the size of the tubes. The results also suggest that the nanotubes have the potential to be used as proton-conducting pores for a variety of biological applications.