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At least 361 records · Page 20

Toxicity of Carbon Nanotubes and Its Implications for Occupational and Environmental Health

Carbon nanotubes (CNTs), which possess desirable electrical and mechanical properties, potentially have wide industrial applications. CNTs exist in two forms, single-wall (SW) and multi-wall (MW). There has been great concern that if CNTs enter the work environment as suspended respirable particulate matter (PM), they could pose an inhalation hazard. The results of recent rodent studies have collectively shown that CNTs can produce inflammation, epithelioid granulomas, fibrosis, and biochemical changes in the lungs. Studies in mice given equal amounts of test dusts showed that CNTs were more toxic than quartz and produced lesions that became progressively more pronounced. These results have led us to recommend that respirable CNT dust be considered a serious occupational health hazard, and that exposure limits be established in the expectation of expanded industrial applications. CNTs, which are totally insoluble and fibrous, would be expected to be more biopersistent than mineral fibers. Biopersistence is the key factor determining the long-term toxicity of mineral fibers and certainly of CNTs too. We have postulated that the electrical and fibrous properties of CNTs also play important roles in the toxicity of CNTs in the lungs. Recently, MWCNTs have been found in ultrafine PM aggregates in combustion streams of methane, propane, and natural-gas flames of typical stoves; indoor and outdoor fine (< 2.5 micron) PM samples were reported to contain significant fractions of MWCNTs. Environmental fine PM is mainly formed from combustion of fuels, and fine PM has been reported to be a major contributor to the induction of cardiopulmonary diseases by pollutants. Given that manufactured SWCNTs and/or MWCNTs have elicited pathological changes in the lungs and heart, we have postulated that exposure to combustion-generated MWCNTs in fine PM in the air may play a significant role in air pollution-related cardiopulmonary diseases. Therefore, CNTs from manufacturing and combustion sources in the environment could have adverse effects on human health.

Lam, Chiu-wing↗

Functionalization of carbon nanotubes

Method and system for functionalizing a collection of carbon nanotubes (CNTs). A selected precursor gas (e.g., H.sub.2 or F.sub.2 or C.sub.nH.sub.m) is irradiated to provide a cold plasma of selected target particles, such as atomic H or F, in a first chamber. The target particles are directed toward an array of CNTs located in a second chamber while suppressing transport of ultraviolet radiation to the second chamber. A CNT array is functionalized with the target particles, at or below room temperature, to a point of saturation, in an exposure time interval no longer than about 30 sec.

Khare, Bishun N.↗

Functionalization of Carbon Nanotubes

Method and system for functionalizing a collection of carbon nanotubes (CNTs). A selected precursor gas (e.g., H2, or F2, or CnHm) is irradiated to provide a cold plasma of selected target particles, such as atomic H or F, in a first chamber. The target particles are directed toward an array of CNTs located in a second chamber while suppressing transport of ultraviolet radiation to the second chamber. A CNT array is functionalized with the target particles, at or below room temperature, to a point of saturation, in an exposure time interval no longer than about 30 sec.

Khare, Bishun N.↗

Elastomer Reinforced with Carbon Nanotubes

Elastomers are reinforced with functionalized, single-walled carbon nanotubes (SWNTs) giving them high-breaking strain levels and low densities. Cross-linked elastomers are prepared using amine-terminated, poly(dimethylsiloxane) (PDMS), with an average molecular weight of 5,000 daltons, and a functionalized SWNT. Cross-link densities, estimated on the basis of swelling data in toluene (a dispersing solvent) indicated that the polymer underwent cross-linking at the ends of the chains. This thermally initiated cross-linking was found to occur only in the presence of the aryl alcohol functionalized SWNTs. The cross-link could have been via a hydrogen-bonding mechanism between the amine and the free hydroxyl group, or via attack of the amine on the ester linage to form an amide. Tensile properties examined at room temperature indicate a three-fold increase in the tensile modulus of the elastomer, with rupture and failure of the elastomer occurring at a strain of 6.5.

Hudson, Jared L.↗

Functionalization of Carbon Nanotubes

Method and system for functionalizing a collection of carbon nanotubes (CNTs). A selected precursor gas (e.g., H2 or F2 or CnHm) is irradiated to provide a cold plasma of selected target species particles, such as atomic H or F, in a first chamber. The target species particles are d irected toward an array of CNTs located in a second chamber while suppressing transport of ultraviolet radiation to the second chamber. A CNT array is functionalized with the target species particles, at or below room temperature, to a point of saturation, in an exposure time interval no longer than about 30 sec. *Discrimination against non-target species is provided by (i) use of a target species having a lifetime that is much greater than a lifetime of a non-target species and/or (2) use of an applied magnetic field to discriminate between charged particle trajectories for target species and for non-target species.

Khare, Bishun N.↗

PECVD Growth of Carbon Nanotubes

Plasma enhanced chemical vapor deposition (PECVD), using inductively coupled plasma, has been used to grow carbon nanotubes (CNTs) and graphitic carbon fibers (GCF) on substrates sputtered with aluminum and iron catalyst. The capacitive plasma's power has been shown to cause a transition from nanotubes to nanofibers, depending on the strength of the plasma. The temperature, placement, and other factors have been shown to affect the height and density of the tube and fiber growth.

McAninch, Ian↗

Customization for Current Market Applications of the Carbon Nanotubes Produced by PNNL’s Regenerable Catalytic Pyrolysis (ReCaP) for Scaled Hydrogen Production

Here, we demonstrated the Regenerative Catalytic Pyrolysis (ReCaP) process that generates carbon dioxide-free hydrogen (CO 2 -free H 2 ) from inexpensive and domestically abundant natural gas (NG), while simultaneously producing H 2 at net production cost of $1.0/kg through the sale of valuable carbon nanotube (CNT) co-product. The specific goal of this project is to 1) scale up the production of CNT, 2) correlate the properties of the CNT with the reaction conditions, 3) perform a techno-economic analysis to obtain minimum selling price of H 2 and CNT, and 4) identify industrial partners interested in the CNT co-product.

03 NATURAL GAS↗

Carbon Nanotubes for Space Applications

The potential of nanotube technology for NASA missions is significant and is properly recognized by NASA management. Ames has done much pioneering research in the last five years on carbon nanotube growth, characterization, atomic force microscopy, sensor development and computational nanotechnology. NASA Johnson Space Center has focused on laser ablation production of nanotubes and composites development. These in-house efforts, along with strategic collaboration with academia and industry, are geared towards meeting the agency's mission requirements. This viewgraph presentation (including an explanation for each slide) outlines the research focus for Ames nanotechnology, including details on carbon nanotubes' properties, applications, and synthesis.

Meyya Meyyappan↗

Superior photodynamic effect of single-walled carbon nanotubes in aprotic media: a kinetic study

It has been confirmed that single-walled carbon nanotubes (SWCNTs) could generate reactive oxygen species in aprotic media by utilizing photon energy. However, the impact of photon irradiation on SWCNTs and the kinetics of the generation process in aprotic media are still unclear, which significantly limits the yield performance. In this work, the kinetics for photodynamic effects has been investigated by performing characterizations on ultraviolet-treated SWCNTs using Raman spectroscopy, conductive atomic force microscope (in-situ), kelvin probe force microscope, and X-ray photoelectron spectroscopy. It is found that ultraviolet-treated SWCNTs are observed to have more defects, lower conductivity, and less surface charge after energy conversion. Starting from the fundamental intrinsic properties of SWCNTs, the kinetics and formation of these changes are thoroughly discussed. It turns out that the dispersion, chirality, and structural integrity of SWCNTs are important for achieving high-performance photodynamic effects, which are validated using several different SWCNTs as well as other carbon nanomaterials. A type of (6,5) s-SWCNTs exhibited the highest energy efficiency among a variety of other carbon nanomaterials. The yield rate is 2.15 mM/h, and the energy consumption is determined to be 2.79 W∙h/mM. This work is expected to help dramatically boost the energy efficiency of the photodynamic effect in aprotic media and pave the way for designing high-performance carbon nanomaterial-based photoinduced devices.

36 MATERIALS SCIENCE↗

Computational Nanomechanics of Carbon Nanotubes and Composites

Nanomechanics of individual carbon and boron-nitride nanotubes and their application as reinforcing fibers in polymer composites has been reviewed with interplay of theoretical modeling, computer simulations and experimental observations. The emphasis in this work is on elucidating the multi-length scales of the problems involved, and of different simulation techniques that are needed to address specific characteristics of individual nanotubes and nanotube polymer-matrix interfaces. Classical molecular dynamics simulations are shown to be sufficient to describe the generic behavior such as strength and stiffness modulus but are inadequate to describe elastic limit and nature of plastic buckling at large strength. Quantum molecular dynamics simulations are shown to bring out explicit atomic nature dependent behavior of these nanoscale materials objects that are not accessible either via continuum mechanics based descriptions or through classical molecular dynamics based simulations. As examples, we discus local plastic collapse of carbon nanotubes under axial compression and anisotropic plastic buckling of boron-nitride nanotubes. Dependence of the yield strain on the strain rate is addressed through temperature dependent simulations, a transition-state-theory based model of the strain as a function of strain rate and simulation temperature is presented, and in all cases extensive comparisons are made with experimental observations. Mechanical properties of nanotube-polymer composite materials are simulated with diverse nanotube-polymer interface structures (with van der Waals interaction). The atomistic mechanisms of the interface toughening for optimal load transfer through recycling, high-thermal expansion and diffusion coefficient composite formation above glass transition temperature, and enhancement of Young's modulus on addition of nanotubes to polymer are discussed and compared with experimental observations.

Srivastava, Deepak↗

Amplitude-mode spectroscopy of chemically injected and photogenerated charge carriers in semiconducting single-walled carbon nanotubes

In one-dimensional semiconductors such as conjugated polymers and semiconducting single-walled carbon nanotubes (s-SWCNTs), injected charge carriers (electrons or holes) can have profound impacts on both electronic conductivity and optical spectra, even at low carrier densities. Understanding charge-related spectral features is a key fundamental challenge with important technological implications. Here, we employ a systematic suite of experimental and theoretical tools to understand the mid-infrared charge signatures of heavily p-type doped polymer-wrapped s-SWCNTs. Across a broad range of nanotube diameters, we find that hole charge carriers induce strong Fano anti-resonances in mid-infrared transmission spectra that correspond to defect-related (D-band) and in-plane tangential (G-band) Raman-active vibrational modes, along with anti-resonances arising from infrared (IR)-active polymer and SWCNT modes. We employ 13C isotope-labeled s-SWCNTs and a removable wrapping polymer to clarify the relative intensities, energies, and sources of all observed anti-resonances. Simulations performed with the "amplitude mode model" are used to quantitatively reproduce Raman spectra and also help to explain the outsized intensity of the D-band anti-resonance, relative to the G-band, observed for both moderately and degenerately doped s-SWCNTs. Here, the results provide a framework for future studies of ground- and excited-state charge carriers in s-SWCNTs and a variety of low-dimensional materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Design and Characterization of Carbon Nanotube Nanocomposites

Revolutionary design concepts in future aerospace vehicles will depend on extraordinary material properties to permit significant reduction of mass and size of components, while imparting intelligence. Due to their combination of remarkable electrical and mechanical properties, carbon nanotubes (CNT) are expected to enable this paradigm shift in design concepts. However, significant challenges still exist in translating these CNT properties into the macrostructures required for future generations of aerospace vehicles. While an accepted route for making the leap from nanostructures to useful macrostructures has not been fully charted, this paper will give an overview of the approach taken by some researchers at NASA Langley Research Center to sort out issues involved in the development of CNT nanocomposites for multifunctional structures. Specifically, the dispersion of carbon nanotubes in polymer matrices, characterization of nanocomposites, the role of quantum computation in providing guidance for processing and the use of computational analysis in data interpretation will be covered. Significant improvements in mechanical and electrical properties of CNT nanocomposites with very low loadings of CNTs are described and lend credence to the potential for using CNTs in achieving technological leaps in composite development.

Siochi, Emilie J.↗

Ultrasensitive Label-free Electronic Chip for DNA Analysis Using Carbon Nanotube Nanoelectrode Arrays

There is a strong need for faster, cheaper, and simpler methods for nucleic acid analysis in today s clinical tests. Nanotechnologies can potentially provide solutions to these requirements by integrating nanomaterials with biofunctionalities. Dramatic improvement in the sensitivity and multiplexing can be achieved through the high-degree miniaturization. Here, we present our study in the development of an ultrasensitive label-free electronic chip for DNA/RNA analysis based on carbon nanotube nanoelectrode arrays. A reliable nanoelectrode array based on vertically aligned multi-walled carbon nanotubes (MWNTs) embedded in a SiO2 matrix is fabricated using a bottom-up approach. Characteristic nanoelectrode behavior is observed with a low-density MWNT nanoelectrode array in measuring both the bulk and surface immobilized redox species. The open-end of MWNTs are found to present similar properties as graphite edge-plane electrodes, with a wide potential window, flexible chemical functionalities, and good biocompatibility. A BRCA1 related oligonucleotide probe with 18 bases is covalently functionalized at the open ends of the MWNTs and specifically hybridized with an oligonucleotide target as well as a PCR amplicon. The guanine bases in the target molecules are employed as the signal moieties for the electrochemical measurements. Ru(bpy)3(2+) mediator is used to further amplify the guanine oxidation signal. This technique has been employed for direct electrochemical detection of label-free PCR amplicon through specific hybridization with the BRCAl probe. The detection limit is estimated to be less than approximately 1000 DNA molecules, approaching the limit of the sensitivity by laser-based fluorescence techniques in DNA microarray. This system provides a general electronic platform for rapid molecular diagnostics in applications requiring ultrahigh sensitivity, high-degree of miniaturization, simple sample preparation, and low- cost operation.

Li, Jun↗

Development of Metal-impregnated Single Walled Carbon Nanotubes for Toxic Gas Contaminant Control in Advanced Life Support Systems

The success of physico-chemical waste processing and resource recovery technologies for life support application depends partly on the ability of gas clean-up systems to efficiently remove trace contaminants generated during the process with minimal use of expendables. Highly purified metal-impregnated carbon nanotubes promise superior performance over conventional approaches to gas clean-up due to their ability to direct the selective uptake gaseous species based both on the nanotube s controlled pore size, high surface area, and ordered chemical structure that allows functionalization and on the nanotube s effectiveness as a catalyst support material for toxic contaminants removal. We present results on the purification of single walled carbon nanotubes (SWCNT) and efforts at metal impregnation of the SWCNT's.

Cinke, Martin↗

Tribological studies of a novel high-performance aromatic thermosetting copolyester containing carbon nanotubes for artificial hip joints

A high-performance aromatic thermosetting copolyester containing multi-walled carbon nanotubes (ATSP-MWNTs) was synthesized, characterized, and tribologically tested against cobalt-chromium-molybdenum (CoCrMo) alloy) as a potential replacement for ultra-high molecular weight polyethylene (UHMWPE) in artificial joints. By investigating the tribological properties of ATSP-MWNTs, crosslinked UHMWPE vs CoCrMo alloy, it was found that ATSP-MWNTs exhibited a lower and more stable friction coefficient and negligible wear. Further, unlike the case of ATSP-MWNTs, an obvious wear was present for UHMWPE. It is believed that transfer films in ATSP-MWNTs help to stabilize and decrease friction and wear. In addition, large and aggregated particles of UHMWPE seem to contribute to an increase in friction and wear.

60 APPLIED LIFE SCIENCES↗

Study of carbon nanotube embedded honey as a resistive switching material

In this paper, natural organic honey embedded with carbon nanotubes (CNTs) was studied as a resistive switching material for biodegradable nonvolatile memory in emerging neuromorphic systems. CNTs were dispersed in a honey-water solution with the concentration of 0.2 wt% CNT and 30 wt% honey. The final honey-CNT-water mixture was spin-coated and dried into a thin film sandwiched in between Cu bottom electrode and Al top electrode to form a honey-CNT based resistive switching memory (RSM). Surface morphology, electrical characteristics and current conduction mechanism were investigated. The results show that although CNTs formed agglomerations in the dried honey-CNT film, both switching speed and the stability in SET and RESET process of honey-CNT RSM were improved. The mechanism of current conduction in CNT is governed by Ohm’s law in low-resistance state and the low-voltage range in high-resistance state, but transits to the space charge limited conduction at high voltages approaching the SET voltage.

36 MATERIALS SCIENCE↗

Strain Dependence of Photoluminescense of Individual Carbon Nanotubes

We have investigated strain dependence of photoluminescense (PL) spectra of single wall carbon nanotubes (SWNT). Nanotubes were sparsely dispersed in a thin PMMA film applied to acrylic bar, and strained in both compression and extension by bending this bar in either direction in a homebuilt four-point bending rig. The average surface strain was measured with high accuracy by a resistive strain gage applied on top of the film. The near infrared imaging and spectroscopy were performed on the inverted microscope equipped with high numerical aperture reflective objective lens and InGaAs CCD cameras. PL was excited with a diode laser at either 658, 730 or 785 nm, linearly polarized in the direction of the strain. We were able to measure (n,m) types and orientation of individual nanotubes with respect to strain direction and strain dependence of their PL maxima. It was found that PL peak shifts with respect to the values measured in SDS micelles are a sum of three components. First, a small environmental shift due to difference in the dielectric constant of the surrounding media, that is constant and independent of the nanotube type. Second, shift due to isotropic compression of the film during drying. Third, shifts produced by the uniaxial loading of the film in the experiment. Second and third shifts follow expression based on the first-order expansion of the TB hamiltonian. Their magnitude is proportional to the nanotube chiral angle and strain, and direction is determined by the nanotube quantum number. PL strain dependence measured for a number of various nanotube types allows to estimate TB carbon-carbon transfer integral.

Nikolaev, Pavel N.↗

Interplay between Electrostatic Properties of Molecular Adducts and Their Positions at Carbon Nanotubes

Formation of the sp 3 -defect due to covalent functionalization of a single-walled carbon nanotube (SWCNT) results in a new red-shifted emissive excitons. Here, using density functional theory, we study the impact of the intrinsic molecular dipole moments and the local charges induced by various molecular adducts on the energy and localization properties of the optically active defect-based exciton in a (10,5) SWCNT. The interplay of two effects plays a role in the localization of the exciton and, therefore, its red shift, but at different scales: The source of the leading order contribution is the defect conformation, resulting in the red shift of the defect-associated exciton with respect to the E 11 band of the pristine SWCNT on the order of ~100 meV, while the individual dipoles and polarization properties of molecular adducts lead to significantly smaller red shifts on the order of ~10 meV. While the species-dependent trends in defect-induced charges do not directly correlate to the exciton red shift, the charge at the sp 3 -defect exhibits a distinct behavior between ortho- and para-defect configurations and is relevant to the chemical reactivity of the defect position depending on the adduct type. Overall, our computational results may be helpful for diverse synthetic strategies to fine-tune emission of SWCNTs toward desired applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗