Single-walled carbon nanotubes (SWCNT) are new materials of emerging technological importance. As SWCNT are introduced into the life cycle of commercial products, their effects on human health and ...

Unusual inflammatory and fibrogenic pulmonary responses to single-walled carbon nanotubes in mice

Nanotechnology has emerged at the forefront of science research and technology development. Carbon nanotubes (CNTs) are major building blocks of this new technology. They possess unique electrical, mechanical, and thermal properties, with potential wide applications in the electronics, computer, aerospace, and other industries. CNTs exist in two forms, single-wall (SWCNTs) and multi-wall (MWCNTs). They are manufactured predominately by electrical arc discharge, laser ablation and chemical vapor deposition processes; these processes involve thermally stripping carbon atoms off from carbon-bearing compounds. SWCNT formation requires catalytic metals. There has been a great concern that if CNTs, which are very light, enter the working environment as suspended particulate matter (PM) of respirable sizes, they could pose an occupational inhalation exposure hazard. Very recently, MWCNTs and other carbonaceous nanoparticles in fine (<2.5 microm) PM aggregates have been found in combustion streams of methane, propane, and natural-gas flames of typical stoves; indoor and outdoor fine PM samples were reported to contain significant fractions of MWCNTs. Here we review several rodent studies in which test dusts were administered intratracheally or intrapharyngeally to assess the pulmonary toxicity of manufactured CNTs, and a few in vitro studies to assess biomarkers of toxicity released in CNT-treated skin cell cultures. The results of the rodent studies collectively showed that regardless of the process by which CNTs were synthesized and the types and amounts of metals they contained, CNTs were capable of producing inflammation, epithelioid granulomas (microscopic nodules), fibrosis, and biochemical/toxicological changes in the lungs. Comparative toxicity studies in which mice were given equal weights of test materials showed that SWCNTs were more toxic than quartz, which is considered a serious occupational health hazard if it is chronically inhaled; ultrafine carbon black was shown to produce minimal lung responses. The differences in opinions of the investigators about the potential hazards of exposures to CNTs are discussed here. Presented here are also the possible mechanisms of CNT pathogenesis in the lung and the impact of residual metals and other impurities on the toxicological manifestations. The toxicological hazard assessment of potential human exposures to airborne CNTs and occupational exposure limits for these novel compounds are discussed in detail. Environmental fine PM is known to form mainly from combustion of fuels, and has been reported to be a major contributor to the induction of cardiopulmonary diseases by pollutants. Given that manufactured SWCNTs and MWCNTs were found to elicit pathological changes in the lungs, and SWCNTs (administered to the lungs of mice) were further shown to produce respiratory function impairments, retard bacterial clearance after bacterial inoculation, damage the mitochondrial DNA in aorta, increase the percent of aortic plaque, and induce atherosclerotic lesions in the brachiocephalic artery of the heart, it is speculated that exposure to combustion-generated MWCNTs in fine PM may play a significant role in air pollution-related cardiopulmonary diseases. Therefore, CNTs from manufactured and combustion sources in the environment could have adverse effects on human health.

/pdf/a-review-of-carbon-nanotube-toxicity-and-assessment-of-4n93flpb4n.pdf

A Review of Carbon Nanotube Toxicity and Assessment of Potential Occupational and Environmental Health Risks

We show that the Raman scattering technique can give complete structural information for one-dimensional systems, such as carbon nanotubes. Resonant confocal micro-Raman spectroscopy of an (n,m) individual single-wall nanotube makes it possible to assign its chirality uniquely by measuring one radial breathing mode frequency omega(RBM) and using the theory of resonant transitions. A unique chirality assignment can be made for both metallic and semiconducting nanotubes of diameter d(t), using the parameters gamma(0) = 2.9 eV and omega(RBM) = 248/d(t). For example, the strong RBM intensity observed at 156 cm(-1) for 785 nm laser excitation is assigned to the (13,10) metallic chiral nanotube on a Si/SiO2 surface.

Structural (n,m) determination of isolated single wall carbon nanotubes by resonant Raman scattering

The extensive development of electronic systems and telecommunications has lead to major concerns regarding electromagnetic pollution. Motivated by environmental questions and by a wide variety of applications, the quest for materials with high efficiency to mitigate electromagnetic interferences (EMI) pollution has become a mainstream field of research. This paper reviews the state-of-the-art research in the design and characterization of polymer/carbon based composites as EMI shielding materials. After a brief introduction, in Section 1, the electromagnetic theory will be briefly discussed in Section 2 setting the foundations of the strategies to be employed to design efficient EMI shielding materials. These materials will be classified in the next section by the type of carbon fillers, involving carbon black, carbon fiber, carbon nanotubes and graphene. The importance of the dispersion method into the polymer matrix (melt-blending, solution processing, etc.) on the final material properties will be discussed. The combination of carbon fillers with other constituents such as metallic nanoparticles or conductive polymers will be the topic of Section 4. The final section will address advanced complex architectures that are currently studied to improve the performances of EMI materials and, in some cases, to impart additional properties such as thermal management and mechanical resistance. In all these studies, we will discuss the efficiency of the composites/devices to absorb and/or reflect the EMI radiation.

Polymer/carbon based composites as electromagnetic interference (EMI) shielding materials

Atmospheric pressure air plasmas are often thought to be in local thermodynamic equilibrium owing to fast interspecies collisional exchange at high pressure. This assumption cannot be relied upon, particularly with respect to optical diagnostics. Velocity gradients in flowing plasmas and/or elevated electron temperatures created by electrical discharges can result in large departures from chemical and thermal equilibrium. This paper reviews diagnostic techniques based on optical emission spectroscopy and cavity ring-down spectroscopy that we have found useful for making temperature and concentration measurements in atmospheric pressure plasmas under conditions ranging from thermal and chemical equilibrium to thermochemical nonequilibrium.

/pdf/optical-diagnostics-of-atmospheric-pressure-air-plasmas-2p0ld2axnb.pdf

Optical diagnostics of atmospheric pressure air plasmas

Mechanisms proposed in the literature are compared with a current scenario for the formation of single-wall carbon nanotubes in the laser-ablation process that is based on our spectral emission and laser-induced fluorescence measurements. It is suggested that the carbon which serves as feedstock for nanotube formation not only comes from the direct ablation of the target, but also from carbon particles suspended in the reaction zone. Fullerenes formed in the reaction zone may be photo-dissociated into C2 and other low molecular weight species, and also may serve as feedstock for nanotube growth. Confinement of the nanotubes in the reaction zone within the laser beam allows the nanotubes to be ‘purified’ and annealed during the formation process by laser heating.

Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process

Spectroscopic analysis and chemical kinetics modeling of a diamond deposition plasma reactor

This paper reviews techniques for determining flow properties in low density arc jets used for materials and structures testing. Properties measured include flow total enthalpy, pressures, heat fluxes, static temperatures, electron density, species concentrations, and flow velocity. The probe techniques covered are pressure, heat flux, electrostatic, and mass sampling. Nonintrusive techniques include emission spectroscopy, laser-induced fluorescence, laser Thomson scattering, and Raman scattering. It is concluded that several techniques must be used in a single facility to obtain all of the flow field properties necessary to predict heat fluxes in a nonequilibrium expansion.

Survey of measurements of flow properties in arcjets

The arc process remains the easiest and cheapest technique to obtain significant quantities of single wall carbon nanotubes (SWCNTs) with excellent structural properties. These nanotubes are quite straight and present few topological defects. However, the major inconvenience of this process remains the difficult in situ control of the final material's purity and physical properties. The first NASA/Rice workshop on growth mechanisms was devoted to addressing some specific questions on how and where the nanotubes are formed in several processes including the arc. Further advancement requires a detailed understanding of the growth mechanisms of fullerene, nanotubes and soot and their connection with process parameters. This approach is not highly developed today because of the coupling made by non-equilibrium plasma with the nonlinear chemical system makes, in which rate coefficients and reactions are not well known and this makes modeling difficult. This article is an attempt to analyze the effect of the individual arc parameters yielding guidelines for building a mechanistic understanding of carbon based nanomaterial growth in the arc discharge.

Review of the arc process modeling for fullerene and nanotube production.

This paper presents diagnostic data obtained from the plume of a graphite composite target during carbon nanotube production by the double-pulse laser oven method. The insitu emission spectrum (300 to 650 nm) is recorded at different locations upstream of the target and at different delay times from the lasers (IR and green). Spectral features are identified as emissions from C2 (Swan System: a (sup 3)pi(sub g) - delta (sup 3)pi(sub u) and C3 (Comet Head System: A (sup 1)pi(sub u) - chi (sup 1)sigma(sub u) (sup +). Experimental spectra are compared with computed spectra to estimate vibrational temperatures of excited state C2 in the range of 2500 to 4000 kappa The temporal evolution of the 510 nm band of C2 is monitored for two target positions in various locations which shows confinement of the plume in the inner tube and increase in plume velocity with temperature. The excitation spectra of C2 are obtained by using a dye laser to pump the (0,1) transition of the Swan System and collecting the Laser Induced Fluorescence signal from C2 These are used to obtain "ground-state" rotational and vibrational temperatures which are close to the oven temperature. Images of the plume are also collected and are compared with the spectral measurements.

/pdf/diagnostics-of-laser-produced-plume-under-carbon-nanotube-157zzm6gt6.pdf

Carl D. Scott

Papers

Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process

Spectroscopic analysis and chemical kinetics modeling of a diamond deposition plasma reactor

Survey of measurements of flow properties in arcjets

Review of the arc process modeling for fullerene and nanotube production.

Diagnostics of Laser Produced Plume Under Carbon Nanotube Growth Conditions