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Ranges of Applicability for the Continuum-beam Model in the Constitutive Analysis of Carbon Nanotubes: Nanotubes or Nano-beams?

Ranges of validity for the continuum-beam model, the length-scale effects and continuum assumptions are analyzed in the framework of scaling analysis of NT structure. Two coupled criteria for the applicability of the continuum model are presented. Scaling analysis of NT buckling and geometric parameters (e.g., diameter and length) is carried out to determine the key non-dimensional parameters that control the buckling strains and modes of NT buckling. A model applicability map, which represents two classes of NTs, is constructed in the space of non-dimensional parameters. In an analogy with continuum mechanics, a mechanical law of geometric similitude is presented for two classes of beam-like NTs having different geometries. Expressions for the critical buckling loads and strains are tailored for the distinct groups of NTs and compared with the data provided by the molecular dynamics simulations. Implications for molecular dynamics simulations and the NT-based scanning probes are discussed.

Harik, Vasyl Michael↗

Mechanics of Nanotubes and Nanotube-Polymer Composites

CNT is a tubular form of carbon with diameter as small as 1 nm. Length: few nm to microns. CNT is configurationally equivalent to a two dimensional graphene sheet rolled into a tube. CNT exhibits extraordinary mechanical properties: Young's modulus over 1 Tera Pascal, as stiff as diamond, and tensile strength approx. 200 GPa. CNT can be metallic or semiconducting, depending on chirality.

Srivastava, Deepak↗

New Method Developed To Purify Single Wall Carbon Nanotubes for Aerospace Applications

Single wall carbon nanotubes have attracted considerable attention because of their remarkable mechanical properties and electrical and thermal conductivities. Use of these materials as primary or secondary reinforcements in polymers or ceramics could lead to new materials with significantly enhanced mechanical strength and electrical and thermal conductivity. Use of carbon-nanotube-reinforced materials in aerospace components will enable substantial reductions in component weight and improvements in durability and safety. Potential applications for single wall carbon nanotubes include lightweight components for vehicle structures and propulsion systems, fuel cell components (bipolar plates and electrodes) and battery electrodes, and ultra-lightweight materials for use in solar sails. A major barrier to the successful use of carbon nanotubes in these components is the need for methods to economically produce pure carbon nanotubes in large enough quantities to not only evaluate their suitability for certain applications but also produce actual components. Most carbon nanotube synthesis methods, including the HiPCO (high pressure carbon monoxide) method developed by Smalley and others, employ metal catalysts that remain trapped in the final product. These catalyst impurities can affect nanotube properties and accelerate their decomposition. The development of techniques to remove most, if not all, of these impurities is essential to their successful use in practical applications. A new method has been developed at the NASA Glenn Research Center to purify gram-scale quantities of single wall carbon nanotubes. This method, a modification of a gas phase purification technique previously reported by Smalley and others, uses a combination of high-temperature oxidations and repeated extractions with nitric and hydrochloric acid. This improved procedure significantly reduces the amount of impurities (catalyst and nonnanotube forms of carbon) within the nanotubes, increasing their stability significantly. The onset of decomposition of the purified nanotubes (determined by thermal gravimetric analysis in air) is more than 300 C higher than that of the crude nanotubes. Transmission electron microscopy analysis of nanotubes purified by this method reveals near complete removal of iron catalyst particles. Analysis of the nanotubes using inductively coupled plasma spectroscopy revealed that the iron content of the nanotubes was reduced from 22.7 wt% in the crude nanotubes to less than 0.02 wt%. X-ray photoelectron spectroscopy revealed a decrease in iron content after purification as well as an increase in oxygen content due to the formation of carboxylic acid groups on the surface of the nanotubes. Nanotubes purified by this improved method can be readily dispersed in common organic solvents, in particular N,N-dimethylformamide, using prolonged ultrasonic treatment. These dispersions can then be used to incorporate single wall carbon nanotubes into polymer films.

Lebron, Marisabel↗

Working Toward Nanotube Composites

One of the most attractive applications of single-wall carbon nanotubes (SWNT) is found in the area of structural materials. Nanotubes have a unique combination of high strength, modulus, and elongation to failure, and therefore have potential to significantly enhance the mechanical properties of today's composites. This is especially attractive for the aerospace industry looking for any chance to save weight. This is why NASA has chosen to tackle this difficult application of SWNT. Nanotube properties differ significantly from that of conventional carbon fibers, and a whole new set of problems, including adhesion and dispersion in the adhesive polymer matrix, must be resolved in order to engineer superior composite materials. From recent work on a variety of applications it is obvious that the wide range of research in nanotubes will lead to advances in physics, chemistry, and engineering. However, the possibility of ultralightweight structures is what causes dreamers to really get excited. One of the important issues in composite engineering is aspect ratio of the fibers, since it affects load transfer in composites. Nanotube length was a gray area for years, since they are formed in bundles, making it impossible to monitor individual nanotube length. Even though bundles are observed to be tens and hundreds of microns long, they can be built of relatively short tubes weakly bound by Van der Waals forces. Nanotube length can be affected by subsequent purification and ultrasound processing, which has been necessary in order to disperse nanotubes and introduce them into a polymer matrix. Some calculations show that nanotubes with 10(exp 5) aspect ratio may be necessary to achieve good load transfer. We show here that nanotubes produced in our laser system are as much as tens of microns long and get cut into lengths of hundreds of nanometers during ultrasound processing. Nanotube length was measured by AFM on pristine nanotube specimens as well, as after sonication. In each case great care was taken to measure individual nanotubes, rather than bundles. Pristine nanotubes were collected on quartz substrates placed directly in the laser oven and exposed for 0.5 s. This results in an equal mix of bundles and individual nanotubes. Nanotube length measurements were limited practically by the lateral span of the AFM scanner, but nanotube length is certainly in excess of 20 micrometers.

Arepalli, Sivaram↗

Toxicity and Radioprotective Effects of DF-1 and Carbon Nanotubes in Human Lung and Liver Cell Lines

The DF-1 compound, a sixty carbon fullerene derivative, has been shown to have antioxidant effects and is thought to possibly help mediate the effects of radiation on cells. While this is potentially useful, it is important to first understand the effect that the DF-1 has on the cells and the growth rate of the cells to determine if the material itself has any innate toxicity. A growth curve was established for both HF-19 cells, human fibroblasts, and HepG2 cells, liver tissue cells in the presence of two different concentrations of DF-1 and for untreated controls. The cells were plated in triplicate in 60mm dishes and were lifted and counted with a hemocytometer daily for one week. The growth curve data for the HF-19 cells show that while the low concentration of DF-1 had no apparent effect on the growth rate, the high concentration of DF-1 appeared to severely inhibit the growth of the HF-19 cells. The growth curve data for the HepG2 cells shows that the DF-1 compound had no significant effect on the rate at which the cells grew. A second growth curve study was performed plain carbon nanotubes, but with only 24 hour exposure to a high and low concentration of material. The carbon nanotubes are another carbon compound similar to DF-1, but in the shape of a tube, rather than a ball. We hypothesize that nanotubes may also mediate the effect of radiation on cells. This time, nanotubes did not showed any significant effect on the growth rate HF-19 or HepG2 cells. A third growth curve study is underway to further determine the effect of DF-1, nanotubes, and a derivatized nanotube (BHT-nanotubes). This derivatized nanotube has been modified with a compound that is known to be very effective at neutralizing free radicals. We expect that the high concentration of DF-1 and possibly the nanotubes and BHT-nanotubes may inhibit the growth of the HF-19 cells while the low concentration will resemble the growth of the control. We also hypothesize that there will be no significant effect on the growth of the HepG2 cells by the nanotubes, and BHT-nanotubes. In order to examine the usefulness of the DF-1, nanotubes, and BHT-nanotubes in mediating the effects of radiation a clonogenic assay is being performed. The HF-19 cells were plated in different concentrations of the various compounds and exposed to varying amounts of radiation. The cells are being allowed to grow in a small enough concentration so that the ability of each cell to divide can be seen by the development of cell clusters. By comparing the irradiated control to the un-irradiated control the effects of radiation alone can be seen. By comparing the compound treated irradiated cells to the irradiated control the usefulness of each compound can be seen. It is thought that Amifostine, the positive control, will have more regularly dividing cells then the irradiated control, as will DF-1 and hopefully both nanotube materials as well.

Burgoyne, Madeline↗

Method for separating single-wall carbon nanotubes and compositions thereof

The invention relates to a process for sorting and separating a mixture of (n, m) type single-wall carbon nanotubes according to (n, m) type. A mixture of (n, m) type single-wall carbon nanotubes is suspended such that the single-wall carbon nanotubes are individually dispersed. The nanotube suspension can be done in a surfactant-water solution and the surfactant surrounding the nanotubes keeps the nanotube isolated and from aggregating with other nanotubes. The nanotube suspension is acidified to protonate a fraction of the nanotubes. An electric field is applied and the protonated nanotubes migrate in the electric fields at different rates dependent on their (n, m) type. Fractions of nanotubes are collected at different fractionation times. The process of protonation, applying an electric field, and fractionation is repeated at increasingly higher pH to separated the (n, m) nanotube mixture into individual (n, m) nanotube fractions. The separation enables new electronic devices requiring selected (n, m) nanotube types.

Smalley, Richard E.↗

Arrays of Bundles of Carbon Nanotubes as Field Emitters

Experiments have shown that with suitable choices of critical dimensions, planar arrays of bundles of carbon nanotubes (see figure) can serve as high-current-density field emitter (cold-cathode) electron sources. Whereas some hot-cathode electron sources must be operated at supply potentials of thousands of volts, these cold-cathode sources generate comparable current densities when operated at tens of volts. Consequently, arrays of bundles of carbon nanotubes might prove useful as cold-cathode sources in miniature, lightweight electron-beam devices (e.g., nanoklystrons) soon to be developed. Prior to the experiments, all reported efforts to develop carbon-nanotube-based field-emission sources had yielded low current densities from a few hundred microamperes to a few hundred milliamperes per square centimeter. An electrostatic screening effect, in which taller nanotubes screen the shorter ones from participating in field emission, was conjectured to be what restricts the emission of electrons to such low levels. It was further conjectured that the screening effect could be reduced and thus emission levels increased by increasing the spacing between nanotubes to at least by a factor of one to two times the height of the nanotubes. While this change might increase the emission from individual nanotubes, it would decrease the number of nanotubes per unit area and thereby reduce the total possible emission current. Therefore, to maximize the area-averaged current density, it would be necessary to find an optimum combination of nanotube spacing and nanotube height. The present concept of using an array of bundles of nanotubes arises partly from the concept of optimizing the spacing and height of field emitters. It also arises partly from the idea that single nanotubes may have short lifetimes as field emitters, whereas bundles of nanotubes could afford redundancy so that the loss of a single nanotube would not significantly reduce the overall field emission.

Manohara, Harish↗

Growing Aligned Carbon Nanotubes for Interconnections in ICs

A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by electron-beam lithography. These and other nanotubes were found to have lengths ranging from 2 to 10 m and diameters ranging from 30 to 200 nm, the exact values of length depending on growth times and conditions and the exact values of diameter depending on the diameters and thicknesses of the catalyst spots. The bottom part of Figure 2 is an SEM of an embedded array of carbon nanotubes after CMP.

Li, Jun↗

Buckling of Carbon Nanotube-Reinforced Polymer Laminated Composite Materials Subjected to Axial Compression and Shear Loadings

A multi-scale method to predict the stiffness and stability properties of carbon nanotube-reinforced laminates has been developed. This method is used in the prediction of the buckling behavior of laminated carbon nanotube-polyethylene composites formed by stacking layers of carbon nanotube-reinforced polymer with the nanotube alignment axes of each layer oriented in different directions. Linking of intrinsic, nanoscale-material definitions to finite scale-structural properties is achieved via a hierarchical approach in which the elastic properties of the reinforced layers are predicted by an equivalent continuum modeling technique. Solutions for infinitely long symmetrically laminated nanotube-reinforced laminates with simply-supported or clamped edges subjected to axial compression and shear loadings are presented. The study focuses on the influence of nanotube volume fraction, length, orientation, and functionalization on finite-scale laminate response. Results indicate that for the selected laminate configurations considered in this study, angle-ply laminates composed of aligned, non-functionalized carbon nanotube-reinforced lamina exhibit the greatest buckling resistance with 1% nanotube volume fraction of 450 nm uniformly-distributed carbon nanotubes. In addition, hybrid laminates were considered by varying either the volume fraction or nanotube length through-the-thickness of a quasi-isotropic laminate. The ratio of buckling load-to-nanotube weight percent for the hybrid laminates considered indicate the potential for increasing the buckling efficiency of nanotube-reinforced laminates by optimizing nanotube size and proportion with respect to laminate configuration.

Riddick, J. C.↗

Covalent Crosslinking of Carbon Nanotube Materials for Improved Tensile Strength

Carbon nanotubes have attracted much interest in recent years due to their exceptional mechanical properties. Currently, the tensile properties of bulk carbon nanotube-based materials (yarns, sheets, etc.) fall far short of those of the individual nanotube elements. The premature failure in these materials under tensile load has been attributed to inter-tube sliding, which requires far less force than that needed to fracture individual nanotubes.1,2 In order for nanotube materials to achieve their full potential, methods are needed to restrict this tube-tube shear and increase inter-tube forces.Our group is examining covalent crosslinking between the nanotubes as a means to increase the tensile properties of carbon nanotube materials. We are working with multi-walled carbon nanotube (MWCNT) sheet and yarn materials obtained from commercial sources. Several routes to functionalize the nanotubes have been examined including nitrene, aryl diazonium, and epoxide chemistries. The functional nanotubes were crosslinked through small molecule or polymeric bridges. Additionally, electron beam irradiation induced crosslinking of the non-functional and functional nanotube materials was conducted. For example, a nanotube sheet material containing approximately 3.5 mol amine functional groups exhibited a tensile strength of 75 MPa and a tensile modulus of 1.16 GPa, compared to 49 MPa and 0.57 GPa, respectively, for the as-received material. Electron beam irradiation (2.2x 1017 ecm2) of the same amine-functional sheet material further increased the tensile strength to 120 MPa and the modulus to 2.61 GPa. This represents approximately a 150 increase in tensile strength and a 360 increase in tensile modulus over the as-received material with only a 25 increase in material mass. Once we have optimized the nanotube crosslinking methods, the performance of these materials in polymer matrix composites will be evaluated.

polymer matrix composites↗

Improved Process for Fabricating Carbon Nanotube Probes

An improved process has been developed for the efficient fabrication of carbon nanotube probes for use in atomic-force microscopes (AFMs) and nanomanipulators. Relative to prior nanotube tip production processes, this process offers advantages in alignment of the nanotube on the cantilever and stability of the nanotube's attachment. A procedure has also been developed at Ames that effectively sharpens the multiwalled nanotube, which improves the resolution of the multiwalled nanotube probes and, combined with the greater stability of multiwalled nanotube probes, increases the effective resolution of these probes, making them comparable in resolution to single-walled carbon nanotube probes. The robust attachment derived from this improved fabrication method and the natural strength and resiliency of the nanotube itself produces an AFM probe with an extremely long imaging lifetime. In a longevity test, a nanotube tip imaged a silicon nitride surface for 15 hours without measurable loss of resolution. In contrast, the resolution of conventional silicon probes noticeably begins to degrade within minutes. These carbon nanotube probes have many possible applications in the semiconductor industry, particularly as devices are approaching the nanometer scale and new atomic layer deposition techniques necessitate a higher resolution characterization technique. Previously at Ames, the use of nanotube probes has been demonstrated for imaging photoresist patterns with high aspect ratio. In addition, these tips have been used to analyze Mars simulant dust grains, extremophile protein crystals, and DNA structure.

Stevens, R.↗

Reconfiguring DNA Nanotube Architectures via Selective Regulation of Terminating Structures

Molecular assemblies inside cells often undergo structural reconfiguration in response to stimuli to alter their function. Adaptive reconfiguration of cytoskeletal networks, for example, enables cellular shape change, movement, and cargo transport and plays a key role in driving complex processes such as division and differentiation. The cellular cytoskeleton is a self-assembling polymer network composed of simple filaments, so reconfiguration often occurs through the rearrangement of its component filaments’ connectivities. DNA nanotubes have emerged as promising building blocks for constructing programmable synthetic analogs of cytoskeletal networks. Nucleating seeds can control when and where nanotubes grow and capping structures can bind nanotube ends to stop growth. Such seeding and capping structure, collectively called termini, can organize nanotubes into larger architectures. However, these structures cannot be selectively activated or inactivated in response to specific stimuli to rearrange nanotube architectures, a key property of cytoskeletal networks. Here we demonstrate how selective regulation of the binding affinity of DNA nanotube termini for DNA nanotube monomers or nanotube ends can direct the reconfiguration of nanotube architectures. Using DNA hybridization and strand displacement reactions that specifically activate or inactivate four orthogonal nanotube termini, we demonstrate that nanotube architectures can be reconfigured by selective addition or removal of unique termini. Lastly, we show how terminus activation could be a sensitive detector and amplifier of a DNA sequence signal. These results could enable the development of adaptive and multifunctional materials or diagnostic tools.

59 BASIC BIOLOGICAL SCIENCES↗

Modeling Ballistic Current Flow in Carbon Nanotube Wires

Experiments have shown carbon nanotubes (CNT) to be almost perfect conductors at small applied biases. The features of the CNT band structure, large velocity of the crossing subbands and the small number of modes that an electron close to the band center / Fermi energy can scatter into, are the reasons for the near perfect small bias conductance. We show that the CNT band structure does not help at large applied biases - electrons injected into the non crossing subbands can either be Bragg reflected or undergo Zener-type tunneling. This limits the current carrying capacity of CNT. We point out that the current carrying capacity of semiconductor quantum wires in the ballistic limit is different, owing to its band structure. The second aspect addressed is the relationship of nanotube chirality in determining the physics of metal-nanotube coupling. We show that a metallic-zigzag nanotube couples better than an armchair nanotube to a metal contact. This arises because in the case of armchair nanotubes, while the pi band couples well, the pi* band does not couple well to the metal. In the case of zigzag nanotube both crossing modes couple reasonably well to the metal. Many factors such as the role of curvature, strain and defects will play a role in determining the suitability of nanotubes as nanowires. From the limited view point of metal-nanotube coupling, we feel that metallic-zigzag nanotubes are preferable to armchair nanotubes.

Anantram, M. P.↗

Functionalized Carbon Nanotubes

Carbon nanotubes have created a great deal of excitement in the Materials Science community because of their outstanding mechanical, electrical, and thermal properties. Use of carbon nanotubes as reinforcements for polymers could lead to a new class of composite materials with properties, durability, and performance far exceeding that of conventional fiber reinforced composites. Organized arrays of carbon nanotubes, e.g., nanotube monolayers, could find applications as thermal management materials, light emitting devices, and sensor arrays. Carbon nanotubes could also be used as templates upon which nanotubes from other materials could be constructed. Successful use of carbon nanotubes in any of these potential applications requires the ability to control the interactions of nanotubes with each other and with other materials, e.g., a polymer matrix. One approach to achieving this control is to attach certain chemical groups to the ends and/or side-walls of the nanotubes. The nature of these chemical groups can be varied to achieve the desired result, such as better adhesion between the nanotubes and a polymer. Under a joint program between NASA Glenn, Clark Atlanta University, and Rice University researchers are working on developing a chemistry "tool-kit" that will enable the functionalization of carbon nanotubes with a variety of chemical groups. Recent results of this effort will be discussed.

Lebron, Marisabel↗

Flame Synthesis Used to Create Metal-Catalyzed Carbon Nanotubes

Metal-catalyzed carbon nanotubes are highly ordered carbon structures of nanoscale dimensions. They may be thought of as hollow cylinders whose walls are formed by single atomic layers of graphite. Such cylinders may be composed of many nested, concentric atomic layers of carbon or only a single layer, the latter forming a single-walled carbon nanotube. This article reports unique results using a flame for their synthesis. Only recently were carbon nanotubes discovered within an arc discharge and recognized as fullerene derivatives. Today metal-catalyzed carbon nanotubes are of great interest for many reasons. They can be used as supports for the metal catalysts like those found in catalytic converters. Open-ended nanotubes are highly desirable because they can be filled by other elements, metals or gases, for battery and fuel cell applications. Because of their highly crystalline structure, they are significantly stronger than the commercial carbon fibers that are currently available (10 times as strong as steel but possessing one-sixth of the weight). This property makes them highly desirable for strengthening polymer and ceramic composite materials. Current methods of synthesizing carbon nanotubes include thermal pyrolysis of organometallics, laser ablation of metal targets within hydrocarbon atmospheres at high temperatures, and arc discharges. Each of these methods is costly, and it is unclear if they can be scaled for the commercial synthesis of carbon nanotubes. In contrast, flame synthesis is an economical means of bulk synthesis of a variety of aerosol materials such as carbon black. Flame synthesis of carbon nanotubes could potentially realize an economy of scale that would enable their use in common structural materials such as car-body panels. The top figure is a transmission electron micrograph of a multiwalled carbon nanotube. The image shows a cross section of the atomic structure of the nanotube. The dark lines are individual atomic layer planes of carbon, seen here in cross section. They form a nested series of concentric cylinders, much like the growth rings on a tree. This sample was obtained by the supported catalyst method, whereby the nanoscale catalysts are dispersed on a substrate providing their support. The substrate with catalyst particles was immersed within an acetylene diffusion flame to which nitrogen had been added to eliminate soot formation. Upon removal from the flame, the nanotubes were dispersed on a holder suitable for electron microscopy. Although not seen in the figure, the tube diameter reflects that of the catalyst particle.

VanderWal, Randy L.↗