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Electrochemical Characterization of Carbon Nanotubes for Fuel Cell MEA's

Single-walled and multi-walled carbon nanotubes from different sources have been evaluated before and after sonication to identify structural differences and evaluate electrochemical performance. Raman spectral analysis and cyclic voltammetry in situ with QCM were the principle means of evaluating the tubes. The raman data indicates that sonication in toluene modifies the structural properties of the nanotubes. Sonication also affects the electrochemical performance of single-walled nanotubes and the multi-walled tubes differently. The characterization of different types of carbon nanotubes leads up to identifying a potential candidate for incorporating carbon nanotubes for fuel cell MEA structures.

Panagaris, Jael↗

Carbon Nanotube Nanoelectrode Array as an Electronic Chip for Ultrasensitive Label-free DNA Detection

A reliable nanoelectrode array based on vertically aligned multi-walled carbon nanotubes (MWNTs) embedded in SiO2 is used for ultrasensitive DNA detection. Characteristic nanoelectrode behavior is observed using low-density MWNT arrays for measuring both bulk and surface immobilized redox species such as K4Fe(CN)6 and ferrocene derivatives. The open-end of MWNTs are found to present similar properties as graphite edge-plane electrodes with wide potential window, flexible chemical functionalities, and good biocompatibility. BRCA1 related oligonucleotide probes with 18 bp are selectively functionalized at the open ends of the nanotube array and specifically hybridized with oligonucleotide targets incorporated with a polyG tag. The guanine groups are employed as the signal moieties in the electrochemical measurements. R(bpy)(sup 2+, sub 3) mediator is used to further amplify the guanine oxidation signal. The hybridization of sub-attomoles of DNA targets is detected electrochemically by combining the MWNT nanoelectrode array with the R(bpy)(sup 2+, sub 3) amplification mechanism. This technique was employed for direct electrochemical detection of label-free PCR amplicon from a healthy donor through specific hybridization with the BRCA1 probe. The detection limit is estimated to be less than 1000 DNA molecules since abundant guanine bases in the PCR amplicon provides a large signal. This system provides a general platform for rapid molecular diagnostics in applications requiring ultrahigh sensitivity, high-degree of miniaturization, and simple sample preparation, and low-cost operation.

Li, Jun↗

Combinatorial Optimization of Heterogeneous Catalysts Used in the Growth of Carbon Nanotubes

Libraries of liquid-phase catalyst precursor solutions were printed onto iridium-coated silicon substrates and evaluated for their effectiveness in catalyzing the growth of multi-walled carbon nanotubes (MWNTs) by chemical vapor deposition (CVD). The catalyst precursor solutions were composed of inorganic salts and a removable tri-block copolymer (EO)20(PO)70(EO)20 (EO = ethylene oxide, PO = propylene oxide) structure-directing agent (SDA), dissolved in ethanol/methanol mixtures. Sample libraries were quickly assayed using scanning electron microscopy after CVD growth to identify active catalysts and CVD conditions. Composition libraries and focus libraries were then constructed around the active spots identified in the discovery libraries to understand how catalyst precursor composition affects the yield, density, and quality of the nanotubes. Successful implementation of combinatorial optimization methods in the development of highly active, carbon nanotube catalysts is demonstrated, as well as the identification of catalyst formulations that lead to varying densities and shapes of aligned nanotube towers.

Cassell, Alan M.↗

Carbon Nanotube Tip Probes: Stability and Lateral Resolution in Scanning Probe Microscopy and Application to Surface Science to Semiconductors

In this paper we present results on the stability and lateral resolution capability of carbon nanotube (CNT) scanning probes as applied to atomic force microscopy (AFM). Surface topography images of ultra-thin films (2-5 nm thickness) obtained with AFM are used to illustrate the lateral resolution capability of single-walled carbon nanotube probes. Images of metal films prepared by ion beam sputtering exhibit grain sizes ranging from greater than 10 nm to as small as approximately 2 nm for gold and iridium respectively. In addition, imaging stability and lifetime of multi-walled carbon nanotube scanning probes are studied on a relatively hard surface of silicon nitride (Si3N4). AFM images Of Si3N4 surface collected after more than 15 hrs of continuous scanning show no detectable degradation in lateral resolution. These results indicate the general feasibility of CNT tips and scanning probe microscopy for examining nanometer-scale surface features of deposited metals as well as non-conductive thin films. AFM coupled with CNT tips offers a simple and nondestructive technique for probing a variety of surfaces, and has immense potential as a surface characterization tool in integrated circuit manufacturing.

Nguyen, Cattien V.↗

Polyimide/carbon Nanocomposites

The goal of this product is to design and characterize well-defined conductive nanocomposite materials. The materials will be composed of a polymer matrix composed of rigid-backbone polyimides, and will be filled with modified or unmodified multi-walled carbon nanotubes (MWNTs). The ultimate design of this project is to create composite materials with optical clarity and a high conductivity.

Harris, Frank W.↗

Preparation and Characterization of PETI-330/Multiwalled Carbon Nanotube Composites

As part of an ongoing effort to incorporate multi-functionality into advanced composites, blends of PETI-330 and multi-walled carbon nanotubes (MWCNTs) were prepared, characterized and fabricated into moldings. The PETI-330/MWCNT mixtures were prepared at concentrations ranging from 3 to 25 weight percent by dry mixing the components in a ball mill. The resulting powders were characterized for degree of mixing, thermal and rheological properties. Based on the characterization results, PETI-330/MWCNT samples were scaled up to approx. 300 g and used to fabricate moldings 10.2 cm x 15.2 cm x 0.32 cm thick. The moldings were fabricated by injecting the mixtures at 260-280 C into a stainless steel tool followed by curing for 1 h at 371 C. The tool was designed to impart high shear during the injection process in an attempt to achieve some alignment of the MWCNTs in the flow direction. Good quality moldings were obtained that were subsequently characterized for thermal, mechanical and electrical properties. The degree of dispersion and alignment of the MWCNTs were investigated using high-resolution scanning electron microscopy and Raman spectroscopy. The preparation and preliminary characterization of PETI-330/MWCNT composites will be discussed. Keywords: phenylethynyl terminated imides, high temperature polymers, nanocomposites,

Ghose, Sayata↗

Physical and Electronic Isolation of Carbon Nanotube Conductors

Multi-walled nanotubes are proposed as a method to electrically and physically isolate nanoscale conductors from their surroundings. We use tight binding (TB) and density functional theory (DFT) to simulate the effects of an external electric field on multi-wall nanotubes. Two categories of multi-wall nanotube are investigated, those with metallic and semiconducting outer shells. In the metallic case, simulations show that the outer wall effectively screens the inner core from an applied electric field. This offers the ability to reduce crosstalk between nanotube conductors. A semiconducting outer shell is found not to perturb an electric field incident on the inner core, thereby providing physical isolation while allowing the tube to remain electrically coupled to its surroundings.

OKeeffe, James↗

Nanotechnology with Carbon Nanotubes: Mechanics, Chemistry, and Electronics

This viewgraph presentation reviews the Nanotechnology of carbon nanotubes. The contents include: 1) Nanomechanics examples; 2) Experimental validation of nanotubes in composites; 3) Anisotropic plastic collapse; 4) Spatio-temporal scales, yielding single-wall nanotubes; 5) Side-wall functionalization of nanotubes; 6) multi-wall Y junction carbon nanotubes; 7) Molecular electronics with Nanotube junctions; 8) Single-wall carbon nanotube junctions; welding; 9) biomimetic dendritic neurons: Carbon nanotube, nanotube electronics (basics), and nanotube junctions for Devices,

Srivastava, Deepak↗

Modeling Intermolecular Interactions in Nanotubes, Fullerenes and Graphite using a New Long-Range Potential

The cohesive energy and compressibility of strands of a single-wall nanotube rope has been computed using a new long-range potential energy function derived from accurate ab initio quantum chemistry calculations of the benzene dimer and calibrated for energetic and mechanical properties of graphite (at pressures up to 12 GPa). We also use this potential to calculate a variety of properties of carbon nanotubes (both single- and multi-wall) and fullerenes. Extensive comparisons are made with previously published potentials.

Jaffe, Richard↗

Improvement of thermal contact resistance by carbon nanotubes and nanofibers

Interfacial thermal resistance results of various nanotube and nanofiber coatings, prepared by chemical vapor deposition (CVD) methods, are reported at relatively low clamping pressures. The five types of samples examined include multi-walled and single-walled nanotubes growth by CVD, multi-walled nanotubes grown by plasma enhanced CVD (PECVD) and carbon nanofibers of differing aspect ratio grown by PECVD. Of the samples examined, only high aspect ratio nanofibers and thermally grown multi-walled nanotubes show an improvement in thermal contact resistance. The improvement is approximately a 60% lower thermal resistance than a bare Si-Cu interface and is comparable to that attained by commercially available thermal interface materials.

Evaluation Studies↗

Characterization of a Structural Transformation of Carbon Nanotube Materials by Raman Spectroscopy

Raman spectra of carbon nanotubes and carbon microstructure materials synthesized on Si substrates by pulsed laser vaporization have been measured in the range of 50/cm to 4500/cm with the excitation of He-Ne laser. It is found that the formation of nanotubes depends strongly on the growth temperatures and high quality multi-wall and single-wall nanotubes were produced at 700 and 990 C, respectively. The Raman spectra of one sample grown at 700 C were found to be dependent on the excitation intensity. The spectra of the sample suggest that the structure is similar to that of multi-wall nanotubes at low excitation intensity (2.5 kW/sq cm) and it converts to the structure of single-wall nanotubes at higher intensity (25 kW/sq cm). Measurements taken while cycling the light intensity indicate a reversible structural transition.

Cui, Y.↗

A Structural Transition of Carbon Nanotubes?

The superior properties of carbon nanotubes (CNT) are good for many applications. A possible temperature-related structural transition is found in the CNT, which may suggest new applications of CNT. CNT materials have been synthesized on Si substrates by pulsed laser vaporization in various temperatures and pressures. Raman spectroscopy and scanning electron microscopy are used to determine the CNT structure and morphology. It is found that the formation of nanotubes depends strongly on the growth temperatures and high quality multi-wall and single-wall nanotubes were produced at 700 and 990 C, respectively. The radial breath modes of Raman spectra measured in the range of 50 cm(exp -1) to 300 cm(exp -1), indicate that one of samples grown at 700 C is to be dependent on the excitation intensity. The spectra of the sample suggest that the structure is similar to that of multi-wall nanotubes at low excitation intensity (2.5 kW per square centimeter) and it converts to the structure of single-wall nanotubes at higher intensity (25 kW per square centimeter). Measurements taken while cycling the light intensity suggests a reversible transition.

Zhu, Shen↗

Flame Synthesis Of Single-Walled Carbon Nanotubes And Nanofibers

Carbon nanotubes are widely sought for a variety of applications including gas storage, intercalation media, catalyst support and composite reinforcing material [1]. Each of these applications will require large scale quantities of CNTs. A second consideration is that some of these applications may require redispersal of the collected CNTs and attachment to a support structure. If the CNTs could be synthesized directly upon the support to be used in the end application, a tremendous savings in post-synthesis processing could be realized. Therein we have pursued both aerosol and supported catalyst synthesis of CNTs. Given space limitations, only the aerosol portion of the work is outlined here though results from both thrusts will be presented during the talk. Aerosol methods of SWNT, MWNT or nanofiber synthesis hold promise of large-scale production to supply the tonnage quantities these applications will require. Aerosol methods may potentially permit control of the catalyst particle size, offer continuous processing, provide highest product purity and most importantly, are scaleable. Only via economy of scale will the cost of CNTs be sufficient to realize the large-scale structural and power applications on both earth and in space. Present aerosol methods for SWNT synthesis include laser ablation of composite metalgraphite targets or thermal decomposition/pyrolysis of a sublimed or vaporized organometallic [2]. Both approaches, conducted within a high temperature furnace, have produced single-walled nanotubes (SWNTs). The former method requires sophisticated hardware and is inherently limited by the energy deposition that can be realized using pulsed laser light. The latter method, using expensive organometallics is difficult to control for SWNT synthesis given a range of gasparticle mixing conditions along variable temperature gradients; multi-walled nanotubes (MWNTs) are a far more likely end products. Both approaches require large energy expenditures and produce CNTs at prohibitive costs, around $500 per gram. Moreover these approaches do not possess demonstrated scalability. In contrast to these approaches, flame synthesis can be a very energy efficient, low-cost process [3]; a portion of the fuel serves as the heating source while the remainder serves as reactant. Moreover, flame systems are geometrically versatile as illustrated by innumerable boiler and furnace designs. Addressing scalability, flame systems are commercially used for producing megatonnage quantities of carbon black [4]. Although it presents a complex chemically reacting flow, a flame also offers many variables for control, e.g. temperature, chemical environment and residence times [5]. Despite these advantages, there are challenges to scaling flame synthesis as well.

Wal, Randy L. Vander↗

Carbon Nanotubes by CVD and Applications

Carbon nanotube (CNT) exhibits extraordinary mechanical and unique electronic properties and offers significant potential for structural, sensor, and nanoelectronics applications. An overview of CNT, growth methods, properties and applications is provided. Single-wall, and multi-wall CNTs have been grown by chemical vapor deposition. Catalyst development and optimization has been accomplished using combinatorial optimization methods. CNT has also been grown from the tips of silicon cantilevers for use in atomic force microscopy.

Cassell, Alan↗

Single Particle Transport Through Carbon Nanotube Wires: Effect of Defects and Polyhedral Cap

The ability to manipulate carbon nanotubes with increasing precision has enabled a large number of successful electron transport experiments. These studies have primarily focussed on characterizing transport through both metallic and semiconducting wires. Tans et al. demonstrated ballistic transport in single-wall nanotubes for the first time, although the experimental configuration incurred large contact resistance. Subsequently, methods of producing low contact resistances have been developed and two terminal conductances smaller than 50 k-ohms have been repeatably demonstrated in single-wall and multi-wall nanotubes. In multi-wall nanotubes, Frank et al. demonstrated a resistance of approximately h/2e(exp 2) in a configuration where the outermost layer made contact to a liquid metal. This was followed by the work of de Pablo et al. where a resistance of h(bar)/27e(exp 2) (approximately 478 ohms) was measured in a configuration where electrical contact was made to many layers of a multi-wall nanotube. Frank et al. and Pablo et al. note that each conducting layer contributes a conductance of only 2e(exp 2)/h, instead of the 4e(exp 2)/h that a single particle mode counting picture yields. These small resistances have been obtained in microns long nanotubes, making them the best conducting molecular wires to date. The large conductance of nanotube wires stems from the fact that the crossing bands of nanotubes are robust to defect scattering.

Anantram, M. P.↗

Carbon Nanotubes Growth on Graphite Fibers

Carbon nanotubes (CNT) were synthesized on graphite fibers by thermal Chemical Vapor Deposition (CVD). On the fiber surface, iron nanoparticles are coated and act as catalysts for CNT growth. The growth temperature ranges from 550 to 1000 C at an ambient pressure. Methane and hydrogen gases with methane contents of 10% to 100% are used for the CNT synthesis. At high growth temperatures (greater than 800 C), the rapid inter-diffusion of the transition metal iron on the graphite surface results in a rough fiber surface with no CNT grown on the surface. When the growth temperature is relatively low (650 - 800 C), CNT are fabricated on the graphite surface with catalytic particles on the nanotube top ends. Using micro Raman spectroscopy in the breath mode region, single-walled or multi-walled CNT can be determined, depending on methane concentrations.

Zhu, Shen↗

Carbon Nanotubes Growth by CVD on Graphite Fibers

Due to the superior electrical and mechanical properties of carbon nanotubes (CNT), synthesizing CNT on various substances for electronics devices and reinforced composites have been engaged in many efforts for applications. This presentation will illustrate CNT synthesized on graphite fibers by thermal CVD. On the fiber surface, iron nanoparticles as catalysts for CNT growth are coated. The growth temperature ranges from 600 to 1000 C and the pressure ranges from 100 Torr to one atmosphere. Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis. At high growth temperatures (greater than or equal to 900 C), the rapid inter-diffusion of the transition metal iron on the graphite surface results in the rough fiber surface without any CNT grown on it. When the growth temperature is relative low (650-800 C), CNT with catalytic particles on the nanotube top ends are fabricated on the graphite surface. (Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis.) (By measuring the samples) Using micro Raman spectroscopy in the breath mode region, single-walled or multi-walled CNT (MWCNT), depending on growth concentrations, are found. Morphology, length and diameter of these MWCNT are determined by scanning electron microscopy and Raman spectroscopy. The detailed results of syntheses and characterizations will be discussed in the presentation.

Zhu, Shen↗

CVD Growth of Carbon Nanotubes: Structure, Catalyst, and Growth

Carbon nanotubes (CNTs) exhibit extraordinary mechanical and unique electronic properties and hence have been receiving much attention in recent years for their potential in nanoelectronics, field emission devices, scanning probes, high strength composites and many more applications. Catalytic decomposition of hydrocarbon feedstock with the aid of supported transition metal catalysts - also known as chemical vapor deposition (CVD) - has become popular to produce single-walled and multi-walled nanotubes (SWNTs, MWNTs) and multiwalled nanofibers (MWNFs). The ability to grow CNTs on patterned substrates and in vertically aligned arrays, and the simplicity of the process, has made CVD growth of CNTs an attractive approach.

Delzeit, Lance↗