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At least 397 records · Page 22

HRTEM Imaging and Mechanistic Insights Into Carbon Nanotube Nucleation and Growth on Fe Nanocatalysts in a Thermal Plasma

Thermal plasma decomposition of natural gas is a scalable pathway for the production of hydrogen alongside high-value carbon nanotubes (CNTs). Metals evaporate from an electrode and condense to form seed nanoparticles that nucleate and grow CNTs. However, the lack of mechanistic understanding of the CNT nucleation and growth processes in thermal plasma makes control over CNT diameter, chirality, length, and yield difficult. We debundled and separated CNTs from soots produced using iron (Fe) nanocatalysts, and distributed them on monolayer graphene for high-resolution transmission electron microscopy (HRTEM) imaging to gain mechanistic insights. Full graphene encapsulation was found for relatively small Fe nanoparticles that were molten at high temperatures. Zigzag single-wall or double-wall CNTs (SWCNTs or DWCNTs) appeared to have grown out directly from the graphene covering on the conical or cylindrical bodies of small molten Fe nanodroplets with high curvature. Also, SWCNTs likely grew out from H- or O-atom etched single-wall carbon nanocones observed on conical Fe nanoparticles. A SWCNT/DWCNT could also be generated from the cracked opening of the graphene covering on a face-centered cubic (FCC) Fe nanoparticle. A simple, plausible pathway is proposed for the growth of an open, H-passivated, zigzag SWCNT involving reaction of CH 2 and CH radicals at high temperatures.

Fe nanocatalysts↗

Laser ablation process for single-walled carbon nanotube production

Different types of lasers are now routinely used to prepare single-walled carbon nanotubes. The original method developed by researchers at Rice University used a "double-pulse laser oven" process. Several researchers have used variations of the lasers to include one-laser pulse (green or infrared), different pulse widths (ns to micros as well as continuous wave), and different laser wavelengths (e.g., CO2, or free electron lasers in the near to far infrared). Some of these variations are tried with different combinations and concentrations of metal catalysts, buffer gases (e.g., helium), oven temperatures, flow conditions, and even different porosities of the graphite targets. This article is an attempt to cover all these variations and their relative merits. Possible growth mechanisms under these different conditions will also be discussed.

Review↗

CO-promoted low-temperature conversion of CH 4 to hydrogen and carbon nanotubes on Nanocrystalline Cr-doped ferrite catalyst

Catalytic decomposition of methane (CDM) to H 2 and multiwalled carbon nanotubes (MWCNTs) was achieved by a nanocrystalline Cr-doped ferrite (FeCr) catalyst at 500 °C and atmospheric pressure with minor cofed CO. The exothermic Boudouard reaction increased the temperature and H 2 from CDM at catalyst surface that induced Fe 2+ reduction to Fe 0 . The Fe 0 clusters along with the CO-originated surface oxygens enabled transfer of C and H to sustain the surface CDM and CO reactions. The metallic Fe-enabled C transfer led to the formation of MWCNTs. The Cr 6+/3+ dopants facilitated the Fe redox cycles and maintained surface oxygens for high catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Aging and Halogen Oxides Formation on Multiwalled Carbon Nanotubes and Fe 3 O 4 @g-C 3 N 4 Coated Conductive Membranes

Electrochemical membrane filtration is widely reported to enhance water contaminants' degradation or rejection via anodic oxidation or cathodic repulsion. Despite their advances, electrochemical membranes or electrocatalysts often suffer from corrosion or passivation, especially under strong electrode potentials or reactions. Moreover, the formation of toxic byproducts, such as chlorinated organic compounds and oxyhalides (e.g., ClO 4 - ) is another major concern. This study investigated the membrane aging processes of two types of conductive membranes, multiwalled carbon nanotubes (MWCNTs) and ferrite/graphitic carbon nitride hybrids (Fe 3 O 4 @g-C 3 N 4 ) coated on ceramic membranes. Under high current densities (~ 20 mA∙cm -2 ) with anodic potentials (~10 V), MWCNTs and Fe 3 O 4 @g-C 3 N 4 catalysts underwent evident oxidation as indicated by an increase of the intensity ratio of the Raman spectral bands (I D /I G ) and charge transfer resistance (R ct ) of two electrochemical membranes. Under variations of electrode potentials, chloride or bromide were shown to be oxidized to bromate (BrO 3 - ) and chlorate (ClO 3 - ) at levels of 1-10 mmol∙L -1 . The formation of BrO 3 - and ClO 3 - was dependent on the solution pH, current densities (1-20 mA∙cm -2 ), and initial concentrations of Br or Cl ions. Finally, to warrant a safe and rational design and operation of electrochemically reactive membrane processes, membrane aging and toxic byproduct's formation deserve careful characterization under relevant water filtration environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Studies of Carbon Nanotubes

The fellowship experience for this summer for 2004 pertains to carbon nanotube coatings for various space-related applications. They involve the following projects: (a) EMI protection films from HiPco-polymers, and (b) Thermal protection nanosilica materials. EMI protection films are targeted to be eventually applied onto casings of laptop computers. These coatings are composites of electrically-conductive SWNTs and compatible polymers. The substrate polymer will be polycarbonate, since computer housings are typically made of carbon composites of this type of polymer. A new experimental copolymer was used last year to generate electrically-conductive and thermal films with HiPco at 50/50 wt/wt composition. This will be one of the possible formulations. Reference films will be base polycarbonate and neat HiPco onto polycarbonate films. Other coating materials that will be tried will be based on HiPco composites with commercial enamels (polyurethane, acrylic, polyester), which could be compatible with the polycarbonate substrate. Nanosilica fibers are planned for possible use as thermal protection tiles on the shuttle orbiter. Right now, microscale silica is used. Going to the nanoscale will increase the surface-volume-per-unit-area of radiative heat dissipation. Nanoscale carbon fibers/nanotubes can be used as templates for the generation of nanosilica. A sol-gel operation is employed for this purpose.

Caneba, Gerard T.↗

Experimental Studies of Carbon Nanotube Materials for Space Radiators

Game ]changing propulsion systems are often enabled by novel designs using advanced materials. Radiator performance dictates power output for nuclear electric propulsion (NEP) systems. Carbon nanotubes (CNT) and carbon fiber materials have the potential to offer significant improvements in thermal conductivity and mass properties. A test apparatus was developed to test advanced radiator designs. This test apparatus uses a resistance heater inside a graphite tube. Metallic tubes can be slipped over the graphite tube to simulate a heat pipe. Several sub ]scale test articles were fabricated using CNT cloth and pitch ]based carbon fibers, which were bonded to a metallic tube using an active braze material. The test articles were heated up to 600 C and an infrared (IR) camera captured the results. The test apparatus and experimental results are presented here.

SanSoucie, MIchael P.↗

Cambered Bipyridyl Ligand with Extended Aryl System Enables Electrochemical Reduction of Carbon Dioxide and Bicarbonate by Mn(bpy)(CO) 3 Br-type Catalyst Immobilized on Carbon Nanotubes

Heterogeneous materials containing molecular catalytic sites show promise for electrocatalytic reduction of CO 2 to energy-enriched carbon products. Interactions between the catalyst and the heterogeneous support increasingly are recognized as important in governing product selectivity and rate. Recent work on Mn(R-bpy)(CO) 3 Br type catalysts immobilized on multiwalled carbon nanotubes (MWCNT) demonstrated control of electrocatalytic behavior with steric modification of the molecular catalyst. Phenyl groups installed in the 4,4' positions of the bipyridine ligand (ph-bpy) maximized performance through π–π interactions with the MWCNT support. Herein we report the outcome of extending the ligand π system with Mn(nap-bpy)(CO) 3 Br (nap-bpy = 4,4'-di(naphthalen-1-yl)-2,2'-bipyridine) and Mn(pyr-bpy)(CO) 3 Br (pyr-bpy = 4,4'-di(pyren-1-yl)-2,2'-bipyridine) immobilized on MWCNT. We demonstrate exceptional electrocatalysis with Mn(nap-bpy)(CO) 3 Br/MWCNT (FE CO > 92%; J CO = 16.5 mA/cm 2 ) and find that this catalyst electrochemically reduces bicarbonate in the absence of deliberately added CO 2 at a remarkable overall selectivity of >80% for carbon products (FE HCOO – = 52% and FE CO = 29%). We show diminishing returns to simply adding aromatic character to the bipyridyl ligand with Mn(pyr-bpy)(CO) 3 Br/MWCNT and observe a unique cambering of the Mn(nap-bpy)(CO) 3 Br bipyridyl ligand that we believe enables selective catalysis. Mechanistic studies were carried out on Mn(nap-bpy)(CO) 3 Br/MWCNT using a novel thin-film infrared spectroelectrochemical (IR-SEC) technique. These experiments observe the immobilized Mn(nap-bpy)(CO) 3 Br undergo single electron reduction to a Mn-centered radical that binds CO 2 in a reduction-coupled process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Performance Hemofiltration via Molecular Sieving and Ultra-Low Friction in Carbon Nanotube Capillary Membranes

Conventional dialyzer membranes typically comprise of unevenly distributed polydisperse, tortuous, rough pores, embedded in relatively thick ≈20–50 µm polymer layers wherein separation occurs via size exclusion as well as differences in diffusivity of the permeating species. However, transport in such polymeric pores is increasingly hindered as the molecule size approaches the pore dimension, resulting in significant retention of undesirable middle molecules (≥15–60 kDa) and uremic toxins. Enhanced removal of middle molecules is usually accompanied by high albumin loss (≈66 kDa) causing hypoalbuminemia. Here, the scalable bottom-up fabrication of wafer-scale carbon nanotube (CNT) membranes with highly aligned, low-friction, straight-channels/capillaries and narrow pore-diameter distributions (≈0.5–4.5 nm) is demonstrated, to overcome persistent challenges in hemofiltration/hemodialysis. Using fluorescein isothiocyanate (FITC)-Ficoll 70 and albumin in phosphate buffered saline (PBS) as well as in bovine blood plasma, it is shown that CNT membranes can allow for significantly higher hydraulic permeability (more than an order of magnitude when normalized to pore area) than commercial high-flux hemofiltration/hemodialysis membranes (HF 400), as well as greatly enhance removal of middle molecules while maintaining comparable albumin retention. These findings are rationalized via an N-pore transport model that highlights the critical role of molecular flexing and deformation during size-selective transport within nanoscale confinements of the CNTs. In conclusion, the unique transport characteristics of CNTs coupled with size-exclusion and wafer-scale fabrication offer transformative advances for hemofiltration, and the obtained insight into molecular transport can aid advancements in several other bio-systems/applications beyond hemofiltration/hemodialysis.

36 MATERIALS SCIENCE↗

Structural, Electrical, and Optical Properties of Single-Walled Carbon Nanotubes Synthesized through Floating Catalyst Chemical Vapor Deposition

Single-walled carbon nanotube (SWCNT) thin films were synthesized by using a floating catalyst chemical vapor deposition (FCCVD) method with a low flow rate (200 sccm) of mixed gases (Ar and H 2 ). SWCNT thin films with different thicknesses can be prepared by controlling the collection time of the SWCNTs on membrane filters. Transmission electron microscopy (TEM) showed that the SWCNTs formed bundles and that they had an average diameter of 1.46 nm. The Raman spectra of the SWCNT films suggested that the synthesized SWCNTs were very well crystallized. Although the electrical properties of SWCNTs have been widely studied so far, the Hall effect of SWCNTs has not been fully studied to explore the electrical characteristics of SWCNT thin films. In this research, Hall effect measurements have been performed to investigate the important electrical characteristics of SWCNTs, such as their carrier mobility, carrier density, Hall coefficient, conductivity, and sheet resistance. The samples with transmittance between 95 and 43% showed a high carrier density of 10 21– 10 23 cm –3 . The SWCNTs were also treated using Brønsted acids (HCl, HNO 3 , H 2 SO 4 ) to enhance their electrical properties. After the acid treatments, the samples maintained their p-type nature. The carrier mobility and conductivity increased, and the sheet resistance decreased for all treated samples. The highest mobility of 1.5 cm 2 /Vs was obtained with the sulfuric acid treatment at 80 °C, while the highest conductivity (30,720 S/m) and lowest sheet resistance (43 ohm/square) were achieved with the nitric acid treatment at room temperature. Different functional groups were identified in our synthesized SWCNTs before and after the acid treatments using Fourier-Transform Infrared Spectroscopy (FTIR).

36 MATERIALS SCIENCE↗

Carbon Nanotube Composites: Strongest Engineering Material Ever?

The primary goal of the carbon nanotube project at Johnson Space Center (JSC) is to fabricate structural materials with a much higher strength-to-weight ratio than any engineered material today, Single-wall nanotubes present extraordinary mechanical properties along with new challenges for materials processing. Our project includes nanotube production, characterization, purification, and incorporation into applications studies. Now is the time to move from studying individual nanotubes to applications work. Current research at JSC focuses on structural polymeric materials to attempt to lower the weight of spacecraft necessary for interplanetary missions. These nanoscale fibers present unique new challenges to composites engineers. Preliminary studies show good nanotube dispersion and wetting by the epoxy materials. Results of tensile strength tests will also be reported. Other applications of nanotubes are also of interest for energy storage, gas storage, nanoelectronics, field emission, and biomedical uses.

Mayeaux, Brian↗

Synthesis of Carbon Nanotubes Array by CVD

Since the properties of multi-wall carbon nanotubes (MWCNT) are superior in many devices such as electronics and sensors, many efforts have been involved in synthesizing particular structural or dimensional MWCNT. Uniform aligned MWCNT array is one of the prototype structures for devices such as filed emission device and microelectromechanical systems in which a large length to diameter ratio may also be required. Most aligned MWCNT recently synthesized by plasma enhanced chemical vapor deposition (CVD) have cone shaped structures. This presentation will illustrate aligned MWCNT array synthesized on silicon substrates using thermal CVD that could produce MWCNT with uniform diameter. An array of nickel particles was used as catalyst for MWCNT growth. A thin Ti or Au buffer layer was coated on the substrate prior to depositing nickel particles. Because the MWCNT size depends on the catalyst particle size, the nickel particle size annealed at various temperatures was investigated. MWCNT were grown on the substrate in the temperature range of 700 C - 1000 C and the pressure range of 1 to 300 torr. Methane and hydrogen gases with methane content of 1 - 10 % were used for the MWCNT synthesis. Morphology, length and diameter of MWCNT were determined by scanning electron microscopy and Raman spectroscopy. The detailed results of synthesis and characterizations will be discussed in the presentation.

Zhu, S.↗

Conductance of AFM Deformed Carbon Nanotubes

This viewgraph presentation provides information on the electrical conductivity of carbon nanotubes upon deformation by atomic force microscopy (AFM). The density of states and conductance were computed using four orbital tight-binding method with various parameterizations. Different chiralities develop bandgap that varies with chirality.

Svizhenko, Alexei↗

Transport in Carbon Nanotubes with Defects

The linear response conductance of a defect free carbon nanotube connected to ideal contacts is approximately 4e(sup 2)/h. In this paper, we first calculate the conductance characteristics of a uniform tube in the presence of an applied bias by assuring different forms of the potential drop across the wire. It is shown that for long tubes, the conduction mechanism involve a only the four non degenerate subands when the electric field drops slowly across the the tube. We then proceed to calculate the transmission and low bias conductance of tubes with defects. Here, we show that a weak uniform disorder in the tube does not cause a dramatic change in the conductance. However the presence of certain substitutional defects, the transmission coefficient versus energy develops a gap and this can cause a dramatic change in the low bias conductance. The effect of coherence is neglected.

Anatram, M. P.↗

Modeling of Gate Bias Modulation in Carbon Nanotube Field-Effect-Transistor

The threshold voltages of a carbon-nanotube (CNT) field-effect transistor (FET) are studied. The CNT channel is so thin that there is no voltage drop perpendicular to the gate electrode plane, and this makes the device characteristics quite unique. The relation between the voltage and the electrochemical potentials, and the mass action law for electrons and holes are examined in the context of CNTs, and inversion and accumulation threshold voltages (V(sub Ti), and V(sub Ta)) are derived. V(sub Ti) of the CNTFETs has a much stronger doping dependence than that of the metal-oxide- semiconductor FETs, while V(sub Ta) of both devices depends weakly on doping with the same functional form.

Toshishige, Yamada↗

Large-Scale Fabrication of Carbon Nanotube Probe Tips For Atomic Force Microscopy Critical Dimension Imaging Applications

Carbon nanotube (CNT) probe tips for atomic force microscopy (AFM) offer several advantages over Si/Si3N4 probe tips, including improved resolution, shape, and mechanical properties. This viewgraph presentation discusses these advantages, and the drawbacks of existing methods for fabricating CNT probe tips for AFM. The presentation introduces a bottom up wafer scale fabrication method for CNT probe tips which integrates catalyst nanopatterning and nanomaterials synthesis with traditional silicon cantilever microfabrication technology. This method makes mass production of CNT AFM probe tips feasible, and can be applied to the fabrication of other nanodevices with CNT elements.

Ye, Qi Laura↗

Carbon Nanotube Activities at NASA-Johnson Space Center

Research activities on carbon nanotubes at NASA-Johnson Space Center include production, purification, characterization and their applications for human space flight. In-situ diagnostics during nanotube production by laser oven process include collection of spatial and temporal data of passive emission and laser induced fluorescence from C2, C3 and Nickel atoms in the plume. Details of the results from the "parametric study" of the pulsed laser ablation process indicate the effect of production parameters including temperature, buffer gas, flow rate, pressure, and laser fluence. Improvement of the purity by a variety of steps in the purification process is monitored by characterization techniques including SEM, TEM, Raman, UV-VIS-NIR and TGA. A recently established NASA-JSC protocol for SWCNT characterization is undergoing revision with feedback from nanotube community. Efforts at JSC over the past five years in composites have centered on structural polymednanotube systems. Recent activities broadened this focus to multifunctional materials, supercapacitors, fuel cells, regenerable CO2 absorbers, electromagnetic shielding, radiation dosimetry and thermal management systems of interest for human space flight. Preliminary tests indicate improvement of performance in most of these applications because of the large surface area as well as high electrical and thermal conductivity exhibited by SWCNTs.

Arepalli, Sivaram↗

Novel Materials Containing Single-Wall Carbon Nanotubes Wrapped in Polymer Molecules

In this design, single-wall carbon nanotubes (SWNTs) have been coated in polymer molecules to create a new type of material that has low electrical conductivity, but still contains individual nanotubes, and small ropes of individual nanotubes, which are themselves good electrical conductors and serve as small conducting rods immersed in an electrically insulating matrix. The polymer is attached through weak chemical forces that are primarily non-covalent in nature, caused primarily through polarization rather than the sharing of valence electrons. Therefore, the electronic structure of the SWNT involved is substantially the same as that of free, individual (and small ropes of) SWNT. Their high conductivity makes the individual nanotubes extremely electrically polarizable, and materials containing these individual, highly polarizable molecules exhibit novel electrical properties including a high dielectric constant.

Smalley, Richard E.↗

Perovskite-Carbon Nanotube Light-Emitting Fibers

Active fibers with electro-optic functionalities are promising building blocks for the emerging and rapidly growing field of fiber and textile electronics. Yet, there remains significant challenges that require improved understanding of the principles of active fiber assembly to enable the development of fiber-shaped devices characterized by having a small diameter, being lightweight, and having high mechanical strength. To this end, the current frameworks are insufficient, and new designs and fabrication approaches are essential to accommodate this unconventional form factor. Here, we present a first demonstration of a pathway that effectively integrates the foundational components meeting such requirements, with the use of a flexible and robust conductive core carbon nanotube fiber and an organic–inorganic emissive composite layer as the two critical elements. We introduce an active fiber design that can be realized through an all solution-processed approach. In conclusion, we have implemented this technique to demonstrate a three- layered light-emitting fiber with a coaxially coated design.

36 MATERIALS SCIENCE↗