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Arepalli, Sivaram

Publications and source records attributed to Arepalli, Sivaram.

At least 37 records · Page 2

Recent Advances in Synthesis and Characterization of SWCNTs produced by laser oven process

Results from the parametric study of the two-laser oven process indicated possible improvements with flow conditions and laser characteristics (ref. 1). Higher flow rates, lower operating pressures coupled with changes in flow tube material are found to improve the nanotube yields. The collected nanotube material is analyzed using a combination of characterization techniques including SEM, TEM, TGA, Raman and UV-VIS-NIR to estimate the purity of the samples. Insitu diagnostics of the laser oven process is now extended to include the surface temperature of the target material. Spectral emission from the target surface is compared with black body type emission to estimate the temperature. The surface temperature seemed to correlate well with the ablation rate as well as the quality of the SWCNTs. Recent changes in improving the production rate by rastering the target and using cw laser will be presented.

Arepalli, Sivaram↗

Nanotube Activities at NASA-Johnson Space Center

Nanotube activities at NASA-Johnson Space Center include production, purification, characterization as well as applications of single wall carbon nanotubes (SWCNTs). A parametric study of the pulsed laser ablation process is recently completed to monitor the effect of production parameters including temperature, buffer gas, flow rate, pressure, and laser fluence. Enhancement of production is achieved by rastering the graphite target and by increasing the target surface temperature with a cw laser. In-situ diagnostics during production included time resolved passive emission and laser induced fluorescence from the plume. The 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 polymer/nanotube 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. Comparison with existing technologies and possible future improvements in the SWCNT materials sill be presented.

Arepalli, Sivaram↗

Fast Characterization of Magnetic Impurities in Single-Wall Carbon Nanotubes

We have demonstrated that the magnetic susceptibility measurement is a non-destructive, fast and accurate method to determine the residual metal catalysts in a few microgram single-wall carbon nanotube (SWCNT) sample. We have studied magnetic impurities in raw and purified SWCNT by magnetic susceptibility measurements, transmission electron microscopy, and thermogravimetry. The data suggest that the saturation magnetic moment and the effective field, which is caused by the interparticle interactions, decreases and increases respectively with the decrease of the particle size. Methods are suggested to overcome the uncertainty associated.

Chen, Feng↗

Review of Laser Ablation Process for Single Wall Carbon Nanotube Production

Different types of lasers are now routinely used to prepare single wall carbon nanotubes (SWCNTs). The original method developed by researchers at Rice University utilized a "double pulse laser oven" process. A graphite target containing about 1 atomic percent of metal catalysts is ablated inside a 1473K oven using laser pulses (10 ns pulse width) in slow flowing argon. Two YAG lasers with a green pulse (532 nm) followed by an IR pulse (1064 nm) with a 50 ns delay are used for ablation. This set up produced single wall carbon nanotube material with about 70% purity having a diameter distribution peaked around 1.4 nm. The impurities consist of fullerenes, metal catalyst clusters (10 to 100 nm diameter) and amorphous carbon. The rate of production with the initial set up was about 60 mg per hour with 10Hz laser systems. Several researchers have used variations of the lasers to improve the rate, consistency and study effects of different process parameters on the quality and quantity of SWCNTs. These variations include one to three YAG laser systems (Green, Green and IR), different pulse widths (nano to microseconds as well as continuous) and different laser wavelengths (Alexandrite, CO, CO2, free electron lasers in the near to far infrared). It is noted that yield from the single laser (Green or IR) systems is only a fraction of the two laser systems. The yield seemed to scale up with the repetition rate of the laser systems (10 to 60 Hz) and depended on the beam uniformity and quality of the laser pulses. The shift to longer wavelength lasers (free electron, CO and CO2) did not improve the quality, but increased the rate of production because these lasers are either continuous (CW) or high repetition rate pulses (kHz to MHz). The average power and the peak power of the lasers seem to influence the yields. Very high peak powers (MegaWatts per square centimeter) are noted to increase ablation of bigger particles with reduced yields of SWCNTs. Increased average powers seem to help the conversion of the carbon from target into vapor phase to improve formation of nanotubes. The use of CW far infrared lasers reduced the need for the oven, at the expense of controlled ablation. Some of these variations are tried with different combinations and concentrations of metal catalysts (Nickel with Cobalt, Iron, Palladium and Platinum) different buffer gases (e.g. Helium); with different oven temperatures (Room temperature to 1473K); under different flow conditions (1 to 1000 kPa) and even different porosities of the graphite targets. It is to be noted that the original Cobalt and Nickel combination worked best, possibly because of improved carbonization with stable crystalline phases. The mean diameter and yield seemed to increase with increasing oven temperatures. Thermal conductivity of the buffer gas and flow conditions dictate the quality as well as quantity of the SWCNTs. Faster flows, lower pressures and heavier gases seem to increase the yields. This review will attempt to cover all these variations and their relative merits. Possible growth mechanisms under these different conditions will also be discussed.

Arepalli, Sivaram↗

Parametric Study of Carbon Nanotube Production by Laser Ablation Process

Carbon nanotubes form a new class of nanomaterials that are presumed to have extraordinary mechanical, electrical and thermal properties. The single wall nanotubes (SWNTs) are estimated to be 100 times stronger than steel with 1/6th the weight; electrical carrying capacity better than copper and thermal conductivity better than diamond. Applications of these SWNTs include possible weight reduction of aerospace structures, multifunctional materials, nanosensors and nanoelectronics. Double pulsed laser vaporization process produces SWNTs with the highest percentage of nanotubes in the output material. The normal operating conditions include a green laser pulse closely followed by an infrared laser pulse. Lasers ab late a metal-containing graphite target located in a flow tube maintained in an oven at 1473K with argon flow of 100 sccm at a 500 Torr pressure. In the present work a number of production runs were carried out, changing one operating condition at a time. We have studied the effects of nine parameters, including the sequencing of the laser pulses, pulse separation times, laser energy densities, the type of buffer gas used, oven temperature, operating pressure, flow rate and inner flow tube diameters. All runs were done using the same graphite target. The collected nanotube material was characterized by a variety of analytical techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman and thermo gravimetric analysis (TGA). Results indicate trends that could be used to optimize the process and increase the efficiency of the production process.

Arepalli, Sivaram↗

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↗

Purification Procedures for Single-Wall Carbon Nanotubes

This report summarizes the comparison of a variety of procedures used to purify carbon nanotubes. Carbon nanotube material is produced by the arc process and laser oven process. Most of the procedures are tested using laser-grown, single-wall nanotube (SWNT) material. The material is characterized at each step of the purification procedures by using different techniques including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), Raman, X-ray diffractometry (XRD), thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR), and high-performance liquid chromatography (HPLC). The identified impurities are amorphous and graphitic carbon, catalyst particle aggregates, fullerenes, and hydrocarbons. Solvent extraction and low-temperature annealing are used to reduce the amount of volatile hydrocarbons and dissolve fullerenes. Metal catalysts and amorphous as well as graphitic carbon are oxidized by reflux in acids including HCl, HNO3 and HF and other oxidizers such as H2O2. High-temperature annealing in vacuum and in inert atmosphere helps to improve the quality of SWNTs by increasing crystallinity and reducing intercalation.

Gorelik, Olga P.↗

In-Situ Diagnostics of Carbon Nanotube Production by Laser Ablation

This presentation involves emission and laser induced fluorescence (LIP) data obtained during carbon nanotube production by double pulse laser oven method. Recent LIP data of nickel indicate longer decay (of the order of few milliseconds) of nickel atomic vapor. This contrasts with less than a millisecond decays of C2 and C3 observed in the plume. The possible role of nickel in the kinetics of carbon nanotube formation will be discussed. Evolution of the laser ablated plume is recorded as plume images which are correlated with the transient emission and LIP data

Arepalli, Sivaram↗

Progress in Laser Based Carbon Nanotube Production and In-Situ Diagnostics at NASA/JSC

This paper focuses on the improvement of carbon nanotube production with the upgraded laser system operating at 60 Hz. The yield has increased by about five times with the new system, while the quality of the single wall nanotube (SWNT) is unchanged. Recent diagnostic data of spatial and temporal evolution of C2 in the laser ablation plume are obtained by imaging the plume area on a gated change coupled device. A three-laser setup is used to monitor nickel atoms in different parts of the plume by laser induced fluorescence (LIF). Measurements are made at different times after the ablating lasers. These results, along with the previous measurements of emission and LIF of C2 will be discussed. Our ultimate goal is to use these measurements to model the nanotube growth mechanism.

Arepalli, Sivaram↗

Purification of Carbon Nanotubes: Alternative Methods

Traditional carbon nanotube purification process involves nitric acid refluxing and cross flow filtration using surfactant TritonX. This is believed to result in damage to nanotubes and surfactant residue on nanotube surface. Alternative purification procedures involving solvent extraction, thermal zone refining and nitric acid refiuxing are used in the current study. The effect of duration and type of solvent to dissolve impurities including fullerenes and P ACs (polyaromatic compounds) are monitored by nuclear magnetic reasonance, high performance liquid chromatography, and thermogravimetric analysis. Thermal zone refining yielded sample areas rich in nanotubes as seen by scanning electric microscopy. Refluxing in boiling nitric acid seem to improve the nanotube content. Different procedural steps are needed to purify samples produced by laser process compared to arc process. These alternative methods of nanotube purification will be presented along with results from supporting analytical techniques.

Files, Bradley↗

Mechanisms of Carbon Nanotube Production by Laser Ablation Process

We will present possible mechanisms for nanotube production by laser oven process. Spectral emission of excited species during laser ablation of a composite graphite target is compared with that of laser irradiated C60 vapor. The similarities in the transient and spectral data suggest that fullerenes are intermediate precursors for nanotube formation. The confinement of the ablation products by means of a 25-mm diameter tube placed upstream of the target seems to improve the production and purity of nanotubes. Repeated laser pulses vaporize the amorphous/graphitic carbon and possibly catalyst particles, and dissociate fullerenes yielding additional feedstock for SWNT growth.

Scott, Carl D.↗

Nanotube Production and Applications at Johnson Space Center

Promise of applications of carbon nanotubes has led to an intense effort at NASA/JSC, especially in the area of nanotube composites. Using the extraordinary mechanical strength of nanotubes, NASA hopes to design this revolutionary lightweight material for use in aerospace applications. Current research focuses on structural polymeric materials to attempt to lower the weight of spacecraft necessary for interplanetary missions. Other applications of nanotubes are also of interest for energy storage, gas storage, nanoelectronics, field emission, and biomedical applications. In pursuit of these goals, we have set up both laser and arc production processes for nanotubes. An in-depth diagnostic study of the plasma plume in front of the laser target has been studied to try to determine nanotube growth mechanisms. Complementary studies of characterization of nanotube product have added to knowledge of growth conditions. Results of our preliminary experiments in incorporating nanotubes into composites will be presented. Morphology and mechanical properties of the nanotubes composites will be discussed.

Nikolaev, Pavel↗

Diagnostics of Laser Produced Plume Under Carbon Nanotube Growth Conditions

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.

Arepalli, Sivaram↗

In situ Diagnostics During Carbon Nanotube Production by Laser Ablation

The preliminary results of spectral analysis of the reaction zone during the carbon nanotube production by laser ablation method indicate synergetic dependence on dual laser setup. The emission spectra recorded from different regions of the laser ablated plume at different delay times from the laser pulses are used to map the temperatures of C2 and C3. These are compared with Laser Induced Fluorescence (LIF) spectra also obtained during production to model the growth mechanism of carbon nanotubes. Experiments conducted to correlate the spectral features with nanotube yields as a function of different production parameters will be discussed.

Arepalli, Sivaram↗

Electronically Excited C2 from Laser Photodissociated C60

Spectral and transient emission measurements are made of radiation from products of laser excitation of buckminsterfullerene (C60) vapor diluted in argon at 973 K. The principal radiation is from the Swan band system of C2 and, at early times, also from a black body continuum. The C2 radiation is observed only when C60 is excited by green (532 nm) and not with IR (1064 nm) laser radiation at energy densities of about 1.5 J/square cm. Transient measurements indicate that there are two characteristic periods of decay of radiation. The first period, lasting about 2 micro seconds, has a characteristic decay time of about 0.3 micro seconds. The second period, lasting at least 50 micro seconds, has a characteristic decay time of about 5 micro seconds. These characteristic times are thought to be associated with cooling of C60 molecules or nanosized carbon particles during the early period; and with electronically excited C2 that is a decomposition product of laser excited C60, C58, ... molecules during the later period.

Arepalli, Sivaram↗

Production and Characterization of Carbon Nanotubes and Nanotube-Based Composites

The Nobel Prize winning discovery of the Buckuball (C60) in 1985 at Rice University by a group including Dr. Richard Smalley led to the whole new class of carbon allotropes including fullerenes and nanotubes. Especially interesting from many viewpoints are single-walled carbon nanotubes, which structurally are like a single graphitic sheet wrapped around a cylinder and capped at the ends. This cylinders have diameter as small as 0.5 - 2 nm (1/100,000th the diameter of a human hair) and are as long as 0.1 - 1 mm. Nanotubes are really individual molecules and believed to be defect-free, leading to high tensile strength despite their low density. Additionally, these fibers exhibit electrical conductivity as high as copper, thermal conductivity as high as diamond, strength 100 times higher than steel at one-sixth the weight, and high strain to failure. Thus it is believed that developments in the field of nanotechnology will lead to stronger and lighter composite materials for next generation spacecraft. Lack of a bulk method of production is the primary reason nanotubes are not used widely today. Toward this goal JSC nanotube team is exploring three distinct production techniques: laser ablation, arc discharge and chemical vapor deposition (CVD, in collaboration with Rice University). In laser ablation technique high-power laser impinges on the piece of carbon containing small amount of catalyst, and nanotubes self-assemble from the resulting carbon vapor. In arc generator similar vapor is created in arc discharge between carbon electrodes with catalyst. In CVD method nanotubes grow at much lower temperature on small catalyst particles from carbon-containing feedstock gas (methane or carbon monoxide). As of now, laser ablation produces cleanest material, but mass yield is rather small. Arc discharge produces grams of material, but purity is low. CVD technique is still in baby steps, but preliminary results look promising, as well as perspective of scaling the process up. We are also working on necessary purification of nanotubes. Applications of nanotubes are in such various fields as lightweight composites, molecular electronics, energy storage (electrodes in Li ion batteries), flat panel displays, conductive polymers, etc. JSC nanotube team is focused on development of lightweight materials. We work on the injection thermoset epoxies reinforced with nanotubes. Early results show good wetting of nanotube surface with epoxy, which is very important. More research will be possible as more nanotubes become available.

Nikolaev, Pavel↗

Measuring Arc-Jet Velocity With Laser-Induced Fluorescence

Laser-induced fluorescence in copper atoms entrained in arc jet provides spectrum from which temperature computed. Velocity of flow calculated from shift in spectrum between different angles of incidence. Two major advantages of this method of measurement: relatively nonintrusive; and laser beam focused to micro-sized region to yield high spatial resolution.

Yuen, Eric H.↗

Copper atom based measurements of velocity and turbulence in arc jet flows

Laboratory and field measurements were combined with a modeling effort to explore the feasibility of using atomic copper laser-induced fluorescence to measure velocity, turbulence, and temperature in arcjet flows. Both CW and pulsed frequency-doubled dye lasers were used to demonstrate the ability to measure velocity with 10 percent accuracy at rates of 200,000 cm/s in a rarefied flow of Cu atoms seeded in He. The pulsed laser established a threshold energy for power-broadening of the absorption line at 3.5 x 10 to the -8th J/sq cm. Field measurements at the NASA/JSC 10-MW arcjet facility demonstrated the ability to perform these measurements under actual test conditions. The use of this technique to measure freestream temperatures in the flow was examined for the 0.08/cm linewidth laser used in the NASA/JSC effort. Finally, single-shot turbulence measurements at the USAF/AEDC 35-MW H2 arcjet facility were measured with 4 percent accuracy using the laser/absorption line-overlap technique.

Marinelli, William J.↗