Engineering topics

Arepalli, Sivaram

Publications and source records attributed to Arepalli, Sivaram.

At least 19 records

NASA NTRS2013

Soft-Bake Purification of SWCNTs Produced by Pulsed Laser Vaporization

The "soft-bake" method is a simple and reliable initial purification step first proposed by researchers at Rice University for single-walled carbon nanotubes (SWCNT) produced by high-pressure carbon mon oxide disproportionation (HiPco). Soft-baking consists of annealing as-produced (raw) SWCNT, at low temperatures in humid air, in order to degrade the heavy graphitic shells that surround metal particle impurities. Once these shells are cracked open by the expansion and slow oxidation of the metal particles, the metal impurities can be digested through treatment with hydrochloric acid. The soft-baking of SWCNT produced by pulsed-laser vaporization (PLV) is not straightforward, because the larger average SWCNT diameters (.1.4 nm) and heavier graphitic shells surrounding metal particles call for increased temperatures during soft-bake. A part of the technology development focused on optimizing the temperature so that effective cracking of the graphitic shells is balanced with maintaining a reasonable yield, which was a critical aspect of this study. Once the ideal temperature was determined, a number of samples of raw SWCNT were purified using the soft-bake method. An important benefit to this process is the reduced time and effort required for soft-bake versus the standard purification route for SWCNT. The total time spent purifying samples by soft-bake is one week per batch, which equates to a factor of three reduction in the time required for purification as compared to the standard acid purification method. Reduction of the number of steps also appears to be an important factor in improving reproducibility of yield and purity of SWCNT, as small deviations are likely to get amplified over the course of a complicated multi-step purification process.

Yowell, Leonard↗

NASA NTRS2010

NASA-JSC Protocol for the Characterization of Single Wall Carbon Nanotube Material Quality

It is well known that the raw as well as purified single wall carbon nanotube (SWCNT) material always contain certain amount of impurities of varying composition (mostly metal catalyst and non-tubular carbon). Particular purification method also creates defects and/or functional groups in the SWCNT material and therefore affects the its dispersability in solvents (important to subsequent application development). A number of analytical characterization tools have been used successfully in the past years to assess various properties of nanotube materials, but lack of standards makes it difficult to compare these measurements across the board. In this work we report the protocol developed at NASA-JSC which standardizes measurements using TEM, SEM, TGA, Raman and UV-Vis-NIR absorption techniques. Numerical measures are established for parameters such as metal content, homogeneity, thermal stability and dispersability, to allow easy comparison of SWCNT materials. We will also report on the recent progress in quantitative measurement of non-tubular carbon impurities and a possible purity standard for SWCNT materials.

Arepalli, Sivaram↗

NASA NTRS2010

Optimizing a Laser Process for Making Carbon Nanotubes

A systematic experimental study has been performed to determine the effects of each of the operating conditions in a double-pulse laser ablation process that is used to produce single-wall carbon nanotubes (SWCNTs). The comprehensive data compiled in this study have been analyzed to recommend conditions for optimizing the process and scaling up the process for mass production. The double-pulse laser ablation process for making SWCNTs was developed by Rice University researchers. Of all currently known nanotube-synthesizing processes (arc and chemical vapor deposition), this process yields the greatest proportion of SWCNTs in the product material. The aforementioned process conditions are important for optimizing the production of SWCNTs and scaling up production. Reports of previous research (mostly at Rice University) toward optimization of process conditions mention effects of oven temperature and briefly mention effects of flow conditions, but no systematic, comprehensive study of the effects of process conditions was done prior to the study described here. This was a parametric study, in which several production runs were carried out, changing one operating condition for each run. The study involved variation of a total of nine parameters: the sequence of the laser pulses, pulse-separation time, laser pulse energy density, buffer gas (helium or nitrogen instead of argon), oven temperature, pressure, flow speed, inner diameter of the flow tube, and flow-tube material.

Arepalli, Sivaram↗

NASA NTRS2009

Room-Temperature Ionic Liquids for Electrochemical Capacitors

A document discusses room-temperature ionic liquids (RTILs) used as electrolytes in carbon-nanotube-based, electrochemical, double-layer capacitors. Unlike the previous electrolyte (EtNB4 in acetonitrile), the RTIL used here does not produce cyanide upon thermal decomposition and does not have a moisture sensitivity.

Fireman, Heather↗

NASA NTRS2008

Control of the Diameter and Chiral Angle Distributions during Production of Single-wall Carbon Nanotubes

Many applications of single wall carbon nanotubes (SWCNT), especially in microelectronics, will benefit from use of certain (n,m) nanotube types (metallic, small gap semiconductor, etc.). However, as produced SWCNT samples are polydispersed, with many (n,m) types present and typical approximate 1:2 metal/semiconductor ratio. It has been recognized that production of SWCNTs with narrow 'tube type populations' is beneficial for their use in applications, as well as for the subsequent sorting efforts. In the present work, SWCNTs were produced by a pulsed laser vaporization (PLV) technique. The nanotube type populations were studied with respect to the production temperature with two catalyst compositions: Co/Ni and Rh/Pd. The nanotube type populations were measured via photoluminescence, UV-Vis-NIR absorption and Raman spectroscopy. It was found that in the case of Co/Ni catalyst, decreased production temperature leads to smaller average diameter, exceptionally narrow diameter distribution, and strong preference toward (8,7) nanotubes. The other nanotubes present are distributed evenly in the 7-30 deg chiral angle range. In the case of Rh/Pd catalyst, a decrease in the temperature leads to a small decrease in the average diameter, with the chiral angle distribution skewed towards 30 o and a preference toward (7,6), (8,6) and (8,7) nanotubes. However, the diameter distribution remains rather broad. These results demonstrate that PLV production technique can provide at least partial control over the nanotube (n,m) populations. In addition, these results have implications for the understanding the nanotube nucleation mechanism in the laser oven.

Nikolaev, Pavel↗

NASA NTRS2008

Single Wall Nanotube Type-Specific Functionalization and Separation

Metallic single-wall carbon nanotubes were selectively solubilized in THF and separated from semiconducting nanotubes. Once separated, the functionalized metallic tubes were de-functionalized to restore their metallic band structure. Absorption and Raman spectroscopy of the enriched samples support conclusions of the enrichment of nanotube samples by metallic type. A scalable method for enriching nanotube conductive type has been developed. Raman and UV-Vis data indicate SWCNT reaction with dodecylbenzenediazonium results in metallic enrichment. It is expected that further refinement of this techniques will lead to more dramatic separations of types and diameters.

Boul, Peter↗

NASA NTRS2007

Developing Carbon Nanotube Standards at NASA

Single wall carbon nanotubes (SWCNTs) are currently being produced and processed by several methods. Many researchers are continuously modifying existing methods and developing new methods to incorporate carbon nanotubes into other materials and utilize the phenomenal properties of SWCNTs. These applications require availability of SWCNTs with known properties and there is a need to characterize these materials in a consistent manner. In order to monitor such progress, it is critical to establish a means by which to define the quality of SWCNT material and develop characterization standards to evaluate of nanotube quality across the board. Such characterization standards should be applicable to as-produced materials as well as processed SWCNT materials. In order to address this issue, NASA Johnson Space Center has developed a protocol for purity and dispersion characterization of SWCNTs. The NASA JSC group is currently working with NIST, ANSI and ISO to establish purity and dispersion standards for SWCNT material. A practice guide for nanotube characterization is being developed in cooperation with NIST. Furthermore, work is in progress to incorporate additional characterization methods for electrical, mechanical, thermal, optical and other properties of SWCNTs.

Nikolaev, Pasha↗

NASA NTRS2007

Strain Dependence of Photoluminescense of Individual Carbon Nanotubes

We have investigated strain dependence of photoluminescense (PL) spectra of single wall carbon nanotubes (SWNT). Nanotubes were sparsely dispersed in a thin PMMA film applied to acrylic bar, and strained in both compression and extension by bending this bar in either direction in a homebuilt four-point bending rig. The average surface strain was measured with high accuracy by a resistive strain gage applied on top of the film. The near infrared imaging and spectroscopy were performed on the inverted microscope equipped with high numerical aperture reflective objective lens and InGaAs CCD cameras. PL was excited with a diode laser at either 658, 730 or 785 nm, linearly polarized in the direction of the strain. We were able to measure (n,m) types and orientation of individual nanotubes with respect to strain direction and strain dependence of their PL maxima. It was found that PL peak shifts with respect to the values measured in SDS micelles are a sum of three components. First, a small environmental shift due to difference in the dielectric constant of the surrounding media, that is constant and independent of the nanotube type. Second, shift due to isotropic compression of the film during drying. Third, shifts produced by the uniaxial loading of the film in the experiment. Second and third shifts follow expression based on the first-order expansion of the TB hamiltonian. Their magnitude is proportional to the nanotube chiral angle and strain, and direction is determined by the nanotube quantum number. PL strain dependence measured for a number of various nanotube types allows to estimate TB carbon-carbon transfer integral.

Nikolaev, Pavel N.↗

NASA NTRS2007

Developing Carbon Nanotube Standards at NASA

Single wall carbon nanotubes (SWCNTs) are currently being produced and processed by several methods. Many researchers are continuously modifying existing methods and developing new methods to incorporate carbon nanotubes into other materials and utilize the phenomenal properties of SWCNTs. These applications require availability of SWCNTs with known properties and there is a need to characterize these materials in a consistent manner. In order to monitor such progress, it is critical to establish a means by which to define the quality of SWCNT material and develop characterization standards to evaluate of nanotube quality across the board. Such characterization standards should be applicable to as-produced materials as well as processed SWCNT materials. In order to address this issue, NASA Johnson Space Center has developed a protocol for purity and dispersion characterization of SWCNTs (Ref.1). The NASA JSC group is currently working with NIST, ANSI and ISO to establish purity and dispersion standards for SWCNT material. A practice guide for nanotube characterization is being developed in cooperation with NIST (Ref.2). Furthermore, work is in progress to incorporate additional characterization methods for electrical, mechanical, thermal, optical and other properties of SWCNTs.

Nikolaev, Pasha↗

NASA NTRS2006

Carbon Nanotube Material Quality Assessment

The nanomaterial activities at NASA Johnson Space Center focus on carbon nanotube production, characterization and their applications for aerospace systems. Single wall carbon nanotubes are produced by arc and laser methods. Characterization of the nanotube material is performed using the NASA JSC protocol developed by combining analytical techniques of SEM, TEM, UV-VIS-NIR absorption, Raman, and TGA. A possible addition of other techniques such as XPS, and ICP to the existing protocol will be discussed. Changes in the quality of the material collected in different regions of the arc and laser production chambers is assessed using the original JSC protocol. The observed variations indicate different growth conditions in different regions of the production chambers.

Yowell, Leonard↗

NASA NTRS2006

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↗

NASA NTRS2006

Measurement Challenges for Carbon Nanotube Material

The advances in large scale applications of carbon nanotubes demand a reliable supply of raw and processed materials. It is imperative to have a consistent quality control of these nanomaterials to distinguish material inconsistency from the modifications induced by processing of nanotubes for any application. NASA Johnson Space Center realized this need five years back and started a program to standardize the characterization methods. The JSC team conducted two workshops (2003 and 2005) in collaboration with NIST focusing on purity and dispersion measurement issues of carbon nanotubes [1]. In 2004, the NASA-JSC protocol was developed by combining analytical techniques of SEM, TEM, UV-VIS-NIR absorption, Raman, and TGA [2]. This protocol is routinely used by several researchers across the world as a first step in characterizing raw and purified carbon nanotubes. A suggested practice guide consisting of detailed chapters on TGA, Raman, electron microscopy and NIR absorption is in the final stages and is undergoing revisions with input from the nanotube community [3]. The possible addition of other techniques such as XPS, and ICP to the existing protocol will be presented. Recent activities at ANSI and ISO towards implementing these protocols as nanotube characterization standards will be discussed.

Sosa, Edward↗

NASA NTRS2005

Nanoscale Materials for Human Space Exploration: Regenerable CO2 Removal

This viewgraph presentation reviews the use of Nanoscale materials in CO2 removal. It presented the background and review work on regenerable CO2 removal for spaceflight application. It demonstrated a new strategy for developing solid-supported amine absorbents based on carbon nanotube materials.

Arepalli, Sivaram↗

NASA NTRS2005

Nanomaterials Work at NASA-Johnson Space Center

Nanomaterials activities at NASA-Johnson Space Center focus on single wall carbon nanotube production, characterization and their applications for aerospace. Nanotubes are produced by arc and laser methods and the growth process is monitored by in-situ diagnostics using time resolved passive emission and laser induced fluorescence of the active species. Parametric study of both these processes are conducted to monitor the effect of production parameters including temperature, buffer gas, flow rate, pressure, laser fluence and arc current. Characterization of the nanotube material is performed using the NASA-JSC protocol developed by combining analytical techniques of SEM, TEM, UV-VIS-NIR absorption, Raman, and TGA. Efforts at JSC over the past five years in composites have centered on structural polymernanotube 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 conductivity exhibited by SWCNTs.

Arepalli, Sivaram↗

NASA NTRS2004

A parametric study of single-wall carbon nanotube growth by laser ablation

Results of a parametric study of carbon nanotube production by the double-pulse laser oven process are presented. The effect of various operating parameters on the production of single-wall carbon nanotubes (SWCNTs) is estimated by characterizing the nanotube material using analytical techniques, including scanning electron microscopy, transmission electron microscopy, thermo gravimetric analysis and Raman spectroscopy. The study included changing the sequence of the laser pulses, laser energy, pulse separation, type of buffer gas used, operating pressure, flow rate, inner tube diameter, as well as its material, and oven temperature. It was found that the material quality and quantity improve with deviation from normal operation parameters such as laser energy density higher than 1.5 J/cm2, pressure lower than 67 kPa, and flow rates higher than 100 sccm. Use of helium produced mainly small diameter tubes and a lower yield. The diameter of SWCNTs decreases with decreasing oven temperature and lower flow rates.

Nanotubes, Carbon/chemistry↗

NASA NTRS2004

Setup for Visual Observation of Carbon-Nanotube Arc Process

A simple optical setup has been devised to enable safe viewing of the arc and measurement of the interelectrode gap in a process in which carbon nanotubes are produced in an arc between a catalyst-filled carbon anode and a graphite cathode. This setup can be used for visually guided manual positioning of the anode to maintain the interelectrode gap at a desired constant value, possibly as a low-technology alternative to the automatic position/voltage control described in Automatic Control of Arc Process for Making Carbon Nanotubes (MSC-23134), NASA Tech Briefs, Vol. 28, No. 3 (March 2004), page 51. The optical setup consists mainly of lenses for projecting an image of the arc onto a wall, plus a calibrated grid that is mounted on the wall so that one can measure the superimposed image of the arc. To facilitate determination of the end point of the process, the anode is notched, by use of a file, at the end of the filled portion that is meant to be consumed in the process. As the anode is consumed and the notch comes into view in the scene projected onto the wall, the process operator switches off the arc current.

Scott, Carl D.↗

NASA NTRS2004

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↗

NASA NTRS2004

Reference standard for carbonaceous impurity measurements in carbon nanotubes

Near-infrared spectroscopy is a convenient tool for measuring nanotube / carbonaceous impurities ratios in carbon nanotube samples. These measurements are based on separation of contributions from nanotubes and impurities to the near-infrared absorption of samples dispersed in DMF, and sample purity is expressed relative to some reference sample. In the current work we produced a reference standard for NIR measurements using purified laser nanotubes. The sample was oxidized slowly using a Temperature Programmed Oxidation (TPO) setup in 2% oxygen / 98 % helium atmosphere. In these conditions, the sample oxidized in several steps, which were attributed to carbonaceous impurities, nanotubes and graphitic shells based on TEM and Raman observations. Stopping oxidation at 625 C (this temperature is sample-specific) allowed us to produce a sample with no carbonaceous impurities and well-defined ratio of nanotubes, graphite and metal catalyst. Since carbonaceous impurities no longer hold nanotubes and particles together, further centrifuging allowed us to remove particles and use this sample as a reference standard in NIR measurements.

Nikolaev, Pavel↗