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All sourcesNASA NTRSDOE OSTI
NASA NTRS2005

Applications of Quantum Chemistry to the Study of Carbon Nanotubes

For several years, scientists at NASA Ames have been studying the properties of carbon nanotubes using various experimental and computational methods. In this talk, I will compare different strategies for using quantum chemistry calculations to describe the electronic structure, deformation and chemical functionalization of single wall carbon nanotubes (SWNT) and the physisorption of small molecules on nanotube surfaces. The SWNT can be treated as an infinite (periodic) or finite length carbon cylinder or as a polycyclic aromatic hydrocarbon (PAH) molecule with an imposed curvature maintained by external constraints (as if it were cut out of the SWNT surface). Calculations are carried out using DFT and MP2 methods and a variety of atomic orbital basis sets from minimal (STO-3G) to valence triple zeta. The optimal approach is based on the particular SWNT property of interest. Examples to be discussed include: nanotube fluorination and other functionalization reactions; coating of nanotubes by water vapor and low-molecular weight organic molecules; and the nature of the interface between SWNT and liquids such as water and amines. In many cases, the quantum chemistry calculations are used to parameterize or validate force fields for molecular dynamics simulations. The results of these calculations have helped explain experimental data and contributed to the design of novel materials and sensors based on carbon nanotubes. Some of this research is described in the following papers:

Jaffe, Richard L.↗
DOE OSTI2024

Characterization of Nitrate, Nitrite, Ammonia, and Tritium in D0220 Cores

This report describes characterization of nitrogen species (nitrate, nitrite, ammonia) in aqueous and solid phases in cores taken in borehole D0220 (well 299-E25-245) under crib 216-A-37-1 at the Hanford Site in 2022 to evaluate (a) the types of nitrogen species currently in the vadose zone and (b) the migration of nitrogen species in the vadose zone. Ammonia and tritium from PUREX decladding condensate were sporadically discharged to the crib from 1977 to 1989. During discharge operations, the estimated travel time through the vadose zone to groundwater was 2.5 to 9 months. By 2003, a characterization borehole (C4106) showed residual pore water with elevated tritium and nitrate in the first 100 ft of the vadose zone, which is likely from the crib. However, there was significantly more nitrate present at the shallowest depth (15 to 22 ft), which may indicate a different source for nitrate, such as adsorbed ammonia slowly being oxidized or nitrogen species precipitates slowly dissolving. In this study, more extensive nitrogen species characterization was done on D0220 cores (drilled in 2022) at 40- and 262-ft depths, which included (a) aqueous nitrate, nitrite, and tritium; (b) adsorbed ammonia; (c) nitrogen in carbonates (or other minerals dissolved in acidic acid); (d) nitrogen in iron oxides (or other minerals dissolved in oxalic acid); and (e) nitrogen in hard-to-extract minerals (minerals dissolved in nitric acid). High pore water nitrate (226 to 331 mg/L) at 40-ft depth measured in D0220 (2022) compared to 60 mg/L at 40-ft depth in C4106 (2003) may indicate nitrate is migrating deeper. Tritium concentrations (pore water 132,000 to 148,000 pCi/L) measured in D0220 at 40-ft depth in 2022 were considerably higher than in C4106 at 40-ft depth (160 pCi/L). Additional nitrogen species mass was present in adsorbed and precipitated phases in D0220 cores. Low adsorbed ammonia was measured at 40.1- and 261.7-ft depths. Low concentrations of carbonate associated nitrogen and iron oxide-associated nitrogen were present at 40.1 and 40.6 ft depths. Nitrogen species in solid phase extractions indicate nitrogen precipitates or aqueous nitrate or ammonia trapped in sediment microfractures that are coated by precipitates. Overall, the nitrogen species and tritium characterization at two depths in D0220 showed that additional nitrogen species were present in the vadose zone. In addition, elevated pore water nitrate in D0220 at 40 ft depth from 2022 may indicate vertical migration compared to C4106 nitrate profile from 2003. Analysis of additional depths in D0220 and spatial variability of the nitrate plume along the length of the crib (from surface electrical resistivity) would be extremely useful for this comparison.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1982

Calculated performance of a Wolter type I X-ray telescope coated by multilayers

Deposition of multilayered diffraction coatings on the reflecting surfaces of a Wolter type I X-ray telescope offers the potential of using Bragg reflection to achieve enhanced effective area in selected high energy bandpasses. The structure of a gold-carbon multilayer has been optimized for study of 1.8 A iron-line emission with an X-ray telescope designed for observations from Spacelab. The response of this mirror assembly has been calculated as a function of X-ray energy and the resulting effective area is enhanced by a factor of 10 and peaks at 160 sq cm with a bandpass of 0.4 keV FWHM. This enhanced response is sufficient to allow study of the angular distribution of iron-line emission from the 20 brightest cluster X-ray sources during a 7 day Spacelab mission. The possibility of achieving X-ray imaging in narrow bandpasses at even higher energies has been investigated. It is concluded that it should be possible to achieve effective areas of approximately 5 sq cm in bandpasses approximately 1 keV wide for energies in the 15-25 keV range, a spectral region of much importance during the impulsive phase of solar flares.

Catura, R. C.↗
NASA NTRS1988

Long-lived thermal control materials for high temperature and deep space applications

Considerable effort has been put into developing thermal-control materials for the Galileo space-craft. This paper presents a summary of these findings to date with emphasis on requirements, testing and results for the post-Challenger Galileo mission. Polyimide film (Kapton), due to its inherent stability in vacuum, UV, and radiation environments, combined with good mechanical properties over a large temperature range, has been the preferred substrate for spacecraft thermal control materials. Composite outer layers, using Kapton substrates, can be fabricated to meet the requirements of severe space environments. Included in the processing of Kapton-based composite outer layers can be the deposition of metal oxide, metallic and/or polymeric thin-film coatings to provide desirable electrical, optical and thermo-optical properties. In addition, reinforcement of Kapton substrates with fabrics and films is done to improve mechanical properties. Also these substrates can be filled with varying amounts of carbon to achieve particular electrical properties. The investigation and material development reported on here has led to improved thermo-gravimetric stability, surface conductivity, RF transparency, radiation and UV stability, flammability and handle-ability of outer layer thermal control materials for deep space and near-sun spacecraft. Designing, testing, and qualifying composite thermal-control film materials to meet the requirements of the Galileo spacecraft is the scope of this paper.

Whitt, Robin↗
NASA NTRS1993

Polymer Infiltration Studies

Significant progress has been made on the preparation of carbon fiber composites using advanced polymer resins during the past three months. Current and ongoing research activities reported herein include: (1) Prepregger Hot Sled Operation; (2) Ribbonizing Powder-Impregnated Towpreg; (3) Textile Composites from Powder-Coated Towpreg: Role of Bulk Factor; and (4) Powder Curtain Prepreg Process. During the coming months research will be directed toward further development of the new powder curtain prepregging method and on ways to customize dry powder towpreg for textile and robotic applications in aircraft part fabrication. Studies of multi-tow powder prepregging and ribbon preparation will be conducted in conjunction with continued development of prepegging technology and the various aspects of composite part fabrication using customized towpreg. Also, work will continue on the analysis of the new solution prepegger.

Marchello, Joseph M.↗
NASA NTRS1995

Germination, growth rates, and electron microscope analysis of tomato seeds flown on the LDEF

The tomato seeds were flown in orbit aboard the Long Duration Exposure Facility (LDEF) for nearly six years. During this time, the tomato seeds received an abundant exposure to cosmic radiation and solar wind. Upon the return of the LDEF to earth, the seeds were distributed throughout the United States and 30 foreign countries for analysis. The purpose of the experiment was to determine the long term effect of cosmic rays on living tissue. Our university analysis included germination and growth rates as well as Scanning Electron Microscopy and X-ray analysis of the control as well as Space-exposed tomato seeds. In analyzing the seeds under the Electron Microscope, usual observations were performed on the nutritional and epidermis layer of the seed. These layers appeared to be more porous in the Space-exposed seeds than on the Earth-based control seeds. This unusual characteristic may explain the increases in the space seeds growth pattern. (Several test results show that the Space-exposed seeds germinate sooner than the Earth-Based seeds. Also, the Space-exposed seeds grew at a faster rate). The porous nutritional region may allow the seeds to receive necessary nutrients and liquids more readily, thus enabling the plant to grow at a faster rate. Roots, leaves and stems were cut into small sections and mounted. After sputter coating the specimens with Argon/Gold Palladium Plasma, they were ready to be viewed under the Electron Microscope. Many micrographs were taken. The X-ray analysis displayed possible identifications of calcium, potassium, chlorine, copper, aluminum, silicon, phosphate, carbon, and sometimes sulfur and iron. The highest concentrations were shown in potassium and calcium. The Space-exposed specimens displayed a high concentration of copper and calcium in the two specimens. There was a significantly high concentration of copper in the Earth-based specimens, whereas there was no copper in the Space-exposed specimens.

Hammond, Ernest C., Jr.↗
NASA NTRS2009

Integrated High Payoff Rocket Propulsion Technology (IHPRPT) SiC Recession Model

SiC stability and recession rates were modeled in hydrogen/oxygen combustion environments for the Integrated High Payoff Rocket Propulsion Technology (IHPRPT) program. The IHPRPT program is a government and industry program to improve U.S. rocket propulsion systems. Within this program SiC-based ceramic matrix composites are being considered for transpiration cooled injector faceplates or rocket engine thrust chamber liners. Material testing under conditions representative of these environments was conducted at the NASA Glenn Research Center, Cell 22. For the study described herein, SiC degradation was modeled under these Cell 22 test conditions for comparison to actual test results: molar mixture ratio, MR (O2:H2) = 6, material temperatures to 1700 C, combustion gas pressures between 0.34 and 2.10 atm, and gas velocities between 8,000 and 12,000 fps. Recession was calculated assuming rates were controlled by volatility of thermally grown silica limited by gas boundary layer transport. Assumptions for use of this model were explored, including the presence of silica on the SiC surface, laminar gas boundary layer limited volatility, and accuracy of thermochemical data for volatile Si-O-H species. Recession rates were calculated as a function of temperature. It was found that at 1700 C, the highest temperature considered, the calculated recession rates were negligible, about 200 m/h, relative to the expected lifetime of the material. Results compared favorably to testing observations. Other mechanisms contributing to SiC recession are briefly described including consumption of underlying carbon and pitting. A simple expression for liquid flow on the material surface was developed from a one-dimensional treatment of the Navier-Stokes Equation. This relationship is useful to determine under which conditions glassy coatings or thermally grown silica would flow on the material surface, removing protective layers by shear forces. The velocity of liquid flow was found to depend on the gas velocity, the viscosity of gas and liquid, as well as the thickness of the gas boundary layer and the liquid layer. Calculated flow rates of a borosilicate glass coating compared well to flow rates observed for this coating tested on a SiC panel in Cell 22.

Opila, E. J.↗
NASA NTRS2012

Plasma Treatment to Remove Carbon from Indium UV Filters

The sounding rocket experiment FIRE (Far-ultraviolet Imaging Rocket Experiment) will improve the science community fs ability to image a spectral region hitherto unexplored astronomically. The imaging band of FIRE (.900 to 1,100 Angstroms) will help fill the current wavelength imaging observation hole existing from approximately equal to 620 Angstroms to the GALEX band near 1,350 Angstroms. FIRE is a single-optic prime focus telescope with a 1.75-m focal length. The bandpass of 900 to 1100 Angstroms is set by a combination of the mirror coating, the indium filter in front of the detector, and the salt coating on the front of the detector fs microchannel plates. Critical to this is the indium filter that must reduce the flux from Lymanalpha at 1,216 Angstroms by a minimum factor of 10(exp -4). The cost of this Lyman-alpha removal is that the filter is not fully transparent at the desired wavelengths of 900 to 1,100 Angstroms. Recently, in a project to improve the performance of optical and solar blind detectors, JPL developed a plasma process capable of removing carbon contamination from indium metal. In this work, a low-power, low-temperature hydrogen plasma reacts with the carbon contaminants in the indium to form methane, but leaves the indium metal surface undisturbed. This process was recently tested in a proof-of-concept experiment with a filter provided by the University of Colorado. This initial test on a test filter showed improvement in transmission from 7 to 9 percent near 900 with no process optimization applied. Further improvements in this performance were readily achieved to bring the total transmission to 12% with optimization to JPL's existing process.

Greer, Harold F.↗
NASA NTRS1988

The effect of insulated combustion chamber surfaces on direct-injected diesel engine performance, emissions, and combustion

The combustion chamber of a single-cylinder, direct-injected diesel engine was insulated with ceramic coatings to determine the effect of low heat rejection (LHR) operation on engine performance, emissions, and combustion. In comparison to the baseline cooled engine, the LHR engine had lower thermal efficiency, with higher smoke, particulate, and full load carbon monoxide emissions. The unburned hydrocarbon emissions were reduced across the load range. The nitrous oxide emissions increased at some part-load conditions and were reduced slightly at full loads. The poor LHR engine performance was attributed to degraded combustion characterized by less premixed burning, lower heat release rates, and longer combustion duration compared to the baseline cooled engine.

Dickey, Daniel W.↗
NASA NTRS1991

Deposition Of Diamondlike Films By ECR Microwave Plasma

Hard, amorphous hydrogenated carbon films of diamondlike quality deposited at room temperature on silicon, optical glass, and quartz through decomposition of CH4 in electron-cyclotron-resonance (ECR) microwave plasma of CH4 diluted with H2. Technique provides hard, abrasion-resistant coatings for lenses and other optical components. Films chemically inert and posses high electrical resistivity and breakdown fields, valuable properties in microelectronics applications.

Pool, Frederick S.↗
NASA NTRS1993

INEL Spray-forming Research

Spray forming is a near-net-shape fabrication technology in which a spray of finely atomized liquid droplets is deposited onto a suitably shaped substrate or mold to produce a coherent solid. The technology offers unique opportunities for simplifying materials processing without sacrificing, and oftentimes substantially improving, product quality. Spray forming can be performed with a wide range of metals and nonmetals, and offers property improvements resulting from rapid solidification (e.g., refined microstructures, extended solid solubilities and reduced segregation). Economic benefits result from process simplification and the elimination of unit operations. Researchers at the Idaho National Engineering Laboratory (INEL) are developing spray-forming technology for producing near-net-shape solids and coatings of a variety of metals, polymers, and composite materials. Results from several spray forming programs are presented to illustrate the range of capabilities of the technique as well as the accompanying technical and economic benefits. Low-carbon steel strip greater than 0.75 mm thick and polymer membranes for gas/gas and liquid/liquid separations that were spray formed are discussed; recent advances in spray forming molds, dies, and other tooling using low-melting-point metals are described.

Mchugh, Kevin M.↗
DOE OSTI2022

Study of carbon nanotube embedded honey as a resistive switching material

In this paper, natural organic honey embedded with carbon nanotubes (CNTs) was studied as a resistive switching material for biodegradable nonvolatile memory in emerging neuromorphic systems. CNTs were dispersed in a honey-water solution with the concentration of 0.2 wt% CNT and 30 wt% honey. The final honey-CNT-water mixture was spin-coated and dried into a thin film sandwiched in between Cu bottom electrode and Al top electrode to form a honey-CNT based resistive switching memory (RSM). Surface morphology, electrical characteristics and current conduction mechanism were investigated. The results show that although CNTs formed agglomerations in the dried honey-CNT film, both switching speed and the stability in SET and RESET process of honey-CNT RSM were improved. The mechanism of current conduction in CNT is governed by Ohm’s law in low-resistance state and the low-voltage range in high-resistance state, but transits to the space charge limited conduction at high voltages approaching the SET voltage.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Development of an all-metal thick film cost effective metallization system for solar cells

Electrodes made with pastes produced under the previous contract were analyzed and compared with raw materials. A needle-like structure observed on the electroded solar cell was identified as eutectic copper-silicon, a phase considered to benefit the electrical and metallurgical properties of the contact. Electrodes made from copper fluorocarbon and copper silver fluoride also contained this phase but had poor adhesion. A liquid medium, intended to provide transport during carbon fluoride decomposition was incorporated into the paste resulting in better adhesion. The product survived preliminary environmental tests. A 2 cm by 2 cm solar cell made with fluorocarbon activated copper electrodes and gave 7% AMI efficiency (without AR coating). Both silver fluoride and fluorocarbon screened paste electrodes can be produced for approximately $0.04 per watt.

Ross, B.↗
NASA NTRS2008

Plasma Processing of Lunar Regolith Simulant for Diverse Applications

Versatile manufacturing technologies for extracting resources from the moon are needed to support future space missions. Of particular interest is the production of gases and metals from lunar resources for life support, propulsion, and in-space fabrication. Deposits made from lunar regolith could yield highly emissive coatings and near-net shaped parts for replacement or repair of critical components. Equally important is development of high fidelity lunar simulants for ground based validation of potential lunar surface operations. Described herein is an innovative plasma processing technique for insitu production of gases, metals, coatings, and deposits from lunar regolith, and synthesis of high fidelity lunar simulant from NASA issued lunar simulant JSC-1. Initial plasma reduction trials of JSC-1 lunar simulant have indicated production of metallic iron and magnesium. Evolution of carbon monoxide has been detected subsequent to reduction of the simulant using the plasma process. Plasma processing of the simulant has also resulted in glassy phases resembling the volcanic glass and agglutinates found in lunar regolith. Complete and partial glassy phase deposits have been obtained by varying the plasma process variables. Experimental techniques, product characterization, and process gas analysis will be discussed.

Schofield, Elizabeth C.↗
NASA NTRS2005

NASA Tech Briefs, June 2005

Topics covered include: Apparatus Characterizes Transient Voltages in Real Time; Measuring Humidity in Sealed Glass Encasements; Adaptable System for Vehicle Health and Usage Monitoring; Miniature Focusing Time-of-Flight Mass Spectrometer; Cryogenic High-Sensitivity Magnetometer; Wheel Electrometer System; Carbon-Nanotube Conductive Layers for Thin-Film Solar Cells; Patch Antenna Fed via Unequal-Crossed-Arm Aperture; LC Circuits for Diagnosing Embedded Piezoelectric Devices; Nanowire Thermoelectric Devices; Code for Analyzing and Designing Spacecraft Power System Radiators; Decision Support for Emergency Operations Centers; NASA Records Database; Real-Time Principal- Component Analysis; Fuzzy/Neural Software Estimates Costs of Rocket- Engine Tests; Multicomponent, Rare-Earth-Doped Thermal-Barrier Coatings; Reactive Additives for Phenylethynyl-Containing Resins; Improved Gear Shapes for Face Worm Gear Drives; Alternative Way of Shifting Mass to Move a Spherical Robot; Parylene C as a Sacrificial Material for Microfabrication; In Situ Electrochemical Deposition of Microscopic Wires; Improved Method of Manufacturing SiC Devices; Microwave Treatment of Prostate Cancer and Hyperplasia; Ferroelectric Devices Emit Charged Particles and Radiation; Dusty-Plasma Particle Accelerator; Frozen-Plug Technique for Liquid-Oxygen Plumbing; Shock Waves in a Bose-Einstein Condensate; Progress on a Multichannel, Dual-Mixer Stability Analyzer; Development of Carbon- Nanotube/Polymer Composites; Thermal Imaging of Earth for Accurate Pointing of Deep-Space Antennas; Modifications of a Composite-Material Combustion Chamber; Modeling and Diagnostic Software for Liquefying- Fuel Rockets; and Spacecraft Antenna Clusters for High EIRP.

Source record↗
NASA NTRS2002

Structural Health Monitoring of Composite Wound Pressure Vessels

The increasing use of advanced composite materials in the wide range of applications including Space Structures is a great impetus to the development of smart materials. Incorporating these FBG sensors for monitoring the integrity of structures during their life cycle will provide valuable information about viability of the usage of such material. The use of these sensors by surface bonding or embedding in this composite will measure internal strain and temperature, and hence the integrity of the assembled engineering structures. This paper focuses on such a structure, called a composite wound pressure vessel. This vessel was fabricated from the composite material: TRH50 (a Mitsubishi carbon fiber with a 710-ksi tensile strength and a 37 Msi modulus) impregnated with an epoxy resin from NEWPORT composites (WDE-3D-1). This epoxy resin in water dispersed system without any solvents and it cures in the 240-310 degrees F range. This is a toughened resin system specifically designed for pressure applications. These materials are a natural fit for fiber sensors since the polyimide outer buffer coating of fiber can be integrated into the polymer matrix of the composite material with negligible residual stress. The tank was wound with two helical patterns and 4 hoop wraps. The order of winding is: two hoops, two helical and two hoops. The wall thickness of the composite should be about 80 mil or less. The tank should burst near 3,000 psi or less. We can measure the actual wall thickness by ultrasonic or we can burst the tank and measure the pieces. Figure 1 shows a cylinder fabricated out of carbon-epoxy composite material. The strain in different directions is measured with a surface bonded fiber Bragg gratings and with embedded fiber Bragg gratings as the cylinder is pressurized to burst pressures. Figure 2 shows the strain as a function of pressure of carbon-epoxy cylinder as it is pressurized with water. Strain is measured in different directions by multiple gratings oriented in both axial and hoops directions.

Joseph Grant↗
DOE OSTI2023

Exploration of LIBS as a novel and rapid elemental mapping technique of nuclear fuels in the form of surrogate TRISO particles

Laser-induced breakdown spectroscopy (LIBS) was employed to characterize coatings on surrogate fuel particles. Tri-structural isotropic (TRISO) particles are a proposed nuclear fuel alternative for high temperature reactors. These particles are constructed of a ZrO 2 kernel (as a surrogate to uranium), surrounded by an inner pyrolytic carbon layer and are surrounded by an outer carbide layer (ZrC, presented here) to act as a barrier to fission products generated during nuclear reactions. These particles are embedded within a graphite compact and housed within the reactor core. Simply put, due to their robust nature, performing elemental analysis of these particles poses a challenge. Presented here, LIBS is explored as a method for characterizing elemental constituents of these particles, with the focus being on rapid elemental mapping and depth profiling. Different from traditional elemental analysis techniques (e.g., inductively coupled plasma – based methods), LIBS is advantageous because it can directly analyze the sample surface and can detect light elements such as C and O, making it a viable technique for the analysis of small, multilayered particles as spatial elemental information is warranted in the production of these particles. In the work presented here, LIBS was successfully used for discerning small layers (30–50 μm), detecting the location of carbon and oxygen layers, providing fast 2-D mapping (<5 min per particle) and rapid depth profiling (10 s per particle).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗