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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS2009

High-Throughput Top-Down and Bottom-Up Processes for Forming Single-Nanotube Based Architectures for 3D Electronics

We have developed manufacturable approaches to form single, vertically aligned carbon nanotubes, where the tubes are centered precisely, and placed within a few hundred nm of 1-1.5 micron deep trenches. These wafer-scale approaches were enabled by chemically amplified resists and inductively coupled Cryo-etchers for forming the 3D nanoscale architectures. The tube growth was performed using dc plasma-enhanced chemical vapor deposition (PECVD), and the materials used for the pre-fabricated 3D architectures were chemically and structurally compatible with the high temperature (700 C) PECVD synthesis of our tubes, in an ammonia and acetylene ambient. Tube characteristics were also engineered to some extent, by adjusting growth parameters, such as Ni catalyst thickness, pressure and plasma power during growth. Such scalable, high throughput top-down fabrication techniques, combined with bottom-up tube synthesis, should accelerate the development of PECVD tubes for applications such as interconnects, nano-electromechanical (NEMS), sensors or 3D electronics in general.

plasma-enhanced chemical vapor deposition (PECVD),↗
NASA NTRS1982

Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts

The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.

Manning, M. P.↗
NASA NTRS2014

Novel Catalysts and Processing Technologies for Production of Aerospace Fuels from Non-Petroleum Raw Materials

Transportation fuels production (including aerospace propellants) from non-traditional sources (gases, waste materials, and biomass) has been an active area of research and development for decades. Reducing terrestrial waste streams simultaneous with energy conversion, plentiful biomass, new low-cost methane sources, and/or extra-terrestrial resource harvesting and utilization present significant technological and business opportunities being realized by a new generation of visionary entrepreneurs. We examine several new approaches to catalyst fabrication and new processing technologies to enable utilization of these nontraditional raw materials. Two basic processing architectures are considered: a single-stage pyrolysis approach that seeks to basically re-cycle hydrocarbons with minimal net chemistry or a two-step paradigm that involves production of supply or synthesis gas (mainly carbon oxides and H2) followed by production of fuel(s) via Sabatier or methanation reactions and/or Fischer-Tröpsch synthesis. Optimizing the fraction of product stream relevant to targeted aerospace (and other transportation) fuels via modeling, catalyst fabrication and novel reactor design are described. Energy utilization is a concern for production of fuels for either terrestrial or space operations; renewable sources based on solar energy and/or energy efficient processes may be mission enabling. Another important issue is minimizing impurities in the product stream(s), especially those potentially posing risks to personnel or operations through (catalyst) poisoning or (equipment) damage. Technologies being developed to remove (and/or recycle) heteroatom impurities are briefly discussed as well as the development of chemically robust catalysts whose activities are not diminished during operation. The potential impacts on future missions by such new approaches as well as balance of system issues are addressed.

space processing↗
NASA NTRS2014

Novel Catalysts and Processing Technologies for Production of Aerospace Fuels from Non-Petroleum Raw Materials

Transportation fuels production (including aerospace propellants) from non-traditional sources (gases, waste materials, and biomass) has been an active area of research and development for decades. Reducing terrestrial waste streams simultaneous with energy conversion, plentiful biomass, new low-cost methane sources, and/or extra-terrestrial resource harvesting and utilization present significant technological and business opportunities being realized by a new generation of visionary entrepreneurs. We examine several new approaches to catalyst fabrication and new processing technologies to enable utilization of these non-traditional raw materials. Two basic processing architectures are considered: a single-stage pyrolysis approach that seeks to basically re-cycle hydrocarbons with minimal net chemistry or a two-step paradigm that involves production of supply or synthesis gas (mainly carbon oxides and hydrogen) followed by production of fuel(s) via Sabatier or methanation reactions and/or Fischer-Tropsch synthesis. Optimizing the fraction of product stream relevant to targeted aerospace (and other transportation) fuels via modeling, catalyst fabrication and novel reactor design are described. Energy utilization is a concern for production of fuels for either terrestrial or space operations; renewable sources based on solar energy and/or energy efficient processes may be mission enabling. Another important issue is minimizing impurities in the product stream(s), especially those potentially posing risks to personnel or operations through (catalyst) poisoning or (equipment) damage. Technologies being developed to remove (and/or recycle) heteroatom impurities are briefly discussed as well as the development of chemically robust catalysts whose activity are not diminished during operation. The potential impacts on future missions by such new approaches as well as balance of system issues are addressed.

propellants↗
NASA NTRS1976

Low cost silicon solar array project. Task 1: Establishment of the feasibility of a process capable of low cost, high volume production of silane, SiH4

The kinetics of the redistribution of dichlorosilane and trichlorosilane vapor over a tertiary amine ion exchange resin catalyst were investigated. The hydrogenation of SiCl4 to form HSiCl3 and the direct synthesis of H2SiCl2 from HCl gas and metallurgical silicon metal were also studied. The purification of SiH4 using activated carbon adsorbent was studied along with a process for storing SiH4 absorbed on carbon. The latter makes possible a higher volumetric efficiency than compressed gas storage. A mini-plant designed to produce ten pounds per day of SiH4 is described.

Breneman, W. C.↗
NASA NTRS1974

Catalytic trimerization of aromatic nitriles for synthesis of polyimide matrix resins

Aromatic nitriles may be trimerized at moderate temperature and pressure with p-toluenesulfonic acid as catalyst. Studies were conducted to establish the effect of the reaction temperature, pressure, time, and catalyst concentration on yield of the trimerized product. Trimerization studies were also conducted to establish the effect of substituting electron donating or withdrawing groups on benzonitrile. Preliminary results of using the catalytic trimerization approach to prepare s-triazine cross-linked polyimide/graphite fiber composites are presented.

Hsu, L. C.↗
NASA NTRS1974

Catalytic trimerization of aromatic nitriles for synthesis of polyimide matrix resins

Aromatic nitriles may be trimerized at moderate temperature and pressure with p-toluenesulfonic acid as catalyst. Studies were conducted to establish the effect of the reaction temperature, pressure, time, and catalyst concentration on yield of the trimerized product. Trimerization studies were also conducted to establish the effect of substituting electron donating or withdrawing groups on benzonitrile. Preliminary results of using the catalytic trimerization approach to prepare s-triazine cross-linked polyimide/graphite fiber composites are presented.

Hsu, L.-C.↗
NASA NTRS2015

Great New Insights from Failed Experiments, Unanticipated Results and Embracing Controversial Observations

Experimental data and observations, whether telescopic or analytical, are never wrong, though data derived from such sources can be misinterpreted or applied inappropriately to derive conclusions that are incorrect. Given that nature always behaves according to the laws of physics and chemistry, rather than according to currently popular models and theories, experimental results should always be considered correct even when the results are far from those that one might initially expect. We discuss a number of cases where the results of experiments, even one carried out as a simple calibration measure, produced wildly different results that generally required many years of effort or contemplation to understand. On the positive side, exploration of the circumstances that produced the errant results often led to new and interesting insights concerning processes that might occur in natural environments and that were well worth the effort involved. Specifically, we show how an experiment that "failed" due to a broken conductor led to experiments that made the first refractory oxide solids containing mass independently fractionated oxygen isotopes and to 1998 predictions of the oxygen isotopic composition of the sun that were confirmed by the analysis of Genesis samples in 2011. We describe a calibration experiment that unexpectedly produced single magnetic domain iron particles. We discuss how tracking down a persistent source of "contamination" in experiments intended to produce amorphous iron and magnesium silicate smokes led to a series of studies on the synthesis of carbonaceous grain coatings that turn out to be very efficient Fischer-Tropsch catalysts and have great potential for trapping the planetary noble gases found in meteorites. We describe how models predicting the instability of silicate grains in circumstellar environments spurred new measurements of the vapor pressure of SiO partially based on previous experiments showing unexpected but systematic non-equilibrium behavior instead of the anticipated equilibrium products resembling meteoritic minerals. We trace the process that led from observations of the presence of crystalline minerals detected in the comae of some comets to the 1999 prediction of large-scale circulation of materials from the hot, innermost regions of the solar nebula out to the cold dark nebular environments where comets form. This large-scale circulation was ultimately confirmed by analyses of highly refractory Stardust samples collected from the Kuiper Belt Comet Wild 2. Finally we discuss a modern and still unresolved conflict between the assumptions built into three well known processes: the CO Self Shielding Model for mass independent isotopic fractionation of oxygen in solar system solids, rapid and thorough mixing within the solar nebula, and the efficient conversion of CO into organic coatings and volatiles on the surfaces of nebular grains via Fischer-Tropsch-type processes.

controversial↗
NASA NTRS1989

Stable carbon and sulfur isotopes as records of the early biosphere

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

Desmarais, David J.↗
NASA NTRS2008

Magnetic Property Measurements on Single Wall Carbon Nanotube-Polyimide Composites

Temperature and magnetic field dependent magnetization measurements were performed on polyimide nanocomposite samples, synthesized with various weight percentages of single wall carbon nanotubes. It was found that the magnetization of the composite, normalized to the mass of nanotube material in the sample, decreased with increasing weight percentage of nanotubes. It is possible that the interfacial coupling between the carbon nanotube (CNT) fillers and the polyimide matrix promotes the diamagnetic response from CNTs and reduces the total magnetization of the composite. The coercivity of the samples, believed to originate from the residual magnetic catalyst particles, was enhanced and had a stronger temperature dependence as a result of the composite synthesis. These changes in magnetic properties can form the basis of a new approach to investigate the interfacial properties in the CNT nanocomposites through magnetic property measurements.

Sun, Keun J.↗
NASA NTRS2004

Spatial Distributions of Metal Atoms During Carbon SWNTs Formation: Measurements and Modelling

Experiments and modelling have been undertaken to clarify the role of metal catalysts during single-wall carbon nanotube formation. For instance, we wonder whether the metal catalyst is active as an atom, a cluster, a liquid or solid nanoparticle [1]. A reactor has been developed for synthesis by continuous CO2-laser vaporisation of a carbon-nickel-cobalt target in laminar helium flow. The laser induced fluorescence technique [2] is applied for local probing of gaseous Ni, Co and CZ species throughout the hot carbon flow of the target heated up to 3500 K. A rapid depletion of C2 in contrast to the spatial extent of metal atoms is observed in the plume (Fig. 1). This asserts that C2 condenses earlier than Ni and Co atoms.[3, 4]. The depletion is even faster when catalysts are present. It may indicate that an interaction between metal atoms and carbon dimers takes place in the gas as soon as they are expelled from the target surface. Two methods of modelling are used: a spatially I-D calculation developed originally for the arc process [5], and a zero-D time dependent calculation, solving the chemical kinetics along the streamlines [6]. The latter includes Ni cluster formation. The peak of C2 density is calculated close to the target surface where the temperature is the highest. In the hot region, C; is dominant. As the carbon products move away from the target and mix with the ambient helium, they recombine into larger clusters, as demonstrated by the peak of C5 density around 1 mm. The profile of Ni-atom density compares fairly well with the measured one (Fig. 2). The early increase is due to the drop of temperature, and the final decrease beyond 6 mm results from Ni cluster formation at the eutectic temperature (approx.1600 K).

Cau, M.↗
NASA NTRS1976

Origin of organic compounds on the primitive earth and in meteorites

The paper examines the role and relative contributions of different forms of energy to the synthesis of amino acids and other organic compounds on the primitive earth and in the solar nebula. Attention is directed mainly to the activation steps and formation of reactive intermediate compounds. Electric discharges appear to be not only the most efficient energy for amino acid synthesis but also yield a mixture of amino acids that is qualitatively and quantitatively the same as that found in the Murchison carbonaceous chondrite. Ultraviolet light is likely to have played a major role in prebiotic synthesis. The reaction of CO plus H2 plus NH3 on the surface of a Fischer-Tropsch catalyst produces reactive intermediates which lead to amino acids and other organic compounds in a much less efficient way than electric discharges.

Miller, S. L.↗
NASA NTRS1980

Perfluroether triazine elastomers

In order to obtain high performance elastomers with the high thermal stability and chemical inertness of perfluoroalkylene triazine and a low glass transition temperature, perfluoroether triazine elastomers were synthesized. The procedure for elastomer synthesis is described as well as general experimental methods. Results are presented and discussed. The screening of catalysts for the dehydration of perfluoroether diamide is also considered.

Korus, R. A.↗
NASA NTRS2003

New Method Developed To Purify Single Wall Carbon Nanotubes for Aerospace Applications

Single wall carbon nanotubes have attracted considerable attention because of their remarkable mechanical properties and electrical and thermal conductivities. Use of these materials as primary or secondary reinforcements in polymers or ceramics could lead to new materials with significantly enhanced mechanical strength and electrical and thermal conductivity. Use of carbon-nanotube-reinforced materials in aerospace components will enable substantial reductions in component weight and improvements in durability and safety. Potential applications for single wall carbon nanotubes include lightweight components for vehicle structures and propulsion systems, fuel cell components (bipolar plates and electrodes) and battery electrodes, and ultra-lightweight materials for use in solar sails. A major barrier to the successful use of carbon nanotubes in these components is the need for methods to economically produce pure carbon nanotubes in large enough quantities to not only evaluate their suitability for certain applications but also produce actual components. Most carbon nanotube synthesis methods, including the HiPCO (high pressure carbon monoxide) method developed by Smalley and others, employ metal catalysts that remain trapped in the final product. These catalyst impurities can affect nanotube properties and accelerate their decomposition. The development of techniques to remove most, if not all, of these impurities is essential to their successful use in practical applications. A new method has been developed at the NASA Glenn Research Center to purify gram-scale quantities of single wall carbon nanotubes. This method, a modification of a gas phase purification technique previously reported by Smalley and others, uses a combination of high-temperature oxidations and repeated extractions with nitric and hydrochloric acid. This improved procedure significantly reduces the amount of impurities (catalyst and nonnanotube forms of carbon) within the nanotubes, increasing their stability significantly. The onset of decomposition of the purified nanotubes (determined by thermal gravimetric analysis in air) is more than 300 C higher than that of the crude nanotubes. Transmission electron microscopy analysis of nanotubes purified by this method reveals near complete removal of iron catalyst particles. Analysis of the nanotubes using inductively coupled plasma spectroscopy revealed that the iron content of the nanotubes was reduced from 22.7 wt% in the crude nanotubes to less than 0.02 wt%. X-ray photoelectron spectroscopy revealed a decrease in iron content after purification as well as an increase in oxygen content due to the formation of carboxylic acid groups on the surface of the nanotubes. Nanotubes purified by this improved method can be readily dispersed in common organic solvents, in particular N,N-dimethylformamide, using prolonged ultrasonic treatment. These dispersions can then be used to incorporate single wall carbon nanotubes into polymer films.

Lebron, Marisabel↗
NASA NTRS1986

Cooperation of catalysts and templates

In order to understand how self-reproducing molecules could have originated on the primitive Earth or extraterrestrial bodies, it would be useful to find laboratory models of simple molecules which are able to carry out processes of catalysis and templating. Furthermore, it may be anticipated that systems in which several components are acting cooperatively to catalyze each other's synthesis will have different behavior with respect to natural selection than those of purely replicating systems. As the major focus of this work, laboratory models are devised to study the influence of short peptide catalysts on template reactions which produce oligonucleotides or additional peptides. Such catalysts could have been the earliest protoenzymes of selective advantage produced by replicating oligonucleotides. Since this is a complex problem, simpler systems are also studied which embody only one aspect at a time, such as peptide formation with and without a template, peptide catalysis of nontemplated peptide synthesis, and model reactions for replication of the type pioneered by Orgel.

White, D. H.↗
NASA NTRS2016

Relating FTS Catalyst Properties to Performance

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.

Zirconia↗