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Product distributions and rate constants for the reactions of ground-state N(+) ions with CO, NO, CO2, and CH4 were measured. Rate constants were obtained using ion-cyclotron-resonance trapped-ion methods, and product distributions were obtained using a tandem (Dempster-ICR) mass spectrometer. Rapid nitrogen isotope exchange was also observed in N(+)-N2 collisions.
The radioisotope Be-7 was discovered in early 1990 on the front surface, and the front surface only, of the LDEF. A working hypothesis is that the isotope, which is known to be mainly produced in the stratosphere by spallation of nitrogen and oxygen nuclei with cosmic ray protons or secondary neutrons, diffuses upward and is absorbed onto metal surfaces of spacecraft. The upward transport must be rapid, that is, its characteristic time scale is similar to, or shorter than, the 53 day half-life of the isotope. It is probably by analogy with meteoritic metal atmospheric chemistry, that the form of the Be at a few 100 km altitude is as the positive ion Be(+) which is efficiently incorporated into the ionic lattice of oxides, such as Al2O3, Cr2O3, Fe2O3, etc., naturally occurring on surfaces of Al and stainless steel. Other radioisotopes of Be, Cl, and C are also produced in the atmosphere, and a search was begun to discover these. Of interest are Be-10 and C-14 for which the production cross sections are well known. The method of analysis is accelerator mass spectrometry. Samples from LDEF clamp plates are being chemically extracted, purified, and prepared for an accelerator run.
Nano-engineered catalysts, and a method of fabricating them, have been developed in a continuing effort to improve the performances of direct methanol fuel cells as candidate power sources to supplant primary and secondary batteries in a variety of portable electronic products. In order to realize the potential for high energy densities (as much as 1.5 W h/g) of direct methanol fuel cells, it will be necessary to optimize the chemical compositions and geometric configurations of catalyst layers and electrode structures. High performance can be achieved when catalyst particles and electrode structures have the necessary small feature sizes (typically of the order of nanometers), large surface areas, optimal metal compositions, high porosity, and hydrophobicity. The present method involves electrodeposition of one or more catalytic metal(s) or a catalytic-metal/polytetrafluoroethylene nanocomposite on an alumina nanotemplate. The alumina nanotemplate is then dissolved, leaving the desired metal or metal/polytetrafluoroethylene-composite catalyst layer. Unlike some prior methods of making fine metal catalysts, this method does not involve processing at elevated temperature; all processing can be done at room temperature. In addition, this method involves fewer steps and is more amenable to scaling up for mass production. Alumina nanotemplates are porous alumina membranes that have been fabricated, variously, by anodizing either pure aluminum or aluminum that has been deposited on silicon by electronbeam evaporation. The diameters of the pores (7 to 300 nm), areal densities of pores (as much as 7 x 10(exp 10)sq cm), and lengths of pores (up to about 100 nm) can be tailored by selection of fabrication conditions. In a given case, the catalytic metal, catalytic metal alloy, or catalytic metal/ polytetrafluoroethylene composite is electrodeposited in the pores of the alumina nanotemplate. The dimensions of the pores, together with the electrodeposition conditions, determine the sizes and surface areas of the catalytic particles. Hence, the small features and large surface areas of the porosity translate to the desired small particle size and large surface area of the catalyst (see figure). When polytetrafluoroethylene is included, it is for the purpose of imparting hydrophobicity in order to prevent water from impeding the desired diffusion of gases through the catalyst layer. To incorporate polytetrafluoroethylene into a catalytic-metal/polytetrafluoroethylene nanocomposite, one suspends polytetrafluoroethylene nanoparticles in the electrodeposition solution. The polytetrafluoroethylene content can be varied to obtain the desired degree of hydrophobicity and permeability by gas.
The 1783-1784 Laki tholeiitic basalt fissure eruption in Iceland was one of the greatest atmospheric pollution events of the past 250 years, with widespread effects in the northern hemisphere. The degassing history and volatile budget of this event are determined by measurements of pre-eruption and residual contents of sulfur, chlorine, and fluorine in the products of all phases of the eruption. In fissure eruptions such as Laki, degassing occurs in two stages: by explosive activity or lava fountaining at the vents, and from the lava as it flows away from the vents. Using the measured sulfur concentrations in glass inclusions in phenocrysts and in groundmass glasses of quenched eruption products, we calculate that the total accumulative atmospheric mass loading of sulfur dioxide was 122 Mt over a period of 8 months. This volatile release is sufficient to have generated approximately 250 Mt of H2SO4 aerosols, an amount which agrees with an independent estimate of the Laki aerosol yield based on atmospheric turbidity measurements. Most of this volatile mass (approximately 60 wt.%) was released during the first 1.5 months of activity. The measured chlorine and fluorine concentrations in the samples indicate that the atmospheric loading of hydrochloric acid and hydrofluoric acid was approximately 7.0 and 15.0 Mt, respectively. Furthermore, approximately 75% of the volatile mass dissolved by the Laki magma was released at the vents and carried by eruption columns to altitudes between 6 and 13 km. The high degree of degassing at the vents is attributed to development of a separated two-phase flow in the upper magma conduit, and implies that high-discharge basaltic eruptions such as Laki are able to loft huge quantities of gas to altitudes where the resulting aerosols can reside for months, or even 1-2 years. The atmospheric volatile contribution due to subsequent degassing of the Laki lava flow is only 18 wt.% of the total dissolved in the magma, and these emissions were confined to the lowest regions of the troposhere and therefore important only over Iceland. This study indicates that determination of the amount of sulfur degassed from the Laki magma batch by measurements of sulfur in the volcanic products (the petrologic method) yields a result which is sufficient to account for the mass of aerosols estimated by other methods.
The purpose of this project was to determine the chemicals desorbing from the space shuttle heat protection tiles. The original protocol for this project involved direct insertion probe mass spectrometry (DIPMS) analysis of the outgassing products from the tiles. However, this method proved unsatisfactory due to the large number of compounds desorbing from the tiles. A purge and trap technique was then employed to collect and separate the chemicals desorbing from the tiles. The maximum temperature in this analysis was 180 C which is the gas chromatograph fused silica capillary column's temperature limit. The desorption was also carried out at atmospheric pressure with helium as the purge gas. A description of the modified protocol is given. All compounds are tentatively identified.
In August, 1997, a NASA workshop was held to assess the prospects emerging from physics that might lead to creating the ultimate breakthroughs in space transportation: propulsion that requires no propellant mass, attaining the maximum transit speeds physically possible, and breakthrough methods of energy production to power such devices. Because these propulsion goals are presumably far from fruition, a special emphasis was to identify affordable, near-term, and credible research that could make measurable progress toward these propulsion goals. Experiments and theories were discussed regarding the coupling of gravity and electromagnetism, vacuum fluctuation energy, warp drives and wormholes, and superluminal quantum tunneling. Preliminary results of this workshop are presented, along with the status of the Breakthrough Propulsion Physics program that conducted this workshop.
Long-duration space missions will benefit from closed-loop life support technologies that minimize mass, volume, and power as well as decrease reliance on Earth-based resupply. A system for In situ production of essential vitamins and nutrients can address the documented problem of degradation of stored food and supplements. Research has shown that the edible yeast Saccharomyces cerevisiae can be used as an on-demand system for the production of various compounds that are beneficial to human health. A critical objective in the development of this approach for long-duration space missions is the effective storage of the selected microorganisms. This research investigates the effects of different storage methods on survival rates of the non-sporulating probiotic S. boulardii, and S. cerevisiae spores and vegetative cells. Dehydration has been shown to increase long-term yeast viability, which also allows increased shelf-life and reduction in mass and volume. The process of dehydration causes detrimental effects on vegetative cells, including oxidative damage and membrane disruption. To maximize cell viability, various dehydration methods are tested here, including lyophilization (freeze-drying), air drying, and dehydration by vacuum. As a potential solution to damage caused by lyophilization, the efficacy of various cryoprotectants was tested. Furthermore, in an attempt to maintain higher survival rates, the effect of temperature during long-term storage was investigated. Data show spores of the wild-type strain to be more resilient to dehydration-related stressors than vegetative cells of either strain, and maintain high viability rates even after one year at room temperature. In the event that engineering the organism to produce targeted nutrient compounds interferes with effective sporulation of S. cerevisiae, a more robust method for improving vegetative cell storage is being sought. Therefore, anhydrobiotic engineering of S. cerevisiae and S. boulardii is being conducted.
Single wall carbon nanotubes (SWNT) are porous objects on the molecular scale and have a low density, which gives them potential applications as adsorbent for molecular hydrogen. Their H2 absorption capacity published in the literature varies from 4 to 10% by mass according to the purity of the materials and storage conditions. Optimization of production methods of SWNTs should permit improving these new materials for storage of hydrogen. In this article, we show the potential of using SWNTs in hydrogen storage. In particular, we pose problems associated with synthesis, purification, and opening up of the nanotubes. We present an electric arc process currently used at laboratory scale to produce single wall carbon nanotubes. We discuss, in particular, operating conditions that permit growth of nanotubes and some plasma parameters that assure control of the material. Analysis of the process is carried out with the aid of local measurements of temperature and scanning and transmission electron microscopy of the materials.
Long-duration space missions will benefit from closed-loop life support technologies that minimize mass, volume, and power as well as decrease reliance on Earth-based resupply. A system for In situ production of essential vitamins and nutrients can address the documented problem of degradation of stored food and supplements. Research has shown that the edible yeast Saccharomyces cerevisiae can be used as an on-demand system for the production of various compounds that are beneficial to human health. A critical objective in the development of this approach for long-duration space missions is the effective storage of the selected microorganisms. This research investigates the effects of different storage methods on survival rates of the non-sporulating probiotic S. boulardii, and S. cerevisiae spores and vegetative cells. Dehydration has been shown to increase long-term yeast viability, which also allows increased shelf-life and reduction in mass and volume. The process of dehydration causes detrimental effects on vegetative cells, including oxidative damage and membrane disruption. To maximize cell viability, various dehydration methods are tested here, including lyophilization (freeze-drying), air drying, and dehydration by vacuum. As a potential solution to damage caused by lyophilization, the efficacy of various cryoprotectants was tested. Furthermore, in an attempt to maintain higher survival rates, the effect of temperature during long-term storage was investigated. Data show spores of the wild-type strain to be more resilient to dehydration-related stressors than vegetative cells of either strain, and maintain high viability rates even after one year at room temperature. In the event that engineering the organism to produce targeted nutrient compounds interferes with effective sporulation of S. cerevisiae, a more robust method for improving vegetative cell storage is being sought. Therefore, anhydrobiotic engineering of S. cerevisiae and S. boulardii is being conducted
Context. The Cassini-Huygens mission has revealed the importance of particle precipitation in the atmosphere of Titan thanks to in-situ measurements. These ionizing particles (electrons, protons, and cosmic rays) have a strong impact on the chemistry, hence must be modeled. Aims. We revisit our computation of ionization in the atmosphere of Titan by cosmic rays. The high-energy high-mass ions are taken into account to improve the precision of the calculation of the ion production profile. Methods. The Badhwahr and O Neill model for cosmic ray spectrum was adapted for the Titan model. We used the TransTitan model coupled with the Planetocosmics model to compute the ion production by cosmic rays. We compared the results with the NAIRAS/HZETRN ionization model used for the first time for a body that differs from the Earth. Results. The cosmic ray ionization is computed for five groups of cosmic rays, depending on their charge and mass: protons, alpha, Z = 8 (oxygen), Z = 14 (silicon), and Z = 26 (iron) nucleus. Protons and alpha particles ionize mainly at 65 km altitude, while the higher mass nucleons ionize at higher altitudes. Nevertheless, the ionization at higher altitude is insufficient to obscure the impact of Saturn s magnetosphere protons at a 500 km altitude. The ionization rate at the peak (altitude: 65 km, for all the different conditions) lies between 30 and 40/cu cm/s. Conclusions. These new computations show for the first time the importance of high Z cosmic rays on the ionization of the Titan atmosphere. The updated full ionization profile shape does not differ significantly from that found in our previous calculations (Paper I: Gronoff et al. 2009, 506, 955) but undergoes a strong increase in intensity below an altitude of 400 km, especially between 200 and 400 km altitude where alpha and heavier particles (in the cosmic ray spectrum) are responsible for 40% of the ionization. The comparison of several models of ionization and cosmic ray spectra (in intensity and composition) reassures us about the stability of the altitude of the ionization peak (65 km altitude) with respect to the solar activity.
An approximate analysis to estimate the quantity of nitric oxide that could be formed in the wake of a reentering lifting spacecraft is reported. Three different approaches are undertaken: two simplified analytical models utilizing the sudden-freezing concept named the 'trailing-edge-freezing' and 'wake-freezing' approximations, and a computer calculation involving numerical integration of chemical rate equations. The three methods predict a maximum nitric oxide production equivalent to 6, 9.5 and 8% of the mass of the spacecraft, respectively. Thus, the amount of nitric oxide expected to be produced by future space activities is negligibly small compared with that produced by the natural processes.
In 1996, NASA established the Breakthrough Propulsion Physics program to seek the ultimate breakthroughs in space transportation: propulsion that requires no propellant mass, propulsion that attains the maximum transit speeds physically possible, and breakthrough methods of energy production to power such devices. Topics of interest include experiments and theories regarding the coupling of gravity and electromagnetism, vacuum fluctuation energy, warp drives and worm-holes, and superluminal quantum effects. Because these propulsion goals are presumably far from fruition, a special emphasis is to identify affordable, near-term, and credible research that could make measurable progress toward these propulsion goals. The methods of the program and the results of the 1997 workshop are presented. This Breakthrough Propulsion Physics program, managed by Lewis Research Center, is one part of a comprehensive, long range Advanced Space Transportation Plan managed by Marshall Space Flight Center.
A low-gravity environment, in space or ground-based facilities such as drop towers, provides a unique setting for study of combustion mechanisms. Understanding the physical phenomena controlling the ignition and spread of flames in microgravity has importance for space safety as well as better characterization of dynamical and chemical combustion processes which are normally masked by buoyancy and other gravity-related effects. Even the use of so-called 'limiting cases' or the construction of 1-D or 2-D models and experiments fail to make the analysis of combustion simultaneously simple and accurate. Ideally, to bridge the gap between chemistry and fluid mechanics in microgravity combustion, species concentrations and temperature profiles are needed throughout the flame. However, restrictions associated with performing measurements in reduced gravity, especially size and weight considerations, have generally limited microgravity combustion studies to the capture of flame emissions on film or video laser Schlieren imaging and (intrusive) temperature measurements using thermocouples. Given the development of detailed theoretical models, more sophisticated studies are needed to provide the kind of quantitative data necessary to characterize the properties of microgravity combustion processes as well as provide accurate feedback to improve the predictive capabilities of the computational models. While there have been a myriad of fluid mechanical visualization studies in microgravity combustion, little experimental work has been completed to obtain reactant and product concentrations within a microgravity flame. This is largely due to the fact that traditional sampling methods (quenching microprobes using GC and/or mass spec analysis) are too heavy, slow, and cumbersome for microgravity experiments. Non-intrusive optical spectroscopic techniques have - up until now - also required excessively bulky, power hungry equipment. However, with the advent of near-IR diode lasers, the possibility now exists to obtain reactant and product concentrations and temperatures non-intrusively in microgravity combustion studies. Over the past ten years, Southwest Sciences has focused its research on the high sensitivity, quantitative detection of gas phase species using diode lasers. Our research approach combines three innovations in an experimental system resulting in a new capability for nonintrusive measurement of major combustion species. FM spectroscopy or high frequency Wavelength Modulation Spectroscopy (WMS) have recently been applied to sensitive absorption measurements at Southwest Sciences and in other laboratories using GaAlAs or InGaAsP diode lasers in the visible or near-infrared as well as lead-salt lasers in the mid-infrared spectral region. Because these lasers exhibit essentially no source noise at the high detection frequencies employed with this technique, the achievement of sensitivity approaching the detector shot noise limit is possible.
This is the third annual technical report for the program entitled, Improved Silicon Carbide for Advanced Heat Engines, for the period February 16, 1987 to February 15, 1988. The objective of the original program was the development of high strength, high reliability silicon carbide parts with complex shapes suitable for use in advanced heat engines. Injection molding is the forming method selected for the program because it is capable of forming complex parts adaptable for mass production on an economically sound basis. The goals of the revised program are to reach a Weibull characteristic strength of 550 MPa (80 ksi) and a Weibull modulus of 16 for bars tested in 4-point loading. Two tasks are discussed: Task 1 which involves materials and process improvements, and Task 2 which is a MOR bar matrix to improve strength and reliability. Many statistically designed experiments were completed under task 1 which improved the composition of the batches, the mixing of the powders, the sinter and anneal cycles. The best results were obtained by an attritor mixing process which yielded strengths in excess of 550 MPa (80 ksi) and an individual Weibull modulus of 16.8 for a 9-sample group. Strengths measured at 1200 and 1400 C were equal to the room temperature strength. Annealing of machined test bars significantly improved the strength. Molding yields were measured and flaw distributions were observed to follow a Poisson process. The second iteration of the Task 2 matrix experiment is described.
A technique was developed for predicting the character and magnitude of the shock wave precursor ahead of an entry vehicle and the effect of this precursor on the vehicle flow field was ascertained. A computational method and program were developed to properly model this precursor. Expressions were developed for the mass production rates of each species due to photodissociation and photoionization reactions. Also, consideration was given to the absorption and emission of radiation and how it affects the energy in each of the energy modes of both the atomic and diatomic species. A series of parametric studies were conducted covering a range of entry conditions in order to predict the effects of the precursor on the shock layer and the radiative heat transfer to the body.
The development of high strength, high reliability silicon carbide parts with complex shapes suitable for use in advanced heat engines is studied. Injection molding was the forming method selected for the program because it is capable of forming complex parts adaptable for mass production on an economically sound basis. The goals were to reach a Weibull characteristic strength of 550 MPa (80 ksi) and a Weibull modulus of 16 for bars tested in four-point loading. Statistically designed experiments were performed throughout the program and a fluid mixing process employing an attritor mixer was developed. Compositional improvements in the amounts and sources of boron and carbon used and a pressureless sintering cycle were developed which provided samples of about 99 percent of theoretical density. Strengths were found to improve significantly by annealing in air. Strengths in excess of 550 MPa (80 ksi) with Weibull modulus of about 9 were obtained. Further improvements in Weibull modulus to about 16 were realized by proof testing. This is an increase of 86 percent in strength and 100 percent in Weibull modulus over the baseline data generated at the beginning of the program. Molding yields were improved and flaw distributions were observed to follow a Poisson process. Magic angle spinning nuclear magnetic resonance spectra were found to be useful in characterizing the SiC powder and the sintered samples. Turbocharger rotors were molded and examined as an indication of the moldability of the mixes which were developed in this program.
In 1996, a team of government, university and industry researchers proposed a program to seek the ultimate breakthroughs in space transportation: propulsion that requires no propellant mass, propulsion that can approach and, if possible, circumvent light speed, and breakthrough methods of energy production to power such devices. This Breakthrough Propulsion Physics program, managed by Lewis Research Center, is one part of a comprehensive, long range Advanced Space Transportation Plan managed by Marshall Space Flight Center. Because the breakthrough goals are beyond existing science, a main emphasis of this program is to establish metrics and ground rules to produce near-term credible progress toward these incredible possibilities. An introduction to the emerging scientific possibilities from which such solutions can be sought is also presented.
Aerogel based insulation systems for ambient pressure environments were developed for liquid hydrogen (LH2) tank applications. Solutions to thermal insulation problems were demonstrated for the Space Shuttle External Tank (ET) through extensive testing at the Cryogenics Test Laboratory. Demonstration testing was performed using a 1/10th scale ET LH2 intertank unit and liquid helium as the coolant to provide the 20 K cold boundary temperature. Cryopumping tests in the range of 20K were performed using both constant mass and constant pressure methods. Long-duration tests (up to 10 hours) showed that the nitrogen mass taken up inside the intertank is reduced by a factor of nearly three for the aerogel insulated case as compared to the un-insulated (bare metal flight configuration) case. Test results including thermal stabilization, heat transfer effectiveness, and cryopumping confirm that the aerogel system eliminates free liquid nitrogen within the intertank. Physisorption (or adsorption) of liquid nitrogen within the fine pore structure of aerogel materials was also investigated. Results of a mass uptake method show that the sorption ratio (liquid nitrogen to aerogel beads) is about 62 percent by volume. A novel liquid nitrogen production method of testing the liquid nitrogen physical adsorption capacity of aerogel beads was also performed to more closely approximate the actual launch vehicle cooldown and thermal stabilization effects within the aerogel material. The extraordinary insulating effectiveness of the aerogel material shows that cryopumping is not an open-cell mass transport issue but is strictly driven by thermal communication between warm and cold surfaces. The new aerogel insulation technology is useful to solve heat transfer problem areas and to augment existing thermal protection systems on launch vehicles. Examples are given and potential benefits for producing launch systems that are more reliable, robust, reusable, and efficient are outlined.