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NASA NTRS2010

Chemical sensors using coated or doped carbon nanotube networks

Methods for using modified single wall carbon nanotubes ("SWCNTs") to detect presence and/or concentration of a gas component, such as a halogen (e.g., Cl.sub.2), hydrogen halides (e.g., HCl), a hydrocarbon (e.g., C.sub.nH.sub.2n+2), an alcohol, an aldehyde or a ketone, to which an unmodified SWCNT is substantially non-reactive. In a first embodiment, a connected network of SWCNTs is coated with a selected polymer, such as chlorosulfonated polyethylene, hydroxypropyl cellulose, polystyrene and/or polyvinylalcohol, and change in an electrical parameter or response value (e.g., conductance, current, voltage difference or resistance) of the coated versus uncoated SWCNT networks is analyzed. In a second embodiment, the network is doped with a transition element, such as Pd, Pt, Rh, Ir, Ru, Os and/or Au, and change in an electrical parameter value is again analyzed. The parameter change value depends monotonically, not necessarily linearly, upon concentration of the gas component. Two general algorithms are presented for estimating concentration value(s), or upper or lower concentration bounds on such values, from measured differences of response values.

Li, Jing↗

NASA NTRS2004

A Preliminary Study on the Toxic Combustion Products Testing of Polymers Used in High-Pressure Oxygen Systems

One likely cause of polymer ignition in a high-pressure oxygen system is adiabatic-compression heating of polymers caused by pneumatic impact. Oxidative _ pyrolysis or combustion of polymers in a high-pressure oxygen system could generate toxic gases. This paper reports the preliminary results of toxic combustion product testing of selected polymers in a pneumatic-impact test system. Five polymers commonly used in high-pressure oxygen systems, Nylon 6/6, polychlorotrifluoroethylene (CTFE), polytetrafluoroethylene (PTFE), fluoroelastomer (Viton(TradeMark) A), and nitrile rubber (Buna N), were tested in a pneumatic-impact test system at 2500- or 3500-psia oxygen pressure. The polymers were ignited and burned, then combustion products were collected in a stainless-steel sample bottle and analyzed by GC/MS/IRD, GC/FID, and GC/Methanizer/FID. The results of adiabatic-compression tests show that combustion of hydrocarbon polymers, nitrogen-containing polymers, and halogenated polymers in high-pressure oxygen systems are relatively complete. Toxicity of the combustion product gas is presumably much lower than the combustion product gas generated from ambient-pressure oxygen (or air) environments. The NASA-Lewis equilibrium code was used to determine the composition of combustion product gas generated from a simulated, adiabatic-compression test of nine polymers. The results are presented and discussed.

Hshieh, Fu-Yu↗

NASA NTRS2010

Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future studies on kimberlitic and subduction zone magmas, which could have significant amount of fluorine, will need to consider the combined effects of F, Cl, and H on their stability and chemical evolution.

Filiberto, Justin↗

NASA NTRS2010

Observed Seasonal to Decadal-Scale Responses in Mesospheric Water Vapor

The 14-yr (1991-2005) time series of mesospheric water vapor from the Halogen Occultation Experiment (HALOE) are analyzed using multiple linear regression (MLR) techniques for their6 seasonal and longer-period terms from 45S to 45N. The distribution of annual average water vapor shows a decrease from a maximum of 6.5 ppmv at 0.2 hPa to about 3.2 ppmv at 0.01 hPa, in accord with the effects of the photolysis of water vapor due to the Lyman-flux. The distribution of the semi-annual cycle amplitudes is nearly hemispherically symmetric at the low latitudes, while that of the annual cycles show larger amplitudes in the northern hemisphere. The diagnosed 11-yr, or solar cycle, max minus min, water vapor values are of the order of several percent at 0.2 hPa to about 23% at 0.01 hPa. The solar cycle terms have larger values in the northern than in the southern hemisphere, particularly in the middle mesosphere, and the associated linear trend terms are anomalously large in the same region. Those anomalies are due, at least in part, to the fact that the amplitudes of the seasonal cycles were varying at northern mid latitudes during 1991-2005, while the corresponding seasonal terms of the MLR model do not allow for that possibility. Although the 11-yr variation in water vapor is essentially hemispherically-symmetric and anti-phased with the solar cycle flux near 0.01 hPa, the concurrent temperature variations produce slightly colder conditions at the northern high latitudes at solar minimum. It is concluded that this temperature difference is most likely the reason for the greater occurrence of polar mesospheric clouds at the northern versus the southern high latitudes at solar minimum during the HALOE time period.

Remsberg, Ellis↗

NASA NTRS2010

Multi-Model Assessment of the Factors Driving the Ozone Evolution Over the 21st Century

The evolution of ozone from 1960 to 2100 is examined in simulations from fourteen chemistry-climate models. There is general agreement among the models at the broadest levels, with all showing column ozone decreasing at all latitudes from 1960 to around 2000, then increasing at all latitudes over the first half of the 21 st century (21 C), and latitudinal variations in the rate of increase and date of return to historical values. In the second half of the century, ozone is projected to carry on increasing, level off or even decrease depending on the latitude, resulting in variable dates of return to historical values at latitudes where column ozone has declined below those levels. Separation into partial column above and below 20 hPa reveals that these latitudinal differences are almost completely due to differences in the lower stratosphere. At all latitudes, upper stratospheric ozone increases throughout the 21 C and returns to 1960 levels before the end of the century, although there is a spread among the models in dates that ozone returns to historical values. Using multiple linear regression the upper stratospheric ozone increase comes from almost equal contributions due to decrease in halogens and cooling from increased greenhouse gas concentrations. The evolution of lower stratospheric ozone differs with latitude. In the tropical lower stratosphere an increase in tropical upwelling causes a steady decrease in ozone through the 21C, and total column ozone does not return to 1960 levels in all models. In contrast, lower stratospheric and total column ozone in middle and high latitudes increases during the 21 C and returns to 1960 levels. For all models there is an earlier return for ozone to historical levels in the northern hemisphere. This is thought to be due to interhemispheric differences in transport.

Oman, L.↗

NASA NTRS2010

Seasonal to Decadal Variations of Water Vapor in the Tropical Lower Stratosphere Observed with Balloon-Borne Cryogenic Frost Point Hygrometers

We investigated water vapor variations in the tropical lower stratosphere on seasonal, quasi-biennial oscillation (QBO), and decadal time scales using balloon-borne cryogenic frost point hygrometer data taken between 1993 and 2009 during various campaigns including the Central Equatorial Pacific Experiment (March 1993), campaigns once or twice annually during the Soundings of Ozone and Water in the Equatorial Region (SOWER) project in the eastern Pacific (1998-2003) and in the western Pacific and Southeast Asia (2001-2009), and the Ticosonde campaigns and regular sounding at Costa Rica (2005-2009). Quasi-regular sounding data taken at Costa Rica clearly show the tape recorder signal. The observed ascent rates agree well with the ones from the Halogen Occultation Experiment (HALOE) satellite sensor. Average profiles from the recent five SOWER campaigns in the equatorial western, Pacific in northern winter and from the three Ticosonde campaigns at Costa Rica (10degN) in northern summer clearly show two effects of the QBO. One is the vertical displacement of water vapor profiles associated with the QBO meridional circulation anomalies, and the other is the concentration variations associated with the QBO tropopause temperature variations. Time series of cryogenic frost point hygrometer data averaged in a lower stratospheric layer together with HALOE and Aura Microwave Limb Sounder data show the existence of decadal variations: The mixing ratios were higher and increasing in the 1990s, lower in the early 2000s, and probably slightly higher again or recovering after 2004. Thus linear trend analysis is not appropriate to investigate the behavior of the tropical lower stratospheric water vapor.

Fujiwara, M.↗

NASA NTRS2011

Two Catalysts for Selective Oxidation of Contaminant Gases

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

Wright, John D.↗

NASA NTRS2011

The Impact of Geoengineering Aerosols on Stratospheric Temperature and Ozone

Anthropogenic greenhouse gas emissions are warming the global climate at an unprecedented rate. Significant emission reductions will be required soon to avoid a rapid temperature rise. As a potential interim measure to avoid extreme temperature increase, it has been suggested that Earth's albedo be increased by artificially enhancing stratospheric sulfate aerosols. We use a 3D chemistry climate model, fed by aerosol size distributions from a zonal mean aerosol model. to simulate continuous injection of 1-10 Mt/a into the lower tropical stratosphere. In contrast to the case for all previous work, the particles are predicted to grow to larger sizes than are observed after volcanic eruptions. The reason is the continuous supply of sulfuric acid and hence freshly formed small aerosol particles, which enhance the formation of large aerosol particles by coagulation and, to a lesser extent, by condensation. Owing to their large size, these particles have a reduced albedo. Furthermore, their sedimentation results in a non-linear relationship between stratospheric aerosol burden and annual injection, leading to a reduction of the targeted cooling. More importantly, the sedimenting particles heat the tropical cold point tropopause and, hence, the stratospheric entry mixing ratio of H2O increases. Therefore, geoengineering by means of sulfate aerosols is predicted to accelerate the hydroxyl catalyzed ozone destruction cycles and cause a significant depletion of the ozone layer even though future halogen concentrations will he significantly reduced.

Heckendorn, P.↗

NASA NTRS2011

Coated or doped carbon nanotube network sensors as affected by environmental parameters

Li, Jing↗

NASA NTRS2011

Spectrally and Radiometrically Stable Wide-Band on Board Calibration Source for In-Flight Data Validation in Imaging Spectroscopy Applications

The quality of the quantitative spectral data collected by an imaging spectrometer instrument is critically dependent upon the accuracy of the spectral and radiometric calibration of the system. In order for the collected spectra to be scientifically useful, the calibration of the instrument must be precisely known not only prior to but during data collection. Thus, in addition to a rigorous in-lab calibration procedure, the airborne instruments designed and built by the NASA/JPL Imaging Spectroscopy Group incorporate an on board calibrator (OBC) system with the instrument to provide auxiliary in-use system calibration data. The output of the OBC source illuminates a target panel on the backside of the foreoptics shutter both before and after data collection. The OBC and in-lab calibration data sets are then used to validate and post-process the collected spectral image data. The resulting accuracy of the spectrometer output data is therefore integrally dependent upon the stability of the OBC source. In this paper we describe the design and application of the latest iteration of this novel device developed at NASA/JPL which integrates a halogen-cycle source with a precisely designed fiber coupling system and a fiber-based intensity monitoring feedback loop. The OBC source in this Airborne Testbed Spectrometer was run over a period of 15 hours while both the radiometric and spectral stabilities of the output were measured and demonstrated stability to within 1% of nominal.

visible spectrometers↗

NASA NTRS2004

Improved Method of Purifying Carbon Nanotubes

An improved method of removing the residues of fabrication from carbon nanotubes has been invented. These residues comprise amorphous carbon and metal particles that are produced during the growth process. Prior methods of removing the residues include a variety of processes that involved the use of halogens, oxygen, or air in both thermal and plasma processes. Each of the prior methods entails one or more disadvantages, including non-selectivity (removal or damage of nanotubes in addition to removal of the residues), the need to dispose of toxic wastes, and/or processing times as long as 24 hours or more. In contrast, the process described here does not include the use of toxic chemicals, the generation of toxic wastes, causes little or no damage to the carbon nanotubes, and involves processing times of less than 1 hour. In the improved method, purification is accomplished by flowing water vapor through the reaction chamber at elevated temperatures and ambient pressures. The impurities are converted to gaseous waste products by the selective hydrogenation and hydroxylation by the water in a reaction chamber. This process could be performed either immediately after growth or in a post-growth purification process. The water used needs to be substantially free of oxygen and can be obtained by a repeated freeze-pump-thaw process. The presence of oxygen will non-selectively attach the carbon nanotubes in addition to the amorphous carbon.

Delzeit, Lance D.↗

NASA NTRS2009

Identifying the Molecular Origin of Global Warming

We have investigated the physical characteristics of greenhouse gases (GHGs) to assess which properties are most important in determining the efficiency of a GHG. Chlorofluorcarbons (CFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), nitrogen fluorides, and various other known atmospheric trace molecules have been included in this study. Compounds containing the halogens F or Cl have in common very polar X-F or X-Cl bonds, particularly the X-F bonds. It is shown that as more F atoms bond to the same central atom, the bond dipoles become larger as a result of the central atom becoming more positive. This leads to a linear increase in the total or integrated XF bond dipole derivatives for the molecule, which leads to a non-linear (quadratic) increase in infrared (IR) intensity. Moreover, virtually all of the X-F bond stretches occur in the atmospheric IR window as opposed to X-H stretches, which do not occur in the atmospheric window. It is concluded that molecules possessing several F atoms will always have a large radiative forcing parameter in the calculation of their global warming potential. Some of the implications for global warming and climate change are discussed.

Bera, Partha P.↗

NASA NTRS2003

Simplified Waterproofing of Aerogels

A relatively simple silanization process has been developed for waterproofing or rewaterproofing aerogels, xerogels, and aerogel/tile composites, and other, similar low-density, highly microporous materials. Such materials are potentially attractive for a variety of applications especially for thermal-insulation panels that are required to be thin and lightweight. Unfortunately, such materials are also hydrophilic and tend to collapse after adsorbing water from the air. Hence, an effective means of waterproofing is necessary to enable practical exploitation of aerogels and the like. Older processes for waterproofing aerogels are time-consuming, labor-intensive, and expensive, relative to the present process. Each of the older processes includes a number of different chemical treatment steps, and some include the use of toxic halogenated surface-modifying compounds, pressures as high as hundreds of atmospheres, and/or temperatures as high as 1,000 C.

Hsu, Ming-Ta S.↗

NASA NTRS2012

Method to Improve Indium Bump Bonding via Indium Oxide Removal Using a Multi-Step Plasma Process

A process for removing indium oxide from indium bumps in a flip-chip structure to reduce contact resistance, by a multi-step plasma treatment. A first plasma treatment of the indium bumps with an argon, methane and hydrogen plasma reduces indium oxide, and a second plasma treatment with an argon and hydrogen plasma removes residual organics. The multi-step plasma process for removing indium oxide from the indium bumps is more effective in reducing the oxide, and yet does not require the use of halogens, does not change the bump morphology, does not attack the bond pad material or under-bump metallization layers, and creates no new mechanisms for open circuits.

Greer, H. Frank↗

NASA NTRS2012

The Influence of Large Solar Proton Events on the Atmosphere

Solar proton events (SPEs) can cause changes in constituents in the Earth s polar middle atmosphere. A number of large SPEs have occurred over the past 50 years and tend to happen most frequently near solar maximum. The highly energetic protons cause ionizations, excitations, dissociations, and dissociative ionizations of the background constituents. Complicated ion chemistry leads to HOx (H, OH, HO2) production and dissociation of N2 leads to NOy (N, NO, NO2, NO3, N2O5, HNO3, HO2NO2, ClONO2, BrONO2) production. Both the HOx and NOy increases can result in changes to ozone in the stratosphere and mesosphere. The HOx increases lead to short-lived (~days) ozone decreases in the mesosphere and upper stratosphere. The NOy increases lead to long-lived (~several months) stratospheric ozone changes because of the long lifetime of NOy constituents in this region. UARS HALogen Occultation Experiment (HALOE) instrument observations showed SPE-caused polar stratospheric NOx (NO+NO2) increases over 10 ppbv in September 2000 due to the very large SPE of July 2000, which are reasonably well simulated with the Whole Atmosphere Community Climate Model (WACCM). WACCM-computed SPE-caused polar stratospheric ozone decreases >10% continued for up to 5 months past the largest events in the past 50 years, however, SPE-caused total ozone changes were not found to be statistically significant. Small polar middle atmospheric temperature changes of <4 K have also been predicted to occur as a result of the larger SPEs. The polar atmospheric effects of large SPEs during solar cycle 23 and 24 will be emphasized in this presentation.

Jackman, Charles H.↗

NASA NTRS2012

Alternative Green Solvents Project

Necessary for safe and proper functioning of equipment. Mainly halogenated solvents. Tetrachloride, Trichloroethylene (TCE), CFC-113. No longer used due to regulatory/safety concerns. Precision Cleaning at KSC: Small % of total parts. Used for liquid oxygen (LOX) systems. Dual solvent process. Vertrel MCA (decafluoropentane (DFP) and trons-dichloroethylene) HFE-7100. DFP has long term environmental concerns. Project Goals: a) Identify potential replacements. b) 22 wet chemical processes. c) 3 alternative processes. d) Develop test procedures. e) Contamination and cleaning. f) Analysis. g) Use results to recommend alternative processes. Conclusions: a) No alternative matched Vertrel in this study. b) No clear second place solvent. c) Hydrocarbons- easy; Fluorinated greases- difficult. d) Fluorinated component may be needed in replacement solvent. e) Process may need to make up for shortcoming of the solvent. f) Plasma and SCC02 warrant further testing.

Maloney, Phillip R.↗

NASA NTRS2013

Spectrally and Radiometrically Stable, Wideband, Onboard Calibration Source

The Onboard Calibration (OBC) source incorporates a medical/scientific-grade halogen source with a precisely designed fiber coupling system, and a fiber-based intensity-monitoring feedback loop that results in radiometric and spectral stabilities to within less than 0.3 percent over a 15-hour period. The airborne imaging spectrometer systems developed at the Jet Propulsion Laboratory incorporate OBC sources to provide auxiliary in-use system calibration data. The use of the OBC source will provide a significant increase in the quantitative accuracy, reliability, and resulting utility of the spectral data collected from current and future imaging spectrometer instruments.

Coles, James B.↗

NASA NTRS2013

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Quinn, Jacqueline↗