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NASA NTRS1985

Metallic and metalloceramic coating by thermal decomposition

Metallic and metalloceramic coatings were prepared by thermal decomposition of a number of inorganic and metallo-organic compounds. The compounds were applied by spraying and by immersion, especially on ceramic fibers and fiber forms, which are easily coated by this procedure. Penetration of low-density ceramics is examined, and procedures are described that were used for converting the deposited materials to metals, oxides, or metal oxide films. Multiple-component films were also prepared. Photomicrographs illustrate the structure of these films.

Hendricks, R. C.↗

NASA NTRS1982

Effective photodissociation cross sections for molecular oxygen and nitric oxide in the Schumann-Runge bands

Accurate calculations of the atmospheric opacity and the photodissociation rate of molecular oxygen in the Schumann-Runge bands (175-205) are necessary for modeling chemistry in the terrestrial upper atmosphere. The present investigation is concerned with a single simple parameterization of effective cross sections which can be used to calculate both O2 opacity and dissociation rates. Use is made of a zenith angle dependent factor which accounts for variations shown in detailed calculations. The conducted analysis is based on the results of Frederick and Hudson (1980). Attention is given to molecular oxygen effective cross sections and nitric oxide effective cross sections. It is found that the depth of the atmosphere to which solar radiation in the 175-200 nm spectral region penetrates is a sensitive function of the rotational line widths in the Schumann-Runge bands. The oscillator strength for each band measures the cross section integrated over the band while the line width determine how the absorption is distributed in wavenumber.

Allen, M.↗

NASA NTRS2020

Unexpected Source and Transport of Iron from the Deep Peru Margin

Iron is the most important micronutrient in the ocean, but the nature and magnitude of its sources and sinks to the ocean are poorly constrained. Here we assess our understanding of the sources and sinks of iron in margin environments by synthesizing observations from the U.S. GEOTRACES GP16 Eastern Tropical Pacific Zonal Transect (EPZT) cruise near the Peru margin. GP16 observations showed elevated dissolved iron (dFe) concentrations along the margin, but a larger westward plume of dFe at slope depths (1000-3000 m) in oxygenated waters, rather than at shelf depths (100-300 m) in oxygen deficient waters. We examine the potential explanations for this unexpected observation. Multiple tracers from GP16 suggest that sediment resuspension was important at slope depths, which would lead to enhanced benthic flux of dFe above what was previously measured. The difference in the apparent persistence and penetration of shelf vs slope plumes of dFe into the interior of the ocean likely results from faster removal rates of the shelf dFe compared to slope dFe. DFe sourced from the shelf was almost entirely in the dFe(II) form, whereas dFe sourced from the slope was almost entirely in the dFe(III) form. Although benthic dFe(II) diffuses into oxygen deficient overlying waters, there is still oxidation of dFe(II), which precipitates to particulate Fe(III). In contrast, the slope plume appears to persist in a stabilized dFe(III) form. We hypothesize that sediment porewaters with moderate organic carbon delivery to sediments and shallow oxygen penetration are especially good sources of persistent dFe to the water column.

iron↗

NASA NTRS2016

Prebiotic Chemistry and Atmospheric Warming of Early Earth by an Active Young Sun

Nitrogen is a critical ingredient of complex biological molecules. Molecular nitrogen, however, which was outgassed Into the Earth's early atmosphere, is relatively chemically inert and nitrogen fixation into more chemically reactive compounds requires high temperatures. Possible mechanisms of nitrogen fixation include lightning, atmospheric shock heating by meteorites, and solar ultraviolet radiation. Here we show that nitrogen fixation in the early terrestrial atmosphere can be explained by frequent and powerful coronal mass ejection events from the young Sun -- so-called superflares. Using magnetohydrodynamic simulations constrained by Kepler Space Telescope observations, we find that successive superflare ejections produce shocks that accelerate energetic particles, which would have compressed the early Earth's magnetosphere. The resulting extended polar cap openings provide pathways for energetic particles to penetrate into the atmosphere and, according to our atmospheric chemistry simulations, initiate reactions converting molecular nitrogen, carbon dioxide and methane to the potent greenhouse gas nitrous oxide as well as hydrogen cyanide, an essential compound for life. Furthermore, the destruction of N2, C02 and CH, suggests that these greenhouse gases cannot explain the stability of liquid water on the early Earth. Instead, we propose that the efficient formation of nitrous oxide could explain a warm early Earth.

Airapetian, V. S.↗

NASA NTRS2018

Mechanisms of Oxide Formation in the Self-Reacting Friction Stir Weld Process

The initial objective of this study was to evaluate the effect of an extended delay time between preweld cleaning and the completion of a self-reacting friction stir welding (SRFSW) process on the resulting quality of various thickness panels of AA2219-T87. The current NASA standard specifies no more than a 48 hour delay between preweld cleaning and actual welding. The concern is whether increasing the cleaning delay time results in development of the residual oxide defect (ROD) in SRFSW. This concern emanates from the possibility of increased time correlating with increased oxide layer thickness on the faying surfaces. Oxide content on the faying surfaces has been reported to correlate with the occurrence of the ROD which reduces mechanical properties. When the SRFSW process was first adopted by the NASA Marshall Space Flight Center (MSFC), unexpected low tensile values that resulted were attributed to oxides within the weld that appeared to follow the former faying surface contours. Mitigation of the ROD was achieved through a combination of modifications to the processing parameters, tool designs, and incorporation of a weld seam offset. Two operations are involved in preweld cleaning: the first is removal of oil and grease, and the second is removal of surface oxides. In arc welding, improper cleaning of the faying surfaces of aluminum welded joints can increase the sensitivity toward development of defects. As the aluminum is locally melted, these contaminants contribute toward the development of porosity, inclusions, entrapped oxides, and other discontinuities which can degrade the strength of the weld joint. For weldment of large structures, the weld joint is typically cleaned, fit-up, and tack welded prior to the final full penetration welding pass. Because of the stringent joint fit-up requirements for mismatch and peaking for launch vehicle structures, the joint fit-up can sometimes contribute to lengthy delays between cleaning and tack welding, especially for circumferential weld joints on large diameter components. When the conventional friction stir welding (CFSW) process was introduced at the NASA MSFC, there was no procedure for cleaning prior to the solid-state joining process. As the process expanded to include SRFSW, preparation of the faying, crown, and root surfaces were implemented to overcome the ROD. Although the solid-state process is not expected to reach temperatures high enough for dissociation of the native oxide layer, concern remained regarding the redeposition of the native oxide layer within the stir zone. NASA has previously established the allowable time at 48 hours between preweld cleaning and a SRFSW process. The effect of potential 2 contamination resulting from an extended delay to 188 hours was subsequently evaluated for SRFSWs using tensile testing and metallographic imaging. Tensile specimens were tested at room temperature (RT), and at cryogenic conditions of liquid nitrogen (LN2) and liquid hydrogen. No detrimental effect on weld quality, as determined by weld strength, was reported for cleaning delays of 48, 120, 168, 240 or 288 hours. While no trends were established in this study, which extended the delay from 48 to 188 hours, there were a few outliers in terms of ultimate tensile strength (UTS). According to M. Fisher's 2014 Boeing Company Memo no. EYBF-MAF-14-029, all outliers were above the minimum acceptance criteria, but out of family with respect to the average values. As the robustness and reliability of any process ultimately depends on the average values as well as the outliers, an understanding of the cause of these outliers will ultimately improve the process. This report examines those outliers and their possible causes.

Schneider, J. A.↗

NASA NTRS2012

Deep Drilling and Sampling via the Wireline Auto-Gopher Driven by Piezoelectric Percussive Actuator and EM Rotary Motor

The ability to penetrate subsurfaces and perform sample acquisition at depths of meters is critical for future NASA in-situ exploration missions to bodies in the solar system, including Mars and Europa. A corer/sampler was developed with the goal of acquiring pristine samples by reaching depths on Mars beyond the oxidized and sterilized zone. To developed rotary-hammering coring drill, called Auto-Gopher, employs a piezoelectric actuated percussive mechanism for breaking formations and an electric motor rotates the bit to remove the powdered cuttings. This sampler is a wireline mechanism that is incorporated with an inchworm mechanism allowing thru cyclic coring and core removal to reach great depths. The penetration rate is being optimized by simultaneously activating the percussive and rotary motions of the Auto-Gopher. The percussive mechanism is based on the Ultrasonic/Sonic Drill/Corer (USDC) mechanism that is driven by piezoelectric stack and that was demonstrated to require low axial preload. The Auto-Gopher has been produced taking into account the a lessons learned from the development of the Ultrasonic/Sonic Gopher that was designed as a percussive ice drill and was demonstrated in Antarctica in 2005 to reach about 2 meters deep. A field demonstration of the Auto-Gopher is currently being planned with objective of reaching as deep as 3 to 5 meters in tufa subsurface.

Auto-Gopher↗

NASA NTRS1973

Aircraft water vapor measurements utilizing an aluminum oxide hygrometer

A hygrometer for water vapor measurements from an aircraft has been developed. An aluminum oxide hygrometer mounted in an aircraft Rosemount air temperature scoop was flown on NASA and USAF aircraft. Water vapor measurements were conducted up to 40,000 feet with penetration into the stratosphere. Good agreement was obtained with simultaneously flown remote sounders of water vapor. During transcontinental flights the hygrometer demonstrated adequate response to measure the natural variability of water vapor near the tropopause. Rapid response was demonstrated in pursuit of the jet wake of an F-104 at 35,000 feet.

Hilsenrath, E.↗

NASA NTRS2019

Reinforcing Additives for Ice Adhesion Reduction Coatings

Adhesion of contaminants has been identified as a ubiquitous issue for aeronautic exterior surfaces. In-flight icing is particularly hazardous for all aircraft and can be experienced throughout the year under the appropriate environmental conditions. On larger vehicles, the accretion of ice could result in loss of lift, engine failure, and potentially loss of vehicle and life were it not for active deicing or anti-icing equipment. Smaller vehicles though cannot support the mass and mechanical complexity of active ice mitigating systems and thus must rely upon passive approaches or avoid icing conditions altogether. One approach that may be applicable to all aircraft is the use of coatings. Durability remains an issue and has prevented realization of coatings for leading edge contamination mitigation. In this work, epoxy coatings were generated as a passive approach for ice adhesion mitigation and methods to improve durability were evaluated. Highly cross-linked epoxy systems can be extremely rigid, which could have deleterious consequences regarding application as a leading edge coating. Incorporation of flexible species, such as poly(ethylene glycol) may improve coating toughness.8 Additionally, core-shell rubber (CSR) particles have been utilized to improve fracture toughness of epoxies.9 Both of these more established additives are investigated in this work. An emerging additive that is also evaluated here is holey graphene. This nanomaterial possesses many of the advantageous properties of graphene (excellent mechanical properties, thermal and electrical conductivity, large surface area, etc.) while also exhibiting behaviors associated with flexible, porous materials (i.e., compressibility, increased permeation, etc.). Holey graphene, HG, was synthesized by the oxidation of defect-rich sites on graphene sheets through controlled thermal expo-sure.10 It is envisioned that the porous nature of HG would allow resin penetration through the graphitic plane, resulting in better interfacial interaction and therefore better translation of the nanomaterial’s properties to the surrounding matrix.

Wohl, Christopher J↗

NASA NTRS2008

Saturn Magnetospheric Impact on Surface Molecular Chemistry and Astrobiological Potential of Enceladus

The active south polar surface of Enceladus is exposed to strong chemical processing by direct interaction with charged plasma and energetic particles in the local magnetospheric environment of this icy moon. Chemical oxidation activity is suggested by detection of H202 at the surface in this region and less directly by substantial presence of C02, CO, and N2 in the plume gases. Molecular composition of the uppermost surface, including ejecta from plume activity, is radiolytically transformed mostly by penetrating energetic electrons with lesser effects from more depleted populations of energetic protons. The main sources of molecular plasma ions and E-ring dust grains in the magnetospheric environment are the cryovolcanic plume emissions from Enceladus. These molecular ions and the dust grains are chemically processed by magnetospheric interactions that further impact surface chemistry on return to Enceladus. For example, H20 neutrals dominating the emitted plume gas return to the surface mostly as H30+ ions after magnetospheric processing. Surface oxidant loading is further increased by return of radiolytically processed ice grains from the E-ring. Plume frost deposition and micrometeoroid gardening protect some fraction of newly produced molecular species from destruction by further irradiation. The evident horizontal and vertical mobility of surface ices in the south polar region drive mixing of these processed materials into the moon interior with potential impacts on deep ice molecular chemistry and plume gas production. Similarly as suggested previously for Europa, the externally driven source of radiolytic oxidants could affect evolution of life in any subsurface liquid water environments of Enceladus.

Cooper, Paul D.↗

NASA NTRS1992

Absolute absorption cross sections of ozone at 300 K, 228 K and 195 K in the wavelength region 185-240 nm

An account is given of progress of work on absorption cross section measurements of ozone at 300 K, 228 K and 195 K in the wavelength region 185-240 nm. In this wavelength region, the penetration of solar radiation into the Earth's atmosphere is controlled by O2 and O3. The transmitted radiation is available to dissociate trace species such as halocarbons and nitrous oxide. We have recently measured absolute absorption cross sections of O3 in the wavelength region 240-350 nm (Freeman et al., 1985; Yoshino et al., 1988). We apply these proven techniques to the determination of the absorption cross section of O3 at 300 K, 228 K and 195 K throughout the wavelength region 185-240 nm. A paper titled 'Absolute Absorption Cross Section Measurements of Ozone in the Wavelength Region 185-254 nm and the Temperature Dependence' has been submitted for publication in the Journal of Geophysical Research.

Yoshino, K.↗

NASA NTRS2013

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Ahlborg, Nadia L.↗

NASA NTRS1992

Characterization of radiation-induced damage in high performance polymers by electron paramagnetic resonance imaging spectroscopy

The potential for long-term human activity beyond the Earth's protective magnetosphere is limited in part by the lack of detailed information on the effectiveness and performance of existing structural materials to shield the crew and spacecraft from highly penetrating space radiations. The two radiations of greatest concern are high energy protons emitted during solar flares and galactic cosmic rays which are energetic ions ranging from protons to highly oxidized iron. Although the interactions of such high-energy radiations with matter are not completely understood at this time, the effects of the incident radiation are clearly expected to include the formation of paramagnetic spin centers via ionization and bond-scission reactions in the molecular matrices of structural materials. Since this type of radiation damage is readily characterized by Electron Paramagnetic Resonance (EPR) spectroscopy, the NASA Langley Research Center EPR system was repaired and brought on-line during the 1991 ASEE term. A major goal of the 1992 ASEE term was to adapt the existing core of the LaRC EPR system to meet the requirements for EPR Imaging--a powerful new technique which provides detailed information on the internal structure of materials by mapping the spatial distribution of unpaired spin density in bulk media. Major impetus for this adaptation arises from the fact that information derived from EPRI complements other methods such as scanning electron microscopy which primarily characterize surface phenomena. The modification of the EPR system has been initiated by the construction of specially designed, counterwound Helmholtz coils which will be mounted on the main EPR electromagnet. The specifications of the coils have been set to achieve a static linear magnetic field gradient of 10 gauss/mm/amp along the principal (Z) axis of the Zeeman field. Construction is also in progress of a paramagnetic standard in which the spin distribution is known in all three dimensions. This sample will be used to assess the linearity of the magnetic field gradient and to ensure authentic image reconstruction. A second major task was to secure the computer capability to enable image reconstruction from projection data generated by the magnetic field gradients. To this end, commercially available and public domain software packages which perform inverse Fourier Transform and convoluted (filtered) back projection functions are being integrated into the existing EPR data processing system.

Suleman, Naushadalli K.↗

NASA NTRS2011

Single-Event Gate Rupture in Power MOSFETs: A New Radiation Hardness Assurance Approach

Almost every space mission uses vertical power metal-semiconductor-oxide field-effect transistors (MOSFETs) in its power-supply circuitry. These devices can fail catastrophically due to single-event gate rupture (SEGR) when exposed to energetic heavy ions. To reduce SEGR failure risk, the off-state operating voltages of the devices are derated based upon radiation tests at heavy-ion accelerator facilities. Testing is very expensive. Even so, data from these tests provide only a limited guide to on-orbit performance. In this work, a device simulation-based method is developed to measure the response to strikes from heavy ions unavailable at accelerator facilities but posing potential risk on orbit. This work is the first to show that the present derating factor, which was established from non-radiation reliability concerns, is appropriate to reduce on-orbit SEGR failure risk when applied to data acquired from ions with appropriate penetration range. A second important outcome of this study is the demonstration of the capability and usefulness of this simulation technique for augmenting SEGR data from accelerator beam facilities. The mechanisms of SEGR are two-fold: the gate oxide is weakened by the passage of the ion through it, and the charge ionized along the ion track in the silicon transiently increases the oxide electric field. Most hardness assurance methodologies consider the latter mechanism only. This work demonstrates through experiment and simulation that the gate oxide response should not be neglected. In addition, the premise that the temporary weakening of the oxide due to the ion interaction with it, as opposed to due to the transient oxide field generated from within the silicon, is validated. Based upon these findings, a new approach to radiation hardness assurance for SEGR in power MOSFETs is defined to reduce SEGR risk in space flight projects. Finally, the potential impact of accumulated dose over the course of a space mission on SEGR susceptibility is explored. SEGR evaluation of gamma-irradiated power MOSFETs suggests a non-significant SEGR susceptibility enhancement due to accumulated dose from gamma rays. During SEGR testing, an unexpected enhanced dose effect from heavy-ion irradiation was detected. We demonstrate that this effect could be due to direct ionization by two or more ions at the same channel location. The probability on-orbit for such an occurrence is near-zero given the low heavy-ion fluence over a typical mission lifetime, and did not affect SEGR susceptibility. The results of this work can be used to bound the risk of SEGR in power MOSFETs considered for insertion into spacecraft and instruments.

Lauenstein, Jean-Marie↗

NASA NTRS1984

Reducing Soot in Diesel Exhaust

Electrically charged fuel improves oxidation. Fuel injection system reduces amount of soot formed in diesel engines. Spray injector electrically charges fuel droplets as they enter cylinder. Charged droplets repel each other, creating, dilute fuel mist easily penetrated by oxygen in cylinder.

Bellan, J.↗

NASA NTRS1982

Inexpensive cross-linked polymeric separators made from water-soluble polymers

Polyvinyl alcohol (PVA), cross-linked chemically with aldehyde reagents, produces membranes which demonstrate oxidation resistance, dimensional stability, low ionic resistivity (less than 0.8 Ohms sq cm), low zincate diffusivity (less than 1 x 10 to the -7th mols/sq cm per min), and low zinc dendrite penetration rate (greater than 350 min) which make them suitable for use as alkaline battery separators. They are intrinsically low in cost, and environmental health and safety problems associated with commercial production appear minimal. Preparation, property measurements, and cell test results in Ni/Zn and Ag/Zn cells are described and discussed.

Hsu, L.-C.↗

NASA NTRS1980

Nitrogen dioxide vapor penetration of chlorobutyl rubber SCAPE under operational conditions

Operational self contained atmospheric protective ensembles (SCAPE suits) and fabric from the suits were subjected to a series of tests designed to determine the amount of exposure a wearer of the suit would receive if a spill of the hypergolic oxidizer nitrogen tetroxide (N2O4) should occur nearby. The results of these tests show that a wearer of a "stock" SCAPE suit equipped with a standard liquid air pack, if exposed to a spill resulting in a 26 percent increase of oxidizer in the surrounding atmosphere, will experiment no detectable concentration of nitrogen dioxide (NO2) inside the suit for 15 minutes. Thereafter, the NO2 concentration within the suit will increase for 35 minutes at a rate of 0.07 ppm per minute and then at a gradually decreasing rate until an equilibrium concentration of 3.4 ppm is attained after 100 minutes. Momentary increases of as much as 1.6 ppm can be expected if the wearer were to rise quickly from a squatting position, but the additional NO2 would be dissipated within three minutes. The effect of liquid and vapor N2O4 and of liquid monomethylhydrazine on permeation rates and tensile strength of the SCAPE suit fabric was also investigated.

Schehl, T. A.↗

NASA NTRS2013

Auto-Gopher: A Wireline Deep Sampler Driven by Piezoelectric Percussive Actuator and EM Rotary Motor

The ability to penetrate subsurfaces and perform sample acquisition at depth of meters may be critical for future NASA in-situ exploration missions to bodies in the solar system, including Mars and Europa. A corer/sampler was developed with the goal of enabling acquisition of samples from depths of several meters where if used on Mars would be beyond the oxidized and sterilized zone. For this purpose, we developed a rotary-hammering coring drill, called Auto-Gopher, which employs a piezoelectric actuated percussive mechanism for breaking formations and an electric motor that rotates the bit to remove the powdered cuttings. This sampler is a wireline mechanism that can be fed into and retrieved from the drilled hole using a winch and a cable. It includes an inchworm anchoring mechanism allowing the drill advancement and weight on bit control without twisting the reeling and power cables. The penetration rate is being optimized by simultaneously activating the percussive and rotary motions of the Auto-Gopher. The percussive mechanism is based on the Ultrasonic/Sonic Drill/Corer (USDC) mechanism that is driven by piezoelectric stack and that was demonstrated to require low axial preload. The design and fabrication of this device were presented in previous publications. This paper presents the results of laboratory and field tests and lessons learned from this development.

piezoactuation↗

NASA NTRS1985

Oxidation resistant slurry coating for carbon-based materials

An oxidation resistant coating is produced on carbon-base materials, and the same processing step effects an infiltration of the substrate with silicon containing material. The process comprises making a slurry of nickel and silicon powders in a nitrocellulose lacquer, spraying onto the graphite or carbon-carbon substrate, and sintering in vacuum to form a fused coating that wets and covers the surface as well as penetrates into the pores of the substrate. Optimum wetting and infiltration occurs in the range of Ni-60 w/o Si to Ni-90 w/o Si with deposited thicknesses of 25-100 mg/sq. cm. Sintering temperatures of about 1200 C to about 1400 C are used, depending on the melting point of the specific coating composition. The sintered coating results in Ni-Si intermetallic phases and SiC, both of which are highly oxidation resistant.

Smialek, J. L.↗