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NASA NTRS2012

Descent with Modification: Thermal Reactions of Subsurface H2O2 of Relevance to Icy Satellites and Other Small Bodies

Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Similarly, cosmic radiation (mainly protons) acting on cometary and interstellar ices can promote extensive chemical change. Among the products that have been identified in irradiated H20-ice is hydrogen peroxide (H202), which has been observed on Europa and is suspected on other worlds. Although the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, the thermally-induced solid-phase chemistry of H2O2 is largely unknown. Therefore, in this presentation we report new laboratory results on reactions at 50 - 130 K in ices containing H2O2 and other molecules, both in the presence and absence of H2O. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to SO4(2-). We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto. If other molecules prove to be just as reactive with frozen H2O2 then it may explain why H2O2 has been absent from surfaces of many of the small icy bodies that are known to be exposed to ionizing radiation. Our results also have implications for the survival of H2O2 as it descends towards a subsurface ocean on Europa.

Hudson, Reggie L.↗

NASA NTRS1989

Environmental definition of the earth's neutral atmosphere

Although number densities are low at altitudes where spacecraft typically operate, high orbital speeds result in incident fluxes and collisional energies large enough to interact with and degrade material surfaces. Global thermospheric models, when combined with orbital mechanics models, may be used to predict atomic oxygen fluence, or total integrated flux incidence on spacecraft sentences. Fluence predictions, when used with STS materials reactivity measurements, provide reliable estimates of the oxidative effects on spacecraft surfaces.

Visentine, James T.↗

NASA NTRS2009

Decay of Reactivity Induced by Simulated Solar Wind Implantation of a Forsteritic Olivine

In returning humans to the Moon, the Lunar Airborne Dust Toxicity Advisory Group (LADTAG) must address many problems faced by the original Apollo astronauts. Major among these is control of the fine dust (<20 microns) that makes up approx.20 wt% portion of the lunar surface. This ubiquitous, clinging, sharp, abrasive, glassy dust caused a plethora of problems with seals, abrasion, and coatings, in addition to possible health problems, including lunar dust hayfever. The lifetime of reactive sites on the surfaces of irradiated lunar dust grains is of interest to those studying human health because of the free radicals and toxic compounds that may be formed and may not passivate quickly when exposed to habitat/spacecraft air.

Kuhlman, K.R.↗

NASA NTRSDate not supplied

Investigating Material Behavior in Atmospheric Entry Conditions: Arc-Jet Testing Insights from Meteorite Ablation to High-Temperature Coatings.

Arc-jet testing is an indispensable tool in elucidating the complex interactions materials undergo when subjected to the extreme thermal and mechanical stresses of atmospheric entry. By replicating these harsh conditions, arc-jets enable researchers to explore critical phenomena such as ablation, melting, and spallation, generating invaluable data that informs the development of sophisticated, physics-based models. These models are pivotal not only in predicting material performance for spacecraft re-entry systems but also in assessing the threat posed by celestial bodies as they encounter Earth’s atmosphere. One of the leading facilities for such investigations is the Hypersonic Materials Environmental Test System (HyMETS) at NASA’s Langley Research Center. A pioneering test campaign conducted at HyMETS focused on unraveling the ablation mechanisms of an ordinary chondrite meteorite (Tamdakht H5) and a terrestrial analog (basalt). These studies unveiled distinct material behaviors: Tamdakht demonstrated a remarkably stable melt flow, with mass loss primarily driven by the volatilization of elements such as iron and sodium, whereas basalt exhibited more aggressive surface degradation due to the rapid decomposition of hydrated minerals, culminating in significant spallation and surface material ejection. Beyond meteorite analysis, HyMETS has also been integral in the exploration of advanced Thermal Protection Systems (TPS) such as Phenolic Impregnated Carbon Ablator (PICA), a material with extensive flight heritage in missions like Stardust, Mars Science Laboratory, Mars 2020, and Osiris-REx. PICA, when coated with NuSil CV-1144-0—a polysiloxane resin designed to prevent particle shedding—undergoes a remarkable transformation upon heating. The resin pyrolyzes to form a thin, oxidation-resistant silicon oxycarbide layer that profoundly influences the material’s thermal response through a sophisticated four-stage process. Initially, the silicon oxycarbide acts as a formidable barrier, impeding reactive interactions with the PICA char and effectively suppressing surface temperature rise and material recession. However, as the heating persists, the protective layer decomposes via carbothermal reduction, exposing the underlying char, which in turn leads to a dramatic spike in surface temperature and accelerated material erosion. In the final stage, equilibrium is reached, with recession rates aligning with those of the virgin material. This intricate understanding of PICA-NuSil behavior under extreme conditions offers valuable insights, enhancing material response models and advancing the development of next-generation TPS for space exploration.

Chemistry↗

NASA NTRS1994

XPS analysis of 440C steel surfaces lubricated with perfluoropolyethers under sliding conditions in high vacuum

This work presents the results of the X-Ray Photoelectron Spectroscopy (XPS) analysis of AISI 440C ball surfaces lubricated with perfluoropolyether (PFPE) oils after friction experiments under sliding conditions at high load in air and vacuum environments. The PFPE lubricants tested were Demnum S100, Fomblin Z-25, and Krytox 143AB. It was found that all the PFPE lubricants were degraded by sliding contact causing the formation of inorganic fluorides on the metallic surfaces and a layer of organic decomposition products. KRYTOX 143AB was the least reactive of the three lubricants tested. It was also found that metal fluoride formed at off-scar areas. This suggests the formation of reactive species, such as COF2 or R(sub f)COF, during sliding experiments, which can diffuse through the lubricant film and react with the metallic surfaces away from the contact region. Comparison of reference specimens before sliding with those that had undergone the sliding tests showed that the amount of non-degraded PFPE remaining on the surface of the balls after the sliding experiments was greater than that of the balls without sliding.

Herrera-Fierro, Pilar↗

NASA NTRS2000

Mathematical Modeling of an Oscillating Droplet

Oscillating droplets are of interest in a number of disciplines. A practical application is the oscillating drop method, which is a technique for measuring surface tension and viscosity of liquid metals. It is especially suited to undercooled and highly reactive metals, because it is performed by electromagnetic levitation. The natural oscillation frequency of the droplets is related to the surface tension of the material, and the decay of oscillations is related to its viscosity. The fluid flow inside the droplet must be laminar in order for this technique to yield good results. Because no experimental method has yet been developed to visualize flow in electromagnetically-levitated oscillating metal droplets, mathematical modeling is required to determine whether or not turbulence occurs. Three mathematical models of the flow: (1) assuming laminar conditions, (2) using the k-epsilon turbulence model, and (3) using the RNG turbulence model, respectively, are compared and contrasted to determine the physical characteristics of the flow. It is concluded that the RNG model is the best suited for describing this problem. The goal of the presented work was to characterize internal flow in an oscillating droplet of liquid metal, and to verify the accuracy of the characterization by comparing calculated surface tension and viscosity.

Berry, S.↗

NASA NTRS2002

Mars Surface Environmental Issues

Planetary exploration by astronauts will require extended periods of habitation on a planet's surface, under the influence of environmental factors that are different from those of Earth and the spacecraft that delivered the crew to the planet. Human exploration of Mars, a possible near-term planetary objective, can be considered a challenging scenario. Mission scenarios currently under consideration call for surface habitation periods of from 1 to 18 months on even the earliest expeditions. Methods: Environmental issues associated with Mars exploration have been investigated by NASA and the National Space Biomedical Research Institute (NSBRI) as part of the Bioastronautics Critical Path Roadmap Project (see http ://criticalpath.jsc.nasa.gov). Results: Arrival on Mars will immediately expose the crew to gravity only 38% of that at Earth's surface in possibly the first prolonged exposure to gravity other than the 1G of Earth's surface and the zero G of weightless space flight, with yet unknown effects on crew physiology. The radiation at Mars' surface is not well documented, although the planet's bulk and even its thin atmosphere may moderate the influx of galactic cosmic radiation and energetic protons from solar flares. Secondary radiation from activated components of the soil must also be considered. Ultrafine and larger respirable and nonrespirable particles in Martian dust introduced into the habitat after surface excursions may induce pulmonary inflammation exacerbated by the additive reactive and oxidizing nature of the dust. Stringent decontamination cannot eliminate mechanical and corrosive effects of the dust on pressure suits and exposed machinery. The biohazard potential of putative indigenous Martian microorganisms may be assessed by comparison with analog environments on Earth. Even in their absence, human microorganisms, if not properly controlled, can be a threat to the crew's health. Conclusions: Mars' surface offers a substantial challenge to the health and safety of future human explorers.

Charles, John↗

NASA NTRS2019

Carbon Nanostructures in Biological Sensors for Space and Terrestrial Applications

Biosensing devices comprised of carbon nanotubes and nanofibers have been developed for astronaut crew point-of-care. Their inherent nanometer scale, high conductivity, wide potential window, good biocompatibility and well-defined surface chemistry make them ideal candidates as biosensor electrodes. Here, we report two studies using carbon nanotube and carbon nanofiber electrodes for biomedical applications. First, a 3x3 electrode device, with each electrode containing 40,000 carbon nanofiber nanoelectrodes was fabricated on silicon using traditional microfabrication processing. The device was demonstrated as a multiplexed immunosensor for simultaneous, label-free detection of cardiac troponin-I, C-reactive protein and myoglobin. Antibodies specific to cardiac troponin-I, C-reactive protein and myoglobin were covalently bound to the CNF surface and were characterized using electrochemical impedance spectroscopy and differential pulse voltammetry. Each step of the modification process resulted in changes in resistance to charge transfer due to the changes at the electrode surface upon antibody immobilization and binding to the specific cardiac protein. The real-time label free detection of the three cardiac markers from pure components and mixtures was demonstrated with high sensitivity, down to 0.2 ng/mL, and good selectivity. Detection in human blood serum did not present false positives from non-specific protein adsorption. More recently, this detection scheme has been applied to inkjet printed carbon nanotube electrodes on Kapton and paper. Printed devices have several unique advantages including simple and inexpensive fabrication. The results demonstrate that these sensors can serve a miniaturized, low cost device for detection of proteins in complex mixtures making this platform a good candidate for early stage diagnosis of myocardial infarction. Future inkjet printed devices can be fabricated have the added advantage in their suitability to be manufactured in an in-space, microgravity environment.

carbon nanotubes↗

NASA NTRS2019

Carbon Nanomaterials for Biosensing Applications

carbon nanotubes↗

NASA NTRS1995

Reactively Deposited Aluminum Oxide and Fluoropolymer Filled Aluminum Oxide Protective Coatings for Polymers

Reactive ion beam sputter deposition of aluminum simultaneous with low energy arrival of oxygen ions at the deposition surface enables the formation of highly transparent aluminum oxide films. Thick (12 200 A), adherent, low stress, reactively deposited aluminum oxide films were found to provide some abrasion resistance to polycarbonate substrates. The reactively deposited aluminum oxide films are also slightly more hydrophobic and more transmitting in the UV than aluminum oxide deposited from an aluminum oxide target. Simultaneous reactive sputter deposition of aluminum along with polytetrafluoroethylene (PTFE Teflon) produces fluoropolymer-filled aluminum oxide films which are lower in stress, about the same in transmittance, but more wetting than reactively deposited aluminum oxide films. Deposition properties, processes and potential applications for these coatings will be discussed.

Rutledge, Sharon K.↗

NASA NTRS1999

Growth of Homoepitaxial ZnO Semiconducting Films

As a high temperature wide-band-gap (3.3 eV at room temperature) semiconductor, ZnO has been used for many applications such as wave-guides, solar cells, and surface acoustic wave devices, Since ZnO has a 60 meV excitonic binding energy that makes it possible to produce excitonic lasing at room temperature, a recent surge of interest is to synthesize ZnO films for UV/blue/green laser diodes. These applications require films with a smooth surface, good crystal quality, and low defect density. Thus, homoepitaxial film growth is the best choice. Homoepitaxial films have been studied in terms of morphology, crystal structure, and electrical and optical properties. ZnO single crystal substrates grown by the hydrothermal method are mechanically polished and annealed in air for four hours before the films are deposited. The annealing temperature-dependence on ZnO substrate morphology and electrical properties is investigated. Films are synthesized by off-axis reactive sputtering deposition. This produces films that have very smooth surfaces with roughness less than or equal to 5 nm on a 5 microns x 5 microns area. The full width at half maximum of film theta rocking curves measured by the x-ray diffraction is slightly larger than that of the crystal substrate. Films are also characterized by measuring resistivity, optical transmittance, and photoluminescence. The properties of ZnO films grown on (0001) ZnO and (0001) sapphire substrates will also be compared and discussed.

Zhu, Shen↗

NASA NTRS2002

Surface Oscillations of An Electromagnetically Levitated Droplet

Oscillating droplets are of interest in a number of disciplines. A practical application is the oscillating drop method, which is a technique for measuring surface tension and viscosity of liquid metals. It is especially suited to undercooled and highly reactive metals, because it is usually performed by electromagnetic levitation. The natural oscillation frequency a f the droplets is related to the surface tension of the material, and the decay of oscillations is related to its viscosity. The fluid flow inside the droplet must be laminar in order for this technique to yield good results. Because no experimental method has yet been developed to visualize flow in electromagnetically-levitated oscillating metal droplets, mathematical modeling is required to determine whether or not turbulence occurs. Three mathematical models of the flow: (1) assuming laminar conditions, (2) using the turbulence model, and (3) using the RNG turbulence model, respectively, are compared and contrasted to determine the physical characteristics of the flow. It is concluded that the RNG model is the best suited for describing this problem. The goal of the presented work was to characterize internal flow in an oscillating droplet of liquid metal, and to verify the accuracy of the characterization by comparing calculated surface tension and viscosity values to experimentally-obtained results.

Berry, S.↗

NASA NTRS1971

A thermosphere composition measurement using a quadrupole mass spectrometer with a side energy focussing quasi-open ion source

The atomic oxygen concentration in the altitude range 130 to 240 km was determined through the use of a quadrupole spectrometer with a strongly focussing ion source. The instrument is used in the Thermosphere Probe in a manner that greatly increases the proportion of measured oxygen ions that have not experienced a surface collision and permits quantitative evaluation of surface recombination and thermalization effects which inevitably enter all spectrometer determinations. The data obtained strengthen the concept that consideration of surface effects is significant in quantifying spectrometer measurements of reactive gases, and tend to be in agreement with von Zahn's recent results.

Niemann, H. B.↗

NASA NTRS1977

Planetary atmospheres with mass spectrometers carried on high-speed probes or satellites

Earth satellite-borne mass spectrometers are considered, taking into account the identification of atomic oxygen in the thermosphere with an 'open' source mass spectrometer flown on a sounding rocket, the conventional closed-source instrument, the mass spectrometers on the Atmosphere Explorer satellites, and mass spectrometer electron multiplier output. A description is presented of mass spectrometers and planetary entry probes. Attention is given to an attempt to obtain an atmospheric composition profile with a terrestrial entry probe, the descending trajectory in the early orbits of the Atmosphere Explorer C satellite, and the molecular nitrogen densities for the descending legs of the orbits. It is pointed out that chemical reactions on the surfaces of the mass spectrometer make the measurement of reactive atmospheric species such as atomic oxygen very difficult.

Nier, A. O.↗

NASA NTRS1980

Method for producing thin sheets of proton-sensitive CR-39 plastic track detectors

Procedures for fabricating large sheets of CR-39 with uniform chemical reactivity and sensitivity and which retain a clear, smooth surface after prolonged etching were investigated. Very thin sheets for certain Spacelab applications were fabricated.

Kinoshita, K.↗

NASA NTRS1985

Ceramic oxide reactions with V2O5 and SO3

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Jones, R. L.↗

NASA NTRS1999

Polarity Effects of Substrate Surface in Epitaxial ZnO Film Growth

Epitaxial ZnO films were grown on the two polar surfaces (0-face and Zn-face) of (0001) ZnO single crystal substrates using off-axis magnetron sputtering deposition. As a comparison, films are also deposited on the (000 I) Al203 substrates. It is found that the two polar surfaces have different photoluminescence (PL) spectrum, surface structure and morphology, which are strongly inference the epitaxial film growth. The morphology and structure of epitaxial films on the ZnO substrates are different from the film on the Al203 substrates. An interesting result shows that high temperature annealing of ZnO single crystals will improve the surface structure on the O-face surface rather than the opposite Surface. The measurements of PL, low-angle incident x-ray diffraction, and atomic force microscopy of ZnO films indicate that the O-terminated surface is better for ZnO epitaxial film growth using reactive sputtering deposition.

Zhu, Shen↗

NASA NTRS2001

An Overview of the SOLVE-THESEO 2000 Campaign

Between November 1999 and April 2000, two major field experiments, the SAGE III Ozone Loss and Validation Experiment (SOLVE) and the Third European Stratospheric Experiment on Ozone (THESEO 2000), collaborated to form the largest field campaign yet mounted to study Arctic ozone loss. This international campaign involved more than 500 scientists from over 20 countries spread across the high and mid-latitudes of the northern hemisphere. The main scientific aims of SOLVE-THESEO 2000 were to study (a) the processes leading to ozone loss in the Arctic vortex and (b) the effect on ozone amounts over northern mid-latitudes. The campaign included satellites, heavy lift balloon launches, 6 different aircraft, ground stations, and scores of ozone-sonde. Campaign activities were principally conducted in 3 intensive measurement phases centered on early December 1999, late January 2000, and early March 2000. Observations made during the campaign showed that temperatures were unusually cold in the polar lower stratosphere over the course of the 1999-2000 winter. These cold temperatures resulted in the formation of extensive polar stratospheric clouds (PSCs) across the Arctic. Heterogeneous chemical reactions on the surfaces of the PSC particles produced high levels of reactive chlorine within the polar vortex by early January. This reactive chlorine catalytically destroyed about 60% of the ozone in a layer near 20 km between late January and mid-March 2000.

Newman, Paul A.↗