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At least 523 records · Page 29

Chemistry of atmosphere-surface interactions on Venus and Mars

Earth-based, earth-orbital, and spacecraft observational data are used in the present evaluation of Venus atmosphere-surface interactions to quantitatively characterize the reactions between C, H, S, Cl, F, and N gases and plausible surface minerals. Calculation results are used to predict stable minerals and mineral assemblages on the Venus surface, in order to ascertain which (if any) of the atmospheric gases are buffeted by mineral assemblages. Chemical equilibrium calculations using extant thermodynamic data on scapolite minerals predict that carbonate-bearing scapolite and sulfate meionite are unstable on the surface of Venus, while chloride-bearing scapolite is stable.

Fegley, Bruce, Jr.↗

An experimental study of growth and phase change of polar stratospheric cloud particles

This report describes the progress made on understanding phase changes related to solutions which may comprise Polar Stratospheric Clouds. In particular, it is concerned with techniques for investigating specific classes of metastability and phase change which may be important not only in Polar Stratospheric Clouds but in all atmospheric aerosols in general. While the lower level atmospheric aerosol consists of mixtures of (NH4)(SO4)2, NH4HSO4, NaCl among others, there is evidence that aerosol at PSC levels is composed of acid aerosol, either injected from volcanic events (such as Pinatubo) or having diffused upward from the lower atmosphere. In particular, sulfuric acid and nitric acid are known to occur at PSC levels, and are suspected of catalyzing ozone destruction reactions by adsorption on surfaces of crystallized particles. The present study has centered on two approaches: (1) the extent of supercooling (with respect to ice) and supersaturation (with respect to hydrate) and the nature of crystal growth in acid solutions of specific molality; and (2) the nature of growth from the vapor of HNO3 - H2O crystals both on a substrate and on a pre-existing aerosol.

Hallett, John↗

Three-dimensional modelling of trace species in the Arctic lower stratosphere

A three-dimensional radiative-dynamical-chemical model has been developed and used to study some aspects of modeling the polar lower stratosphere. The model includes a comprehensive gas-phase chemistry scheme as well as a treatment of heterogeneous reactions occurring on the surface of polar stratospheric clouds. Tracer transport is treated by an accurate, nondispersive scheme with little diffusion suited to the representation of strong gradients. Results from a model simulation of early February 1990 are presented and used to illustrate the importance of the model transport scheme. The model simulation is also used to examine the potential for Arctic ozone destruction and the relative contributions of the chemical cycles responsible.

Chipperfield, Martyn↗

Carbonates and sulfates in the Chassigny meteorite: Further evidence for aqueous chemistry on the SNC parent planet

Scanning electron microscopy and energy-dispersive X-ray spectrometry of untreated interior chips from three different specimens of the Chassigny meteorite confirm the presence of discrete grains of Ca-carbonate, Mg-carbonate, and Ca-sulfate. Morphologies of these salt grains suggest that the Ca-carbonate is calcite (CaCO3) and that the Ca-sulfate is gypsum (CaSO4-2H2O) or bassanite (CaSO4-1/2H2O). The morphologic identification of the Mg-carbonate is equivocal, but rhombohedral and acicular crystal habits suggest magnesite and hydromagnesite, respectively. The salts in Chassigny occur as discontinuous veins in primary igneous minerals and are similar to those previously documented in the nakhlites, Nakhla and Lafayette, and in shergottite EETA79001. Unlike those in nakhlites, however, the Chassigny salts occur alone, without associated ferric oxides or aluminosilicates clays. Traces of Cl and P in Chassigny salts are consistent with precipitation of the salts from short-lived, saline, aqueous solutions that postdated igneous crystallization. In contrast with the clear case for nakhlites, stratigraphic evidence for a preterrestrial origin of the salts in Chassigny is ambiguous; however, a preterrestrial origin of the Chassigny salts best explains all available evidence. The water-precipitated salts provide clear physical evidence for the hypothesis, proposed by other workers, that the igneous amphiboles in Chassigny might have experienced isotope-exchange reactions with near-surface water, thereby compromising the original stable-isotope signature of any magmatic water in melt inclusions.

Wentworth, Susan J.↗

Observations of lower-stratospheric ClONO2, HNO3, and aerosol by the UARS CLAES experiment between January 1992 and April 1993

This paper discusses simultaneous measurements of stratospheric ClONO2, HNO3, temperature, and aerosol extinction coefficient by the Cryogenic Limb Array Etalon Spectrometer (CLAES) on the NASA Upper Atmosphere Research Satellite (UARS), obtained over the period 9 January 1992 through 23 April 1993. The discussion concentrates on the stratosphere region near 21 km of particular interest to heterogeneously driven ozone depletion. For periods between 12 June and 1 September 1992 at latitudes poleward of about 60 deg S, when temperatures were below type I polar stratospheric cloud (PSC) formation thresholds throughout the lower stratosphere, CLAES observed high levels of PSCs coincident with highly depleted fields of both HNO3 and ClONO2. By 17 September, the incidence of PSCs had greatly diminished in the lower stratosphere, but both CLONO2 and HNO3 remained highly depleted. These observations are consistent with the removal of gaseous HNO3 through the formation of nitric acid trihydrate (NAT) particles and the removal of ClONO2 through heterogeneous reactions on the particle surfaces. They also suggest substantial denitrification of the lower Antarctic vortex through sedimentation of PSC particles. In the Northern Hemisphere winter of 1992/93 far fewer PSCs were observed in the Arctic lower-stratosphere vortex, which had shorter periods and more localized regions of cold temperatures. Both HNO3 and ClONO2 maintained much higher levels inside the Arctic vortex than seen in the Antarctic throughout the winter/spring period. Following 28 February 1993 when Arctic vortex temperatures rose above 195 K, ClONO2 was observed in large quantities (greater than 2.1 ppbv near 21 km) inside the vortex. The persistence of relatively high levels of HNO3 inside the Arctic spring vortex compared with the low levels seen in the Antarctic spring vortex suggest a much lower level of denitrification in the Arctic.

Roche, A. E.↗

Detection of Polar Stratospheric Clouds Using AVHRR Imagery

In recent years, the role of PSCs in the ozone depletion process has become better understood. PSCs provide the surfaces upon which heterogeneous reactions take place that affect the gas phase partitioning between active and reservoir chlorine and nitrogen species. Present methods of PSC detection include in situ measurements by lidar and various satellite-borne instruments such as the Stratospheric Aerosol Measurement II (SAM II) on the Nimbus 7 spacecraft, which produced PSC measurements from 1978 to 1994 and several instruments onboard the Upper Atmospheric Research Satellite (UARS) such as the Cryogenic Limb Array Etalon Spectrometer (CLAES) which provided measurements for 1991-1993. All of the PSC-detection methods devised so far have been hampered by incomplete sampling of the places and times in which PSCs are likely to form. There is a need to understand the climatology of PSCS, in particular the timing of their onset and duration, their vertical distribution, geographic extent, annual variability and responses to volcanic aerosol forcing. Poole and Pitts [1994] assembled a PSC climatology based on SAM II data, but this climatology is incomplete, as it is limited to the edge of the polar night due to the limitations of the solar occultation scan geometry. The Advanced Very High Resolution Radiometer (AVHRR) five- channel sensors onboard the NOAA polar-orbiting satellites have been collecting data over the polar regions continuously since 1979. These operational satellites provide unmatched coverage in space and time of both polar regions, but were not designed for the detection of optically-thin PSCS. However, the AVHRR data archive would be an invaluable source for the construction of a long-term climatology of PSCs if techniques can be developed and tested to detect PSCs in AVHRR data. In the last few years, the members of our group at San Francisco State University and NASA Ames Research Center have been engaged in the development of various PSC detection methods using AVHRR data. There is strong evidence that a subset of PSCS, those that are optically thick, can be readily identified in the AVHRR data set. Our group has also made significant progress in the identification of optically thinner PSCs using a variety of techniques.

Garcia, Oswaldo↗

Hydrogen in rocks: an energy source for deep microbial communities

To survive in deep subsurface environments, lithotrophic microbial communities require a sustainable energy source such as hydrogen. Though H2 can be produced when water reacts with fresh mineral surfaces and oxidizes ferrous iron, this reaction is unreliable since it depends upon the exposure of fresh rock surfaces via the episodic opening of cracks and fissures. A more reliable and potentially more voluminous H2 source exists in nominally anhydrous minerals of igneous and metamorphic rocks. Our experimental results indicate that H2 molecules can be derived from small amounts of H2O dissolved in minerals in the form of hydroxyl, OH- or O3Si-OH, whenever such minerals crystallized in an H2O-laden environment. Two types of experiments were conducted. Single crystal fracture experiments indicated that hydroxyl pairs undergo an in situ redox conversion to H2 molecules plus peroxy links, O3Si/OO\SiO3. While the peroxy links become part of the mineral structure, the H2 molecules diffused out of the freshly fractured mineral surfaces. If such a mechanism occurred in natural settings, the entire rock column would become a volume source of H2. Crushing experiments to facilitate the outdiffusion of H2 were conducted with common crustal igneous rocks such as granite, andesite, and labradorite. At least 70 nmol of H2/g diffused out of coarsely crushed andesite, equivalent at standard pressure and temperature to 5,000 cm3 of H2/m3 of rock. In the water-saturated, biologically relevant upper portion of the rock column, the diffusion of H2 out of the minerals will be buffered by H2 saturation of the intergranular water film.

Hydrogen/analysis↗

Epoxy Crosslinked Silica Aerogels (X-Aerogels)

NASA is interested in the development of strong lightweight materials for the dual role of thermal insulator and structural component for space vehicles; freeing more weight for useful payloads. Aerogels are very-low density materials (0.010 to 0.5 g/cc) that, due to high porosity (meso- and microporosity), can be, depending on the chemical nature of the network, ideal thermal insulators (thermal conductivity approx. 15 mW/mK). However, aerogels are extremely fragile. For practical application of aerogels, one must increase strength without compromising the physical properties attributed to low density. This has been achieved by templated growth of an epoxy polymer layer that crosslinks the "pearl necklace" network of nanoparticles: the framework of a typical silica aerogel. The requirement for conformal accumulation of the epoxy crosslinker is reaction both with the surface of silica and with itself. After cross-linking, the strength of a typical aerogel monolith increases by a factor of 200, in the expense of only a 2-fold increase in density. Strength is increased further by coupling residual unreacted epoxides with diamine.

fabrizio, Eve↗

Detection of Ice Polar Stratospheric Clouds from Assimilation of Atmospheric Infrared Sounder Data

A novel technique is presented for detection of ice polar stratospheric clouds (PSCs) that form at extremely low temperatures in the lower polar stratosphere during winter. Temperature is a major factor in determining abundance of PSCs, which in turn provide surfaces for heterogeneous chemical reactions leading to ozone loss and radiative cooling. The technique infers the presence of ice PSCs using radiances from the Atmospheric Infrared Sounder (AIRS) in the Goddard Earth Observing System version 5 (GEOS-5) data assimilation system. Brightness temperatures are computed from short-term GEOS-5 forecasts for several hundred AIRS channels, using a radiation transfer module. The differences between collocated AIRS observations and these computed values are the observed-minus-forecast (O-F) residuals in the assimilation system. Because the radiation model assumes clear-sky conditions, we hypothesize that these O-F residuals contain quantitative information about PSCs. This is confirmed using sparse data from the Polar Ozone and Aerosol Measurement (POAM) III occultation instrument. The analysis focuses on 0-F residuals for the 6.79pm AIRS moisture channel. At coincident locations, when POAM III detects ice clouds, the AIRS O-F residuals for this channel are lower than -2K. When no ice PSCs are evident in POAM III data, the AIRS 0-F residuals are larger. Given this relationship, the high spatial density of AIRS data is used to construct maps of regions where 0-F residuals are lower than -2K, as a proxy for ice PSCs. The spatial scales and spatio-temporal variations of these PSCs in the Antarctic and Arctic are discussed on the basis of these maps.

Stajner, Ivanka↗

Nano-Ceramic Coated Plastics

Plastic products, due to their durability, safety, and low manufacturing cost, are now rapidly replacing cookware items traditionally made of glass and ceramics. Despite this trend, some still prefer relatively expensive and more fragile ceramic/glassware because plastics can deteriorate over time after exposure to foods, which can generate odors, bad appearance, and/or color change. Nano-ceramic coatings can eliminate these drawbacks while still retaining the advantages of the plastic, since the coating only alters the surface of the plastic. The surface coating adds functionality to the plastics such as self-cleaning and disinfectant capabilities that result from a photocatalytic effect of certain ceramic systems. These ceramic coatings can also provide non-stick surfaces and higher temperature capabilities for the base plastics without resorting to ceramic or glass materials. Titanium dioxide (TiO2) and zinc oxide (ZnO) are the candidates for a nano-ceramic coating to deposit on the plastics or plastic films used in cookware and kitchenware. Both are wide-bandgap semiconductors (3.0 to 3.2 eV for TiO2 and 3.2 to 3.3 eV for ZnO), so they exhibit a photocatalytic property under ultraviolet (UV) light. This will lead to decomposition of organic compounds. Decomposed products can be easily washed off by water, so the use of detergents will be minimal. High-crystalline film with large surface area for the reaction is essential to guarantee good photocatalytic performance of these oxides. Low-temperature processing (<100 C) is also a key to generating these ceramic coatings on the plastics. One possible way of processing nanoceramic coatings at low temperatures (< 90 C) is to take advantage of in-situ precipitated nanoparticles and nanostructures grown from aqueous solution. These nanostructures can be tailored to ceramic film formation and the subsequent microstructure development. In addition, the process provides environment- friendly processing because of the aqueous solution. Low-temperature processing has also shown versatility to generate various nanostructures. The growth of low-dimensional nanostructures (0-D, 1-D) provides a means of enhancing the crystallinity of the solution-prepared films that is of importance for photocatalytic performance. This technology can generate durable, fully functional nano-ceramic coatings (TiO2, ZnO) on plastic materials (silicone, Teflon, PET, etc.) that can possess both photocatalytic oxide properties and flexible plastic properties. Processing cost is low and it does not require any expensive equipment investment. Processing can be scalable to current manufacturing infrastructure.

Cho, Junghyun↗

Pterodactyl: Control System Demonstrator Development for Integrated Control Design of a Mechanically Deployed Entry Vehicle

The NASA-funded Pterodactyl project is a design, test, and build capability to (i) advance the current state of the art for Deployable Entry Vehicle (DEV) guidance and control (G&C), and (ii) determine the feasibility of control system integration for various entry vehicle types including those without aeroshells. This capability is currently being used to develop control systems for one such unconventional entry vehicle, the Lifting Nano-ADEPT (LNA) vehicle. ADEPT offers the possibility of integrating control systems directly onto the mechanically deployed structure and building hardware demonstrators will help assess integration and design challenges. Control systems based on aerodynamic control surfaces, mass movement, and reaction control systems (RCS) are currently being investigated for a down-select to the most suitable control architecture for the LNA.To that effect, in this submission, we detail the efforts of the Pterodactyl project to develop a series of hardware demonstrators for the different LNA control systems. Rapid prototypes, for a set of quarter- model or eighth-model vehicle segments, will be developed for all three architectures to validate mechanical design assumptions, and hardware-in-the-loop (HIWL) control approaches. A ground test control system demonstrator will be designed and built after the trade study is complete. The industrial-grade demonstrator will be designed so that it can be incorporated into a HWIL simulation to further validate the findings of the initial trade study. The HWIL simulation will leverage the iPAS environment developed at NASA's Johnson Space Center which facilitates integration testing to support technology maturation and risk reduction, necessary elements for the hardware demonstration development detailed in this paper.

Margolis, Benjamin W.↗

Atomic Oxygen Environment and Effects Overview

Atomic oxygen is the most predominant constituent in the low Earth orbital environment between the altitudes of 180 and 650 km. It is also a major constituent of the Mars orbital environment. It is very chemically reactive and can oxidize many spacecraft surfaces to form volatile reaction products. The importance of understanding atomic oxygen reactions with materials has led to both flight experiments in low Earth orbit and ground-based testing in vacuum chambers containing atomic oxygen to study its’ effect on materials. Testing has been performed in order to determine the extent of the atomic oxygen reaction and assess material and component durability. In addition, the effectiveness of mitigation techniques such as application of a protective coating, adding fillers, or using shielding and getter materials has also been studied both in flight and ground-based experiments. This presentation will focus on defining atomic oxygen environments, discussing its effect on spacecraft materials, and describing some of the testing and mitigation techniques that have been investigated.

Atomic Oxygen, Low Earth Orbit, Low Mars Orbit, ox↗

Reaction of sulfur dioxide with modified 440C, studied by Auger electron spectroscopy and depth profiling

Auger electron spectroscopy and sputtering were used to study the interaction of SO2 with modified 440C, which is a nominally 77-wt%-Fe, 14-wt%-Cr, and 4-wt%-Mo bearing steel with C, S, Si, Ni, V, P, and Mn making up the balance. The sample was polycrystalline. Three temperatures were used: room temperature, 500 C, and 600 C. The reaction time was varied from 30 minutes to 2 hours. A surface cleaned of oxides was the starting point for each reaction. For reactions at 500 C, the major constituents Cr, O, Fe, and S were present in the surface film. At 600 C, the principal constituents of the film were Cr, O, and S with no Fe present. Therefore, a transition in film composition occurred between 500 and 600 C. Oxides were the primary constituents of the films at both temperatures. Room-temperature reactions indicated that SO2 adsorbed dissociatively, with approximately equal quantities of S and O on the surface. For the same reaction time (1 hr) and pressure, a strong temperature dependence of film thickness was observed. The film formed at 600 C was approximately seven times thicker than that formed at 500 C.

Ferrante, J.↗

Oxygen atom reaction with shuttle materials at orbital altitudes

Surfaces of materials used in the space shuttle orbiter payload bay and exposed during STS-1 through STS-3 were examined after flight. Paints and polymers, in particular Kapton used on the television camera thermal blanket, showed significant change. Generally, the change was a loss of surface gloss on the polymer with apparent aging on the paint surfaces. The Kapton surfaces showed the greatest change, and postflight analyses showed mass loss of 4.8 percent on STS-2 and 35 percent on STS-3 for most heavily affected surfaces. Strong shadow patterns were evident. The greatest mass loss was measured on surfaces which were exposed to solar radiation in conjunction with exposure in the vehicle velocity vector. A mechanism which involves the interaction of atomic oxygen with organic polymer surfaces is proposed. Atomic oxygen is the major ambient species at low orbital altitudes and presents a flux of 8 x 10 to the 14th power atoms/cu cm sec for reaction. Correlation of the expected mass loss based on ground-based oxygen atom/polymer reaction rates shows lower mass loss of the Kapton than measured. Consideration of solar heating effects on reaction rates as well as the high oxygen atom energy due to the orbiter's orbital velocity brings the predicted and measured mass loss in surprisingly good agreement. Flight sample surface morphology comparison with ground based Kapton/oxygen atom exposures provides additional support for the oxygen interaction mechanism.

Leger, L. J.↗

Atomic Oxygen Treatment as a Method of Recovering Smoke Damaged Paintings

Smoke damage, as a result of a fire, can be difficult to remove from some types of painting media without causing swelling, leaching or pigment movement or removal. A non-contact technique has been developed which can remove soot from the surface of a painting by use of a gently flowing gas containing atomic oxygen. The atomic oxygen chemically reacts with the soot on the surface creating gasses such as carbon monoxide and carbon dioxide which can be removed through the use of an exhaust system. The reaction is limited to the surface so that the process can be timed to stop when the paint layer is reached. Atomic oxygen is a primary component of the low Earth orbital environment, but can be generated on Earth through various methods. This paper will discuss the results of atomic oxygen treatment of soot exposed acrylic gesso, ink on paper, and a varnished oil painting. Reflectance measurements were used to characterize the surfaces before and after treatment.

Rutledge, Sharon K.↗

Surface Hardness Testing of Mobile Launcher 1 (ML-1) Vehicle Support Posts (VSP) Following Artemis I Launch Exposure

Following the successful launch of Artemis I on November 16th, 2022 (Fig 1), a surface hardness assessment was performed on the eight primary VSPs (Figs. 2, 3) located on the Zero Deck of the ML. This assessment was performed as part of an instrument investigation for strain gauges installed on VSP interior surfaces that had a “strange reaction”. This report does not address the VSP strain gauge investigation, but rather VSP structural integrity for future service (Artemis II, III, …). Surface hardness measurements were taken to assess the strength of the ASTM A148 steel castings to confirm thermal exposure from launch had not reannealed the VSPs. However unlikely, it is possible high temperature may have heated and tempered (reannealed) the VSPs, resulting in a change of built-in stresses. This loss in built-in stress may explain the change in off-set measured by the strain gauges. Initial hardness measurements were made at two interior surfaces of VSPs near the strain gauges and the corresponding exterior surfaces (engine hole-facing). Field hardness measurements on the exterior, engine hole surface-facing surfaces for all eight VSPs ranged from 175 to 226 HB/P, well below the minimum hardness of 302 Brinell (HB). Opposing interior surface hardness measurements near strain gauges ranged from 264 to 358 HB/P. In all cases for flight VSPs, a drop in interior-to-exterior hardness ranging from 70 to 132 HB/P was measured. Surface hardness measurements were then made on the two spare VSPs not exposed to launch temperatures for baseline comparison. These two spare VSPs had a drop in Brinell hardness from interior to exterior surfaces ranging from 3 to 17 HB/P. The large interior-to-exterior delta hardness for eight flight VSPs but not for the two spare VSPs suggests launch exposure temperatures softened the exterior surfaces, raising two questions: 1) Are the VSPs compromised for future use, and 2) How deep is the exterior surface softening effect? To address concerns of low surface hardness values at non-critical exterior surfaces, additional field surface hardness measurements were taken at high-stress locations on VSP3: Both door jams, back radius, and internal left and right radius near the base. These values came in well above the required minimum hardness (317 to 365 HB/P). For a more representative pre-launch versus post-launch surface hardness comparison, VSP Acceptance Data Packages (ADPs) were reviewed, and hardness measurements were made at the same eight original locations on VSP3 where hardness measurements were made at the foundry. To determine the degree of softening, 1/8” of material was machined away at three exterior surfaces of engine hole-facing side (Fig. 4). A significant increase in surface hardness was measured ranging from 50 to 86 HB/P. Values at these three locations were still slightly below the required minimum hardness, so an additional 1/8” material was machined away, and hardness values were retaken. At the ¼” depth, hardness values increased to 321 to 324 HB/P. These values fall above the required minimum, concluding surface hardness testing. Rationale for VSP continued use was reached with no restrictions during a Chief Engineering Review based on hardness values exceeding minimum at critical locations and subsurface locations for VSP #3.

Artemis I↗

Experimental Study of the Stability of Aircraft Fuels at Elevated Temperatures

An experimental study of fuel stability was conducted in an apparatus which simulated an aircraft gas turbine fuel system. Two fuels were tested: Jet A and Number 2 Home Heating oil. Jet A is an aircraft gas turbine fuel currently in wide use. No. 2HH was selected to represent the properties of future turbine fuels, particularly experimental Reference Broad Specification, which, under NASA sponsorship, was considered as a possible next-generation fuel. Tests were conducted with varying fuel flow rates, delivery pressures and fuel pretreatments (including preheating and deoxygenation). Simulator wall temperatures were varied between 422K and 672K at fuel flows of 0.022 to 0.22 Kg/sec. Coking rate was determined at four equally-spaced locations along the length of the simulator. Fuel samples were collected for infrared analysis. The dependence of coking rate in Jet A may be correlated with surface temperature via an activation energy of 9 to 10 kcal/mole, although the results indicate that both bulk fluid and surface temperature affect the rate of decomposition. As a consequence, flow rate, which controls bulk temperature, must also be considered. Taken together, these results suggest that the decomposition reactions are initiated on the surface and continue in the bulk fluid. The coking rate data for No. 2 HH oil are very highly temperature dependent above approximately 533K. This suggests that bulk phase reactions can become controlling in the formation of coke.

Vranos, A.↗