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NASA NTRS2025

Erosion Results of the MISSE 9-15 Polymers and Composites Experiment 1-4 (PCE 1-4)

Polymers and other oxidizable materials on the exterior of spacecraft in the low Earth orbit (LEO) space environment can be eroded from reaction with atomic oxygen (AO). Therefore, in order to design durable spacecraft it is important to know the extent of erosion that will occur during a mission. This can be determined by knowing the LEO AO erosion yield, E y (volume loss per incident oxygen atom), of materials susceptible to AO reaction. In addition, recent flight experiments have shown that the AO E y can vary with the AO fluence and/or solar exposure. Therefore, obtaining AO E y data for materials flown on various spaceflight missions is important. NASA Glenn Research Center has flown numerous experiments as part of the Materials International Space Station Experiment (MISSE) missions on the exterior of the International Space Station (ISS) to characterize the LEO E y of polymers, composites, protective coatings, and other spacecraft materials. Recently, four Glenn experiments with 365 flight (F) samples were flown on ISS’s MISSE-Flight Facility (MISSE-FF). These experiments are the Polymers and Composites Experiment-1 (PCE-1) flown as part of the MISSE-9 mission, the PCE-2 flown as part of the MISSE-10 mission, the PCE-3 flown as part of the MISSE-12 and MISSE-15 missions, and the PCE-4 flown as part of the MISSE-13 mission. Although each experiment had numerous sample objectives, the primary objective was to determine the LEO AO E y of various spacecraft materials as a function of solar irradiation and AO fluence. This paper provides a summary of the erosion data for the PCE 1-4 AO E y samples. The AO E y for 150 samples flown in either the LEO ram, wake, zenith or nadir directions are provided. The AO ram fluence varied from 2.97×10 20 atoms/cm 2 after 0.89 years of direct space exposure (with relatively high levels of Si contamination) on MISSE 12 to 3.93×10 20 atoms/cm 2 after 1.17 years of direct space exposure on MISSE-10. The ram AO E y values for uncoated polymers range from 3.81×10 –25 cm 3 /atom for polytetrafluoroethylene (M9R-C20 F) exposed to an AO fluence of 3.44×10 20 atoms/cm 2 on MISSE-9 to 4.43×10 –23 cm 3 /atom for AO etched low density polyimide aerogel (M12R-C21 F) exposed to an AO fluence of 2.97×10 21 atoms/cm 2 on MISSE-12. Because of the low AO fluence and relatively high Si contamination, a number of PCE-3 wake samples experienced mass gain. Thus, AO E y values are not provided for these samples. Although there are calculated AO E y values for the zenith, wake and nadir samples, the ram AO E y for a particular material is a more reliable value in terms of AO exposure because the zenith, wake and nadir directions were exposed to either no or very little AO fluence and thus other space environmental factors (i.e. vacuum, thermal extremes and thermal cycling, and/or various types of radiation) are responsible for the mass loss.

Erosion yield↗
NASA NTRSDate not supplied

Metallic Powder Core Tubular Wire (PCTW) Development for Additive Manufacturing

NASA Langley Research Center (LaRC) in Hampton, VA, and the Center for Welding, Joining, and Coating Research (CWJCR) in the Department of Metallurgical and Materials Engineering at the Colorado School of Mines (CSM) in Golden, CO, have collaborated for nearly fifteen years to develop metallic powder core tubular wire (PCTW) feedstock for additive manufacturing (AM) using electron beam deposition. The motivation for this development was to offset dealloying observed during deposition of titanium and aluminum alloy solid wire feedstock in the LaRC electron beam freeform fabrication (EBF3) system and to explore novel alloy compositions by tailoring the powder fill. EBF3 is a fusion-based AM process that is performed under vacuum and is consequently prone to vaporization loss of low vapor pressure alloying elements. Research spanning four graduate student research projects succeeded in developing the basic methodology to fabricate PCTW, the mass balance equations used to define the powder fill, microstructure control through particulate inoculation, and the feasibility of producing metal matrix composite materials. Metallic PCTW is comprised of a thin foil sheath wrapped around a powder blend. Fabrication of PCTW at CSM was accomplished using a tubular wire mill system to first bend a flat strip into a u-shaped cross section, deposit a powder fill, create a lap joint to seal the wire, and draw to final diameter. Powder management systems were developed to ensure uniform mixing of powder constituents and identify feed rates for optimum fill ratios. Processing parameters were successfully developed for titanium and aluminum alloy sheaths to account for material work hardening during drawing. Mass balance equations were developed to account for compositional contributions of the sheath and powder fill. PCTW composition can be adjusted through selection of the sheath or powder materials. PCTWs were successfully developed to offset Al loss in deposits of Ti-6-4 and Mg loss in Al 6061, resulting in deposits that were within the composition limits for each material. Ti-6-4 deposits were fabricated using PCTW comprised of commercially pure (CP) titanium sheath and a fill of pre-alloyed Ti-6-4 powder with additions of elemental Al and V powders. Additions of both elements were required to account for the CP Ti from the sheath, and Al was further enhanced to offset documented losses in EBF3 deposits. For Al 6061 deposits, composition was modulated through the choice of sheath material. The PCTW was made using an Al 5052 sheath to supplement Mg content and a fill composition of pre-alloyed 6061 powder with additions of Si and Cu.The slower solidification rate of the EBF3 process compared with laser powder bed fusion processes can lead to coarse-grained microstructures and mechanical property anisotropy. EBF3deposits of Ti-6-4 exhibited large epitaxially grown β grains, which result in degraded mechanical properties in the deposition direction. Microstructure refinement was achieved through a combination of electron beam modulation and the use of a PCTW designed for Ti-6-4 deposits and modified by the addition of powder made from Fe and B. Resulting deposits exhibited reductions in β grain size, α phase colony intercept length and lath width, and an increased volume fraction of β phase. The mechanism of microstructure refinement was related to precipitation of boride particles. Hardness testing confirmed that mechanical property anisotropy was reduced and an overall increase in hardness was achieved.Metal matrix composite (MMC) materials offer strength and stiffness benefits over unreinforced materials. Two methods were investigated using PCTW technology for producing Al 6061 basedMMC materials; the direct addition of SiC reinforcing particles and the in-situ generation of reinforcements through reaction synthesis of precursor powders. Al 6061 based MMCs reinforced with SiC exhibited particle clustering and formation of aluminum carbides during deposition. The application of a Ni coating to the SiC particles prior to incorporation into the powder fill eliminated aluminum carbide formation and aided particle distribution during deposition. Modulation of beam focus and power further reduced aluminum carbide formation and aided particle distribution. In reaction synthesis, precursor additions undergo an exothermic reaction during deposition to form new ceramic products, generally of finer scale than the initial precursor components. The product phases provide reinforcement in the MMC and act as nucleation sites during solidification, resulting in grain refinement, improved mechanical properties, and reduced susceptibility to solidification cracking. Higher tensile strength and stiffness were demonstrated in Al 6061 based MMCs with 2 vol% reinforcement. These combined research efforts demonstrate the potential of PCTW technology for customizing of alloy composition and achieving microstructure control. A manufacturing process for titanium- and aluminum-based PCTWs was developed based on iterative design, theoretical calculations, and empirical data. PCTW technology successfully mitigated Al loss from Ti-6-4 and Mg loss in Al 6061, resulted in grain refinement in Ti-6-4, and demonstrated fabrication of Al based MMCs

Marcia S Domack↗
NASA NTRS1986

Tougher Addition Polyimides Containing Siloxane

Laminates show increased impact resistances and other desirable mechanical properties. Bismaleamic acid extended by reaction of diaminosiloxane with maleic anhydride in 1:1 molar ratio, followed by reaction with half this molar ratio of aromatic dianhydride. Bismaleamic acid also extended by reaction of diaminosiloxane with maleic anhydride in 1:2 molar ratio, followed by reaction with half this molar ratio of aromatic diamine (Michael-addition reaction). Impact resistances improved over those of unmodified bismaleimide, showing significant increase in toughness. Aromatic addition polyimides developed as both matrix and adhesive resins for applications on future aircraft and spacecraft.

St. Clair, T. L.↗
NASA NTRS2007

The Effect of Increasing Inertia upon Vertical Ground Reaction Forces during Locomotion

The addition of inertia to exercising astronauts could increase ground reaction forces and potentially provide a greater health benefit. However, conflicting results have been reported regarding the adaptations to additional mass (inertia) without additional net weight (gravitational force) during locomotion. We examined the effect of increasing inertia while maintaining net gravitational force on vertical ground reaction forces and kinematics during walking and running. Vertical ground reaction force was measured for ten healthy adults (5 male/5 female) during walking (1.34 m/s) and running (3.13 m/s) using a force-measuring treadmill. Subjects completed locomotion at normal weight and mass, and at 10, 20, 30, and 40% of added inertial force. The added gravitational force was relieved with overhead suspension, so that the net force between the subject and treadmill at rest remained equal to 100% body weight. Peak vertical impact forces and loading rates increased with increased inertia during walking, and decreased during running. As inertia increased, peak vertical propulsive forces decreased during walking and did not change during running. Stride time increased during walking and running, and contact time increased during running. Vertical ground reaction force production and adaptations in gait kinematics were different between walking and running. The increased inertial forces were utilized independently from gravitational forces by the motor control system when determining coordination strategies.

DeWitt, John K.↗
NASA NTRS1992

Nonenzymatic template-directed synthesis on oligodeoxycytidylate sequences in hairpin oligonucleotides

We have developed a novel method for studying template-directed synthesis in hairpin oligonucleotides. An unpaired segment at the 5'-terminus of the hairpin acts as an intramolecular template for the extension of the paired 3'-terminus. Products are analyzed by denaturing gel electrophoresis of [32P]-labeled hairpins. Using this system, we have studied the synthesis of oligoguanylates on an oligodeoxycytidylate template. We find that guanosine 5'-phosphoro(2-methyl)imidazolide adds efficiently to a terminal riboguanylate residue at temperatures in the range 0-37 degrees C but not at 50 degrees C. At 0 degree C, the half-time for addition of the first G residue is about 3 h, and the reaction rate is independent of pH in the range 6.5-8.0. The first addition reaction results in the formation of a predominantly 3'-5'-internucleotide bond. When the 3'-terminal riboguanylate residue is placed by a deoxyguanylate residue, the half-time for the first addition increases from about 3 to about 30 h.

NASA Discipline Exobiology↗
NASA NTRS1994

Heterogeneous Reaction of ClONO2(g) + NaCl(s) to Cl2(g) + NaNO3(s)

The heterogeneous reaction of ClON02 + NaCl yields Cl2 + NaNO3 (eq 1) was investigated over a temperature range 220-300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer. Partial pressures of ClON02 in the range 10(exp -8) - 10(exp -5) Torr were used. Granule sizes and surface roughness of the NaCl substrates were determined by using a scanning electron microscope, and in separate experiments, surface areas of the substrates were measured by using BET analysis of gas-adsorption isotherms. For dry NaCl substrates, both the decay rates of ClON02 and the growth rates Of C12 were used to obtain reaction probabilities, gamma(sub l) = (4.6 +/- 3.0) x 10(exp -3) at 296 K and (6.7 +/- 3.2) x 10(exp -1) at 225 K, after considering the internal surface area, The error bars represent 1 standard deviation. The Cl2 yield based on the ClONO2 reacted was measured to be 1.0 +/- 0.2. In order to mimic the conditions encountered in the lower stratosphere, the effect of water vapor pressures between 5 x 10(exp -5) and 3 x 10(exp -4) Torr on reaction 1 was also studied. With added H20, reaction probabilities, gamma = (4.1 +/- 2.1) x 10(exp -3) at 296 K and (4.7 +/- 2.9) x 10(exp -3) at 225 K, were obtained. A trace of HOCl, the reaction product from the ClON02 + H20 yield HOCl + HN03 reaction, was observed in addition to the C12 product from reaction 1. The implications of this result for the enhancement of hydrogen chloride in the stratosphere after the El Chichon volcanic eruption and for the marine troposphere are discussed.

Timonen, Raimo S.↗
NASA NTRS1992

Ignition delays, heats of combustion, and reaction rates of aluminum alkyl derivatives used as ignition and combustion enhancers for supersonic combustors

The work was based on adapting an apparatus and procedure developed at Southwest Research Institute for rating the ignition quality of fuels for diesel engines. Aluminum alkyls and various Lewis-base adducts of these materials, both neat and mixed 50/50 with pure JP-10 hydrocarbon, were injected into the combustion bomb using a high-pressure injection system. The bomb was pre-charged with air that was set at various initial temperatures and pressures for constant oxygen density. The ignition delay times were determined for the test materials at these different initial conditions. The data are presented in absolute terms as well as comparisons with the parent alkyls. The relative heats of reaction of the various test materials were estimated based on a computation of the heat release, using the pressure data recorded during combustion in the bomb. In addition, the global reaction rates for each material were compared at a selected tmperature and pressure.

Ryan, T. W., III↗
NASA NTRSDate not supplied

Fixed-Bed Columns for Adsorption of C2H2 in Metal Organic Frameworks for Hydrogen Recovery in Long-Duration Human Space Flight

To live and work in space, astronauts must have a breathable atmosphere. Current life support system technology utilizes the electrolysis of water to recover O2 as the main method of Oxygen recovery. In addition, the Sabatier Reaction is used to recover H2O from the CO2 produced by human respiration. The current atmosphere revitalization architecture onboard the International Space Station (ISS) has an efficiency of approximately 54% oxygen recovery. Therefore, these systems require substantial resupplies of water to sustain this environment, which make long-duration space flight missions, such as Martian transit, expensive and difficult. In order to support these missions, oxygen recovery must exceed 75-90% efficiency. Additional research has shown that with the addition of a Plasma Pyrolysis system, CH4 produced by the Sabatier reaction may be broken down into H2 and C2H2 and the H2 may be recycled. However, the Hydrogen must be separated from the highly volatile C2H2. There are many potential separation methods. A promising method includes the adsorption of the C2H2 into Metal Organic Frameworks (MOFs) using Vacuum Swing Adsorption. Due to the fragile nature of the MOFs and hazards present in producing C2H2, the columns must have a design that is compatible to both materials and that has the potential to operate in extraterrestrial environments. Successful design and testing of this Hydrogen separation system would allow the PPA to be fully integrated into the current oxygen regeneration system, resulting in a theoretical O2 recovery of 91.3%.

Hannah K Davis↗
NASA NTRS2001

Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

Iraci, Laura T.↗
NASA NTRS1986

Kinetic studies of the reaction of the SO radical with NO2 and ClO from 210 to 363 K

The rates of the reactions of the SO radical with NO2 and ClO (significant in the upper atmosphere of earth and Venus) were determined in a discharge flow system near 1 torr pressure with detection of radical and molecular species using collision-free sampling mass spectrometry. The rate constants were obtained from the decay of SO radicals in the presence of an excess of NO2 and ClO. The NO2 reaction was examined between 210 and 363 K and found to be temperature invariant: SO + NO2 yields SO2 + NO; k1 = (1.37 + or - 0.10) x 10 to the -11th cu cm/s. In addition, the ClO reaction was observed to be independent of temperature between 248 and 363 K: SO + ClO yields SO2 + Cl; k2 = (3.22 + or - 0.48) x 10 to the -11th cu cm/s. A comparison was made with previous investigations of these reactions at room temperature and with other radical-radical reactions involving SO or ClO.

Brunning, J.↗
NASA NTRS1985

Effect of argon and hydrogen on deposition of silicon from tetrochlrosilane in cold plasmas

The roles of Ar and H2 on the decomposition of SiCl4 in cold plasma were investigated by Langmuir probes and mass spectrometry. Decomposition of the reactant by Ar only has been found to be very slow. In presence of H2 in the plasma SiCl4 is decomposed by fast radical-molecule reactions which are further enhanced by Ar due to additional ion-molecule reactions in which more H radicals are produced. A model for the plasma-surface interactions during deposition of mu-Si in the Ar + H2 + SiCl4 system is presented.

Manory, R. R.↗
NASA NTRS1977

Recent results from the Viking Labeled Release experiment on Mars

The Labeled Release (LR) life detection experiment seeks detection of heterotrophic metabolism by monitoring radio-active gas evolution following the addition of a radioactive nutrient containing seven C-14 labeled organic substrates to surface material. LR results obtained on Mars prior to conjunction showed rapid evolution of radioactive counts upon addition of the nutrient to a fresh surface sample. The responses at both landing sites were quite similar. The additional results summarized in the present paper provide further information on the gas kinetics following a second injection of nutrient and on the effect of 'cold sterilization' of the Martian surface material. Specifically, it is shown that the production of gas from the LR nutrient is remarkably uniform; after reaction approaches completion, addition of more nutrient results in a net loss of the radioactive gas; the reactant in the Mars soil is completely inhibited by heating the soil to 160 C, and is largely inhibited by heating to 46 C. In contrast, exposure to 18 C for 2 sol (1 sol = 24.6 hr) does not appear to inhibit the reaction.

Levin, G. V.↗
NASA NTRS1993

Convective instabilities in traveling fronts of addition polymerization

An autocatalytic reaction in an unstirred vessel can support a constant velocity wavefront resulting from the coupling of diffusion to the chemical reaction. A flare front is a common example in which heat is the autocatalytic species that diffuses into unreacted regions stimulating a reaction that produces more heat. Traveling fronts were studied in synthetic polymerization reactions under high pressure by workers in the former USSR. More recently, propagating fronts of methacrylic acid polymerization were studied under ambient conditions, both with video techniques and by NMR.

Pojman, John A.↗
NASA NTRS2001

The Behavior of Methane-Air Partially Premixed Flames Under Normal- and Zero-G Conditions

Partially premixed flames (PPFs) represent a class of hybrid flames containing multiple reaction zones. These flames are established when less than stoichiometric quantity of oxidizer is molecularly mixed with the fuel stream before entering the reaction zone where additional oxidizer is available for complete combustion. This mode of combustion can be used to exploit the advantages of both nonpremixed and premixed flames regarding operational safety, lower pollutant emissions and flame stabilization. A double flame containing a fuel-rich premixed reaction zone, which is anchored by a nonpremixed reaction zone, is one example of a partially premixed flame. A triple flame is also a PPF that contains three reaction zones, namely, a fuel-rich premixed zone, a fuel-lean premixed zone, and a nonpremixed reaction zone. Herein we focus on two aspects of our investigation, one involving the development of optical diagnostics that can be used on a microgravity rig, which has been recently fabricated, and the other on the numerically predicted differences between normal- and zero-gravity PPFs. Both the measurements and simulations examine the detailed structure of methane-air PPFs stabilized on a Wolfhard-Parker slot burner.

Puri, Ishwar K.↗
NASA NTRS2004

Simulation of Aerosols and Chemistry with a Unified Global Model

This project is to continue the development of the global simulation capabilities of tropospheric and stratospheric chemistry and aerosols in a unified global model. This is a part of our overall investigation of aerosol-chemistry-climate interaction. In the past year, we have enabled the tropospheric chemistry simulations based on the GEOS-CHEM model, and added stratospheric chemical reactions into the GEOS-CHEM such that a globally unified troposphere-stratosphere chemistry and transport can be simulated consistently without any simplifications. The tropospheric chemical mechanism in the GEOS-CHEM includes 80 species and 150 reactions. 24 tracers are transported, including O3, NOx, total nitrogen (NOy), H2O2, CO, and several types of hydrocarbon. The chemical solver used in the GEOS-CHEM model is a highly accurate sparse-matrix vectorized Gear solver (SMVGEAR). The stratospheric chemical mechanism includes an additional approximately 100 reactions and photolysis processes. Because of the large number of total chemical reactions and photolysis processes and very different photochemical regimes involved in the unified simulation, the model demands significant computer resources that are currently not practical. Therefore, several improvements will be taken, such as massive parallelization, code optimization, or selecting a faster solver. We have also continued aerosol simulation (including sulfate, dust, black carbon, organic carbon, and sea-salt) in the global model to cover most of year 2002. These results have been made available to many groups worldwide and accessible from the website http://code916.gsfc.nasa.gov/People/Chin/aot.html.

Chin, Mian↗
NASA NTRS1987

Potential energy surfaces for atomic oxygen reactions: Formation of singlet and triplet biradicals as primary reaction products with unsaturated organic molecules

The experimental study of the interaction of atomic oxygen with organic polymer films under LEO conditions has been hampered by the inability to conduct detailed experiments in situ. As a result, studies of the mechanism of oxygen atom reactions have relied on laboratory O-atom sources that do not fully reproduce the orbital environment. For example, it is well established that only ground electronic state O atoms are present at LEO, yet most ground-based sources are known to produce singlet O atoms and molecules and ions in addition to O(3P). Engineers should not rely on such facilities unless it can be demonstrated either that these different O species are inert or that they react in the same fashion as ground state atoms. Ab initio quantum chemical calculations have been aimed at elucidating the biradical intermediates formed during the electrophilic addition of ground and excited-state O atoms to carbon-carbon double bonds in small olefins and aromatic molecules. These biradicals are critical intermediates in any possible insertion, addition and elimination reaction mechanisms. Through these calculations, we will be able to comment on the relative importance of these pathways for O(3P) and O(1D) reactions. The reactions of O atoms with ethylene and benzene are used to illustrate the important features of the mechanisms of atomic oxygen reaction with unsaturated organic compounds and polymeric materials.

Jaffe, Richard L.↗
NASA NTRS1975

Chemical reactions of metal powders with organic and inorganic liquids during ball milling

Chromium and/or nickel powders were milled in metal chlorides and in organic liquids representative of various functional groups. The powders always reacted with the liquid and became contaminated with elements from them. The milled powders had specific surface areas ranging from 0.14 to 37 sq m/g, and the total contamination with elements from the milling liquid ranged from 0.01 to 56 weight percent. Compounds resulting from substitution, addition, or elimination reactions formed in or from the milling liquid.

Arias, A.↗