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At least 271 records · Page 15

Effects of atomic oxygen and ultraviolet radiation on candidate elastomeric materials for long duration missions. Test series no.1

Research was conducted at MSFC on the behavior of elastomeric materials after exposure to simulated space environment. Silicone S383 and Viton V747 samples were exposed to thermal vacuum, ultraviolet radiation, and atomic oxygen and then evaluated for changes in material properties. Characterization of the elastomeric materials included weight, hardness, optical inspection under normal and black light, spectrofluorescence, solar absorptance and emittance, Fourier transform infrared spectroscopy, and permeability. These results indicate a degree of sensitivity to exposure and provided some evidence of UV and atomic oxygen synergism.

Linton, R. C.↗

Systematic Sensitivity Analysis of Metabolic Controllers During Reductions in Skeletal Muscle Blood Flow

An acute reduction in oxygen delivery to skeletal muscle is generally associated with profound derangements in substrate metabolism. Given the complexity of the human bioenergetic system and its components, it is difficult to quantify the interaction of cellular metabolic processes to maintain ATP homeostasis during stress (e.g., hypoxia, ischemia, and exercise). Of special interest is the determination of mechanisms relating tissue oxygenation to observed metabolic responses at the tissue, organ, and whole body levels and the quantification of how changes in oxygen availability affect the pathways of ATP synthesis and their regulation. In this study, we apply a previously developed mathematical model of human bioenergetics to study effects of ischemia during periods of increased ATP turnover (e.g., exercise). By using systematic sensitivity analysis the oxidative phosphorylation rate was found to be the most important rate parameter affecting lactate production during ischemia under resting conditions. Here we examine whether mild exercise under ischemic conditions alters the relative importance of pathways and parameters previously obtained.

Radhakrishnan, Krishnan↗

Oxygen Compatibility Testing of Composite Materials

Composite materials offer significant weight-saving potential for aerospace applications in propellant and oxidizer tanks. This application for oxygen tanks presents the challenge of being oxygen compatible in addition to complying with the other required material characteristics. This effort reports on the testing procedures and data obtained in examining and selecting potential composite materials for oxygen tank usage. Impact testing of composites has shown that most of these materials initiate a combustion event when impacted at 72 ft-lbf in the presence of liquid oxygen, though testing has also shown substantial variability in reaction sensitivities to impact. Data for screening of 14 potential composites using the Bruceton method is given herein and shows that the 50-percent reaction frequencies range from 17 to 67 ft-lbf. The pressure and temperature rises for several composite materials were recorded to compare the energy releases as functions of the combustion reactions with their respective reaction probabilities. The test data presented are primarily for a test pressure of 300 psia in liquid oxygen. The impact screening process is compared with oxygen index and autogenous ignition test data for both the composite and the basic resin. The usefulness of these supplemental tests in helping select the most oxygen compatible materials is explored. The propensity for mechanical impact ignition of the composite compared with the resin alone is also examined. Since an ignition-free composite material at the peak impact energy of 72 ft-lbf has not been identified, composite reactivity must be characterized over the impact energy level and operating pressure ranges to provide data for hazard analyses in selecting the best potential material for liquid tank usage.

Engel, Carl D.↗

MHD performance calculations with oxygen enrichment

The impact of oxygen enrichment of the combustion air on the generator and overall plant performance was studied for the ECAS-scale MHD/steam plants. A channel optimization technique is described and the results of generator performance calculations using this technique are presented. Performance maps were generated to assess the impact of various generator parameters. Directly and separately preheated plant performance with varying O2 enrichment was calculated. The optimal level of enrichment was a function of plant type and preheat temperature. The sensitivity of overall plant performance to critical channel assumptions and oxygen plant performance characteristics was also examined.

Pian, C. C. P.↗

A scalable and autoclavable oxygen nanosensor platform for metabolic monitoring of Saccharomyces cerevisiae in a bioreactor and other in situ systems

Polymer-encapsulated dye nanoparticle sensors are a valuable approach to achieving in situ analyte measurements with luminescence; however, typical emulsion-based nanosensors are poorly suited for large-scale biological samples due to limitations of synthesis scalability and stability. Branched polyethylenimine (PEI) is a versatile polymer scaffold ideal for constructing nanoparticles with various covalently conjugated moieties due to their high density of reactive primary amines, high water solubility, and biological stability. In this work, we used branched polyethylenimine as a scaffold-based approach for making a stable and scalable ratiometric oxygen sensor. Pt (II) tetracarboxyporphine was used as an oxygen-sensing dye and coumarin 343 as a reference dye, all covalently linked to the PEI scaffold producing a product that could withstand sterilization procedures and easily be scaled. To minimize toxicity from the PEI scaffold, we conjugated it with 2000 MW PEG. The applicability of the sensors was demonstrated in a 200 mL Saccharomyces cerevisiae yeast culture, using orthogonal luminescent and electrochemical oxygen measurements to validate sensor response and measure the metabolic activity of the yeast in our culture. Further, this approach was able to match the sensitivity of our electrochemical measurements while improving upon drawbacks of other luminescent methods of oxygen detection, demonstrating effective monitoring for at least 20 h. Our scaffold-based approach is a modular and easily translatable technology that could be useful in various biotechnological applications.

59 BASIC BIOLOGICAL SCIENCES↗

On the Sensitivity of Coastal Hypoxia to Its External Physical Forcings

Abstract The development of low‐oxygen zones threatening marine life (hypoxia) occurs annually in multiple coastal regions of the world. The largest estuary of the continental United States, the Chesapeake Bay, typically has ≈10 km 3 of water with dioxygen concentrations <3 mg L −1 in July. As numerical methods for refining model resolutions in targeted areas are becoming common, there is interest in assessing the feasibility of simulating coastal hazards such as hypoxia in Earth System Models (ESMs). These coupled models are typically not constrained by observations and thus likely to feature systematic biases in their land, atmosphere, or ocean components. This study relies on four numerical experiments to evaluate the sensitivity of Chesapeake Bay hypoxia to changes or biases in its external physical forcings. Hypoxia exhibits only a minor decrease (−1.6%) after reducing the Bay's terrestrial freshwater discharge by 9.5% (but keeping terrestrial nutrient loadings the same). Changes in freshwater discharges have their largest impact on hypoxia during one extreme event (−37% during 2011 tropical storm Lee). Similarly, changing oceanic conditions on the shelf or their temporal frequency impact hypoxia by only 5%–6%, indicating that the latter is predominantly dictated by local conditions. Although these results are promising from the perspective of ESMs, additional components of ESMs will need to be evaluated before general conclusions can be reached. We notably speculate that the Bay's hypoxia would exhibit higher sensitivity to other forcings not examined here, notably air temperatures and nutrient loadings.

Meteorology & Atmospheric Sciences↗

Revealing the Surface Structure of CdSe Nanocrystals by Dynamic Nuclear Polarization-Enhanced 77 Se and 113 Cd Solid-State NMR Spectroscopy

Dynamic nuclear polarization (DNP) solid-state NMR (SSNMR) spectroscopy was used to obtain detailed surface structures of zinc blende CdSe nanocrystals (NCs) with plate or spheroidal morphologies which are capped by carboxylic acid ligands. 1D 113 Cd and 77 Se cross-polarization magic angle spinning (CPMAS) NMR spectra revealed distinct signals from Cd and Se atoms on the surface of the NCs, and those residing in bulk-like environments, below the surface. 113 Cd cross-polarization magic-angle-turning (CP-MAT) experiments identified CdSe 3 O, CdSe 2 O 2 , and CdSeO 3 Cd coordination environments on the surface of the NCs, where the oxygen atoms are presumably from coordinated carboxylate ligands. The sensitivity gain from DNP enabled natural isotopic abundance 2D homonuclear 113 Cd– 113 Cd and 77 Se– 77 Se and heteronuclear 113 Cd– 77 Se scalar correlation solid-state NMR experiments which revealed the connectivity of the Cd and Se atoms. Importantly, 77 Se{ 113 Cd} scalar heteronuclear multiple quantum coherence ( J -HMQC) experiments were used to selectively measure one-bond 77 Se– 113 Cd scalar coupling constants ( 1 J ( 77 Se, 113 Cd)). With knowledge of 1 J ( 77 Se, 113 Cd), heteronuclear 77 Se{ 113 Cd} spin echo ( J -resolved) NMR experiments were used to determine the number of Cd atoms bonded to Se atoms and vice versa. Furthermore, the J -resolved experiments directly confirmed that major Cd and Se surface species have CdSe 2 O 2 and SeCd 4 stoichiometries, respectively. Considering the crystal structure of zinc blende CdSe and the similarity of the solid-state NMR data for the platelets and spheroids, we conclude that the surface of the spheroidal CdSe NCs is primarily composed of {100} facets. The methods outlined here will generally be applicable to obtain detailed surface structures of various main group semiconductor nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Susceptibility to hot corrosion of four nickel-base superalloys, NASA-TRW VIA, B-1900, 713C and IN-738

The susceptibility to hot corrosion of four nickel-base, cast superalloys has been studied at 900 and 1000 C. The test consisted of coating alloy samples with known amounts of Na2SO4 and oxidizing the coated samples isothermally in 1 atmosphere of slowly flowing oxygen, the weight-gain being monitored on a sensitive recording microbalance. Susceptibility to hot corrosion decreased in the order of decreasing molybdenum content of the alloys. Preoxidation of samples before hot-corrosion testing markedly increased the induction period observed prior to the inception of hot corrosion for all alloys tested. X-ray diffraction analyses of the oxide scales were made. All samples that underwent hot corrosion showed the presence of a (Ni,Co)MoO4 layer near the alloy-oxide interface. Several specimens displayed resistance to hot corrosion and these showed NaTaO3 as a prominent feature in their oxide scale. Our results may be interpreted as indicating that molybdenum in an alloy is detrimental, with respect to hot corrosion, while tantalum is beneficial.

Stearns, C. A.↗

Airborne Lidar measurements of the atmospheric pressure profile with tunable Alexandrite lasers

The first remote measurements of the atmospheric pressure profile made from an airborne platform are described. The measurements utilize a differential absorption lidar and tunable solid state Alexandrite lasers. The pressure measurement technique uses a high resolution oxygen A band where the absorption is highly pressure sensitive due to collision broadening. Absorption troughs and regions of minimum absorption were used between pairs of stongly absorption lines for these measurements. The trough technique allows the measurement to be greatly desensitized to the effects of laser frequency instabilities. The lidar system was set up to measure pressure with the on-line laser tuned to the absorption trough at 13147.3/cm and with the reference laser tuned to a nonabsorbing frequency near 13170.0/cm. The lidar signal returns were sampled with a 200 range gate (30 vertical resoltion) and averaged over 100 shots.

Korb, C. L.↗

The surface variation of Ti-14Al-21Nb as a function of temperature under ultrahigh vacuum conditions

The effect of temperature, at conditions of ultrahigh vacuum, on the surface composition of the Ti-14Al-21Nb (in wt pct) alloy was investigated in samples heated to 1000 C in 100 C increments. Results of AES spectroscopy revealed that the Ti-14Al-21Nb alloy surface is extremely sensitive to temperature. At 300 C, the carbon and oxygen began to rapidly dissolve into the alloy, and at 600 C, bulk S segregated to the surface. The variation in the surface composition was extensive and different over the temperature range studied, indicating that there may be substantial changes in the hydrogen transport.

Lee, W. S.↗

Advanced Material Options for the Portable Life Support System

Meeting an aggressive mass requirement is a challenge for new space suit development efforts, including that of the Exploration Extravehicular Mobility Unit Portable Life Support System (PLSS) government reference design. To reduce overall system mass, titanium was selected as the primary metal for the PLSS backplate and thermal loop. However, galvanically compatible metals (Hastelloy, Inconel, Monel) have relatively high densities and require further design complexities such as coatings and more challenging manufacturing. Efforts to reduce the mass of the government reference design for an International Space Station (ISS) or lunar mission were halted due to the government’s transition to a commercial Extravehicular Activity (EVA) services approach, but research was conducted into methodologies for mass savings using advanced materials. With the advent of a lunar Artemis mission and potential for future Mars missions, mass becomes a more critical driver going forward. Therefore, alternative materials and processes must be considered to fully close the mass requirement. There are many new materials and processes that can be considered; however, considerations must be made to ensure galvanic compatibility, radiation concerns for sensitive electronics, vacuum compatibility, tight tolerances, fluid compatibility with oxygen and water, and thread insert options. Individual PLSS components may have different requirements and need to be considered separately for reducing overall mass. This report will touch on comparisons between advanced materials, focusing on composites, additive manufacturing, and plastics. It will also address the different processes that may need to be applied when using these materials in the harsh environment of space. Lastly, it will look at specific components and make recommendations for options to reduce the mass of each one.

Ryan Ogilvie↗

Advanced Material Options for the Portable Life Support System (PLSS)

Meeting an aggressive mass requirement is a challenge for new space suit development efforts, including that of the Exploration Extravehicular Mobility Unit Portable Life Support System (PLSS) government reference design. To reduce overall system mass, titanium was selected as the primary metal for the PLSS backplate and thermal loop. However, galvanically compatible metals (Hastelloy, Inconel, Monel) have relatively high densities and require further design complexities such as coatings and more challenging manufacturing. Efforts to reduce the mass of the government reference design for an International Space Station (ISS) or lunar mission were halted due to the government’s transition to a commercial Extravehicular Activity (EVA) services approach, but research was conducted into methodologies for mass savings using advanced materials. With the advent of a lunar Artemis mission and potential for future Mars missions, mass becomes a more critical driver going forward. Therefore, alternative materials and processes must be considered to fully close the mass requirement. There are many new materials and processes that can be considered; however, considerations must be made to ensure galvanic compatibility, radiation concerns for sensitive electronics, vacuum compatibility, tight tolerances, fluid compatibility with oxygen and water, and thread insert options. Individual PLSS components may have different requirements and need to be considered separately for reducing overall mass. This report will touch on comparisons between advanced materials, focusing on composites, additive manufacturing, and plastics. It will also address the different processes that may need to be applied when using these materials in the harsh environment of space. Lastly, it will look at specific components and make recommendations for options to reduce the mass of each one.

Ryan Ogilvie↗

Thermal structure of the primitive ionosphere

Exospheric neutral and electron temperatures have been estimated for the primitive upper atmosphere and ionosphere with various oxygen content in the scheme of our previous model (Shimizu and Shimazaki, 1976). The exospheric neutral temperature has been shown to be rather insensitive to the change of oxygen content, justifying our previous assumption for the temperature variation, while the exospheric electron temperature has been found to be quite sensitive to the compositional change, mainly owing to the strong dependence of electron density on the oxygen concentration.

Ashihara, O.↗

Discrimination of phosgene from cyanogen chloride in recovered chemical munitions using tagged neutron interrogation with high-resolution gamma-ray spectroscopy

The Associated Particle technique has recently been utilized with a germanium-based high-resolution $\gamma$-ray spectrometer and assessed for its capability to improve field identification of recovered chemical warfare (CW) materiel through prompt gamma-ray neutron activation analysis (PGNAA) measurements. An accurate chemical identification is necessary for the safe handling, destruction, and disposal of such hazardous items. A particularly challenging pair of CW agents commonly found in recovered munitions are phosgene (CG) and cyanogen chloride (CK), which have two of three elements in common, i.e. chlorine and carbon, but differ in the third being either oxygen or nitrogen. The detection of both latter elements is complicated by high oxygen concentration in the field environment which interferes with the small signal produced from the chemical agents. The matter is further complicated by the precautionary field practice of overpacking recovered munitions with vermiculite in larger steel multiple round containers (MRCs), which places additional oxygen-rich material around the munition while further attenuating an already weak signal emitted from the munition center. Here, this work reports quantitative results from realistic field measurements of CG and CK simulants in mock 4.2-inch mortar rounds overpacked with vermiculite in a large MRC. Results obtained with the AP technique are compared to those obtained with the traditional PGNAA approach for both overpacked- and bare-munition measurements. The AP technique is shown to provide a much more confident discrimination between the two chemicals, particularly for the more challenging field-relevant overpacked measurements, where a significant gain in sensitivity to all the key elements chlorine, carbon, nitrogen and oxygen is achieved.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Mechanical Consequences of Oxygen Inhibition in Vat Polymerization

Vat polymerization is a type of additive manufacturing that is used extensively to produce micro-architected structures for mechanical applications, which brings the mechanical properties of photopolymerized resins into sharp focus. However, it is known that photopolymerization is sensitive to a number of factors, perhaps the most notorious of which is oxygen inhibition. Herein, the degree to which oxygen inhibition influences the macroscopic and microscopic properties of structures made using vat polymerization is explored. This work is motivated by an observation of lattices being >4 times softer in the experiment than predicted by simulation, which is hypothesized to be due to the material at the surface being incompletely cured. Furthermore, this hypothesis is supported by four-point bending tests in which flexural modulus is found to increase with beam thickness. Nanoindentation and bulk compression studies show that this surface softening is present for three distinct resins. Importantly, it is observed that structures post-print cured in nitrogen are stiffer than those post-print cured in air, however, regardless of the post-print curing environment, printing samples in the presence of oxygen makes them softer than samples photocured in nitrogen. Collectively, these results show the outsized influence of oxygen inhibition on micro-architected structures realized using vat polymerization.

36 MATERIALS SCIENCE↗

CeO2 Nanoparticle Doping as a Probe of Active Site Speciation in the Catalytic Hydrolysis of Organophosphates

Organophosphate hydrolysis is important for degrading environmentally harmful compounds and recovering phosphate ions in biological molecules. CeO2 nanocrystals have been well-studied for dephosphorylation via hydrolysis owing to the accessible and tunable distribution of Ce3+ and Ce4+ ions. However, there remains uncertainty in the literature regarding which surface defect properties direct catalytic activity, such as the Ce3+/Ce4+ distribution, oxygen vacancies, faceting, and dopants, and to what degree they contribute to efficient hydrolysis. Trivalent (M3+) dopants serve as a tool for manipulating defects, including the concentration of Ce3+ and oxygen vacancies, thereby influencing the hydrolytic activity of CeO2. Herein, trivalent metal ions (M = Y3+, Cr3+, In3+, and Gd3+) were employed to modulate the active sites on the CeO2 nanocrystal surface, and the effects of each metal dopant on the cerium oxide active sites for organophosphate hydrolysis were investigated. M-doped CeO2 nanoparticles were synthesized via hydrothermal methods, followed by annealing to remove ligands and prime the nanocrystal surface for catalysis. Catalytic performance was evaluated using dimethyl-p¬-nitrophenyl phosphate (DMNP) as a model organophosphate substrate, with degradation monitored over time using UV-visible absorption spectroscopy. Powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy revealed successful doping of CeO2 in all cases, albeit with distinctive characteristics demonstrating how M3+ dopants affect catalysis. We show that CeO2 exhibits high sensitivity to dopants that generate lattice strain, Ce3+ ions, and oxygen vacancy defects. Consequently, achieving high catalytic efficiency within CeO2 requires a balanced active site ensemble, wherein defects are maintained at optimal concentrations and distributions on the nanocrystal surface.

Miura-Stempel, Emily L.↗

Evaluation of the energy balance of chemical looping combustion of solid fuels using CuO-based oxygen carriers

Chemical looping combustion (CLC) can inherently capture the CO2 generated during thermal energy production. When using CuO-based oxygen carriers, the reactions in both the fuel reactor (FR) and air reactor (AR) are exothermic, facilitating autothermal operation. To prevent the oxygen carrier from becoming agglomerated while ensuring a sufficient oxygen release rate, it is necessary to predict the FR temperature and remove an appropriate amount of heat from the AR when burning high-rank fuels. Here in this work, the energy balance of a CuO-based CLC system firing various solid fuels (biomass, coal, and petroleum coke) was investigated by establishing a thermodynamic model using FactSage. The energy distribution characteristics of the FR were quantified based on a virtual five-step thermodynamic sequence. The effects of fuel properties, oxygen carrier properties, and operating conditions on the energy balance were evaluated systematically. The results indicate that the temperature difference between the FR and AR is not very sensitive to the heating value of the fuel, while the CuO loading of the oxygen carrier, the heat capacity of the support material, and the flow rate of the fluidizing gas have significant impact. The insights obtained in this work will help improve the design and heat management of CLC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The oxygen and carbon dioxide balance in the earth's atmosphere

The oxygen-carbon dioxide cycle is described in detail, and steps which are sensitive to perturbation or instability are identified. About half of the carbon dioxide consumption each year in photosynthesis occurs in the oceans. Phytoplankton, which are the primary producers, have been shown to assimilate insecticides and herbicides. The impact of such materials on phytoplankton photosynthesis, both direct and as the indirect result of detrimental effects higher up in the food chain, cannot be assessed. Net oxygen production is very small in comparison with the total production and occurs almost exclusively in a few ocean areas with anoxic bottom conditions and in peat-forming marshes which are sensitive to anthropogenic disturbances. The carbon dioxide content of the atmosphere is increasing at a relatively rapid rate as the result of fossil fuel combustion. Increases in photosynthesis as the result of the hothouse effect may in turn reduce the carbon dioxide content of the atmosphere, leading to global cooling.

Johnson, F. S.↗