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Manganese and Vanadium Co-Exposure Induces Severe Neurotoxicity in the Olfactory System: Relevance to Metal-Induced Parkinsonism
Chronic environmental exposure to toxic heavy metals, which often occurs as a mixture through occupational and industrial sources, has been implicated in various neurological disorders, including Parkinsonism. Vanadium pentoxide (V 2 O 5 ) typically presents along with manganese (Mn), especially in welding rods and high-capacity batteries, including electric vehicle batteries; however, the neurotoxic effects of vanadium (V) and Mn co-exposure are largely unknown. In this study, we investigated the neurotoxic impact of MnCl 2 , V 2 O 5 , and MnCl 2 -V 2 O 5 co-exposure in an animal model. C57BL/6 mice were intranasally administered either de-ionized water (vehicle), MnCl 2 (252 µg) alone, V 2 O 5 (182 µg) alone, or a mixture of MnCl 2 (252 µg) and V 2 O 5 (182 µg) three times a week for up to one month. Following exposure, we performed behavioral, neurochemical, and histological studies. Our results revealed dramatic decreases in olfactory bulb (OB) weight and levels of tyrosine hydroxylase, dopamine, and 3,4-dihydroxyphenylacetic acid in the treatment groups compared to the control group, with the Mn/V co-treatment group producing the most significant changes. Interestingly, increased levels of α-synuclein expression were observed in the substantia nigra (SN) of treated animals. Additionally, treatment groups exhibited locomotor deficits and olfactory dysfunction, with the co-treatment group producing the most severe deficits. The treatment groups exhibited increased levels of the oxidative stress marker 4-hydroxynonenal in the striatum and SN, as well as the upregulation of the pro-apoptotic protein PKCδ and accumulation of glomerular astroglia in the OB. The co-exposure of animals to Mn/V resulted in higher levels of these metals compared to other treatment groups. Taken together, our results suggest that co-exposure to Mn/V can adversely affect the olfactory and nigral systems. These results highlight the possible role of environmental metal mixtures in the etiology of Parkinsonism.
Mass fractionation during transonic escape and implications for loss of water from Mars and Venus
Hydrodynamic escape of hydrogen from a planetary atmosphere can remove heavier gases as well as hydrogen, provided that the escape rate is sufficiently large. Analytic approximations for the degree of mass fractionation of a trace species during hydrodynamic escape are compared with accurate numerical solutions for the case of transonic outflow. The analytic approximations are most accurate when the ratio of molecular weights of the heavier and lighter constituents is large so that nonlinear terms in the momentum equation for the heavy constituent become small. The simplest analytic formula is readily generalized to the case where a heavy constituent is also a major species. Application of the generalized formula to hypothetical episodes of hydrodynamic escape from Venus and Mars suggests that both hydrogen and oxygen could have escaped; thus, substantial quantities of water may have been lost without the need to oxidize large amounts of the crust.
SiC Recession Due to SiO2 Scale Volatility Under Combustor Conditions
One of today's most important and challenging technological problems is the development of advanced materials and processes required to design and build a fleet of supersonic High Speed Civil Transport (HSCT) airliners, a follow-up to the Concorde SST. The innovative combustor designs required for HSCT engines will need high-temperature materials with long-term environmental stability. Higher combustor liner temperatures than today's engines and the need for lightweight materials will require the use of advanced ceramic-matrix composites (CMC's) in hot-section components. The HSCT is just one example being used to demonstrate the need for such materials. This thesis evaluates silicon carbide (SiC) as a potential base material for HSCT and other similar applications. Key issues are the environmental durability for the materials of interest. One of the leading combustor design schemes leads to an environment which will contain both oxidizing and reducing gas mixtures. The concern is that these environments may affect the stability of the silica (SiO2) scale on which SiC depends for environmental protection. A unique High Pressure Burner Rig (HPBR) was developed to simulate the combustor conditions of future gas turbine engines, and a series of tests were conducted on commercially available SiC material. These tests are intended as a feasibility study for the use of these materials in applications such as the HSCT. Linear weight loss and surface recession of the SiC is observed as a result of SiO2 volatility for both fuel-lean and fuel-rich gas mixtures. These observations are compared and agree well with thermogravimetric analysis (TGA) experiments. A strong Arrhenius-type temperature dependence exists. In addition, the secondary dependencies of pressure and gas velocity are defined. As a result, a model is developed to enable extrapolation to points outside the experimental space of the burner rig, and in particular, to potential gas turbine engine conditions.
Advanced Ceramics for NASA's Current and Future Needs
Ceramic composites and monolithics are widely recognized by NASA as enabling materials for a variety of aerospace applications. Compared to traditional materials, ceramic materials offer higher specific strength which can enable lighter weight vehicle and engine concepts, increased payloads, and increased operational margins. Additionally, the higher temperature capabilities of these materials allows for increased operating temperatures within the engine and on the vehicle surfaces which can lead to improved engine efficiency and vehicle performance. To meet the requirements of the next generation of both rocket and air-breathing engines, NASA is actively pursuing the development and maturation of a variety of ceramic materials. Anticipated applications for carbide, nitride and oxide-based ceramics will be presented. The current status of these materials and needs for future goals will be outlined. NASA also understands the importance of teaming with other government agencies and industry to optimize these materials and advance them to the level of maturation needed for eventual vehicle and engine demonstrations. A number of successful partnering efforts with NASA and industry will be highlighted.
Armalcolite stability as a function of pressure and oxygen fugacity
High-pressure experiments in a piston-cylinder apparatus with silver-palladium containers were conducted to study the stability of synthetic armalcolite, (Fe,Mg)Ti2O5, as a function of pressures up to 15 kbar at 1000, 1100, and 1200 C. Three armalcolite compositions were used, each with an initial Fe/(Fe + Mg) ratio of 0.5. Composition I contained no zirconium, whereas compositions II and III were prepared with 4% and 10% by weight ZrO2. Difference in stability due to the presence or absence of Zr in these synthetic armalcolites is discussed. 4 wt% ZrO2 appears to saturate armalcolite at 1200 C and 1 atm. Zirconium is found to reduce armalcolite stability, but this effect is not great. The stability of armalcolite as a function of oxygen fugacity is determined thermogravimetrically at 1200 C and 1 atm. Knowledge of the range of oxygen fugacity at which armalcolite is stable and of the equilibrium oxide mineral assemblages outside this range provides important information about lunar cooling histories in terms of oxygen fugacity.
Vapor deposited emittance/catalysis coatings for superalloys in heatshield applications
Statically oxidized Inconel 617 and MA 956 superalloys were prepared with vapor deposited aluminosilicate layers and exposed to temperatures which simulated reentry conditions. The aluminosilicate layers were 1-2 microns thick. The trials consisted of exposures to 1500-2300 F heat while surface temperatures were monitored with pyrometers. Analyses were then performed of the catalytic activity, oxidation phenomena, and radiative properties after thermal cycling the specimens for 8 hr. Both alloys were found to be catalytic to the recombination processes of dissociated species in the reentry environment. The coatings reduced the catalytic activity by 40 percent for both alloys but did not change the emittance. An enhanced Cr depletion zone was detected in the Inconel samples, implying that the coating did not prevent diffusion loss of Cr. The coated MA 956, on the other hand, gained weight over the course of the trials.
Polyimide/Carbon Nanotube Composite Films for Electrostatic Charge Mitigation
Low color, space environmentally durable polymeric films with sufficient electrical conductivity to mitigate electrostatic charge (ESC) build-up have potential applications on large, deployable, ultra-light weight Gossamer spacecraft as thin film membranes on antennas, solar sails, thermal/optical coatings, multi-layer insulation blankets, etc.. The challenge has been to develop a method to impart robust electrical conductivity into these materials without increasing solar absorptivity (alpha ) or decreasing optical transparency or film flexibility. Since these spacecraft will require significant compaction prior to launch, the film portion of the spacecraft will require folding. The state-of-the-art clear, conductive coating (e.g. indium-tin-oxide, ITO) is brittle and cannot tolerate folding. In this report, doping a polymer with single-walled carbon nanotubes (SWNTs) using two different methods afforded materials with good flexibility and surface conductivities in the range sufficient for ESC mitigation. A coating method afforded materials with minimal effects on the mechanical, optical, and thermo-optical properties as compared to dispersal of SWNTs in the matrix. The chemistry and physical properties of these nanocomposites are discussed.
Single-Crystal NiAl-X Alloys Tested for Hot Corrosion
Single-crystal nickel aluminide (NiAl) has been investigated extensively throughout the last several years as a potential structural material in aero-gas turbine engines. The attractive features of NiAl in comparison to Ni-base superalloys include a higher melting point, lower density, higher thermal conductivity, and excellent oxidation resistance. However, NiAl suffers from a lack of ductility and fracture toughness at low temperatures and a low creep strength at high temperatures. Alloying additions of hafnium (Hf), gallium (Ga), titanium (Ti), and chromium (Cr) have each shown some benefit to the mechanical properties over that of the binary alloy. However, the collective effect of these alloying additions on the environmental resistance of NiAl-X was unclear. Hence, the present study was undertaken to examine the hot corrosion behavior of these alloys. A companion study examined the cyclic oxidation resistance of these alloys. Several single-crystal NiAl-X alloys (where X is Hf, Ti, Cr, or Ga) underwent hot corrosion testing in a Mach 0.3 burner rig at the NASA Lewis Research Center. Samples were tested for up to 300 1-hr cycles at a temperature of 900 C. It was found that increasing the Ti content from 1 to 5 at.% degraded the hot corrosion behavior. This decline in the behavior was reflected in high weight gains and large corrosion mound formation during testing (see the figures). However, the addition of 1 to 2 at.% Cr to alloys containing 4 to 5 at.% Ti appeared to greatly reduce the susceptibility of these alloys to hot corrosion attack and negated the deleterious effect of the increased Ti addition.
Experimental reduction of simulated lunar glass by carbon and hydrogen and implications for lunar base oxygen production
The most abundant element in lunar rocks and soils is oxygen which makes up approximately 45 percent by weight of the typical lunar samples returned during the Apollo missions. This oxygen is not present as a gas but is tightly bound to other elements in mineral or glass. When people return to the Moon to explore and live, the extraction of this oxygen at a lunar outpost may be a major goal during the early years of operation. Among the most studied processes for oxygen extraction is the reduction of ilmenite by hydrogen gas to form metallic iron, titanium oxide, and oxygen. A related process is proposed which overcomes some of the disadvantages of ilmenite reduction. It is proposed that oxygen can be extracted by direct reduction of native lunar pyroclactic glass using either carbon, carbon monoxide, or hydrogen. In order to evaluate the feasibility of this proposed process a series of experiments on synthetic lunar glass are presented. The results and a discussion of the experiments are presented.
Activation of nuclear transcription factor-kappaB in mouse brain induced by a simulated microgravity environment
Microgravity induces inflammatory responses and modulates immune functions that may increase oxidative stress. Exposure to a microgravity environment induces adverse neurological effects; however, there is little research exploring the etiology of these effects resulting from exposure to such an environment. It is also known that spaceflight is associated with increase in oxidative stress; however, this phenomenon has not been reproduced in land-based simulated microgravity models. In this study, an attempt has been made to show the induction of reactive oxygen species (ROS) in mice brain, using ground-based microgravity simulator. Increased ROS was observed in brain stem and frontal cortex with concomitant decrease in glutathione, on exposing mice to simulated microgravity for 7 d. Oxidative stress-induced activation of nuclear factor-kappaB was observed in all the regions of the brain. Moreover, mitogen-activated protein kinase kinase was phosphorylated equally in all regions of the brain exposed to simulated microgravity. These results suggest that exposure of brain to simulated microgravity can induce expression of certain transcription factors, and these have been earlier argued to be oxidative stress dependent.
Magnesium production by molten salt electrolysis with liquid tin cathode and multiple effect distillation
Low-cost clean primary production of magnesium metal is important for its use in many applications, from light-weight structural components to energy technologies. This work describes new experiments and cost and emissions analysis for a magnesium metal production process. The process combines molten salt electrolysis of MgO using MgF₂-CaF₂ electrolyte and a reactive liquid tin cathode, with gravity-driven multiple effect thermal system (G-METS) distillation to separate out the magnesium product, and re-use of the tin. Electrolysis experiments with carbon anodes showed current yield above 90%, while a yttria-stabilized zirconia solid oxide membrane (SOM) anode experiment showed 84% current yield. G-METS distillation is an important component of the envisioned process. It can potentially lower costs and energy use considerably compared with conventional magnesium distillation. Techno-economic analysis including detailed mass and energy balances shows that this electrolyte composition could lower costs by utilizing CaO, which is the primary impurity in MgO, as the Hall-Héroult process uses the sodium impurity in alumina. Analysis options include: raw material types (magnesite rock vs. brine or seawater), drying and calcining using electricity vs. natural gas, and carbon vs. SOM anode type. Using SOM inert anodes results in a cost premium around 10%–15%, mostly due to higher electrical energy usage resulting from membrane resistance, and reduces GHG emissions by approximately 1 kg CO₂/kg Mg product. Capital and operating cost estimates, and cradle to gate greenhouse gas (GHG) emissions analysis under several raw material and process technology scenarios, show comparable costs and emissions to those of aluminum production.
Electrocomposite of Alumina in Nickel Matrix
Nickel/aluminum oxide composite was electroformed in a sulfamate bath with 50 g/L of 0.05-micron aluminum oxide powder. Different plating methods including direct current plating, periodic pulse plating, and periodic reverse pulse plating were used. With conventional direct current plating, the maximum particle inclusion in the nickel matrix remains about 2% (wt). However, much higher percentile particle inclusions were achieved when a specific pulse reversal plating technique was applied. The particle incorporation approaches theoretical maximum when the deposit thickness per cycle approaches the particle diameter size at lower duty cycle. The highest particle incorporation achieved is 23% (by weight). Conceptual models interpreting the dramatic differences in the results of these plating methods were also proposed.
Solar Concentrator Demonstrator for Lunar Regolith Processing
NASA at the Marshall Space Flight Center (MSFC) is building a portable inflatable solar concentrator ground demonstrator for use in testing in-situ resource utilization (ISRU) lunar regolith processing methods. Of primary interest is the production of oxygen as a propellant oxidizer and for life support. There are various processes being proposed for the in-situ reduction of the lunar regolith, the leading processes are hydrogen reduction, carbothermal reduction and vapor phase pyrolysis. The concentrator system being built at MSFC could support demonstrations of all of these processes. The system consists of a light inflatable concentrator that will capture sunlight and focus it onto a receiver inside a vacuum chamber. Inflatable concentrators are good for space based applications due to their low weight and dense packaging at launch. The hexapod design allows the spot size to be increased to reduce the power density if needed for the process being demonstrated. In addition to the hardware development, a comprehensive simulation model is being developed and will be verified and validated using the system hardware. The model will allow for the evaluation of different lunar locations and operational scenarios for the lunar regolith processing with a high confidence in the predicted results.
Development of Aluminum Feedstock for Additive Manufacturing
The rapid evolution of materials science and manufacturing technologies in recent years has offered new pathways to manipulate materials for bespoke manufacturing. Here we aim to develop feedstocks for applications such as radiator panels, fuel tanks, and structural components for outfitting. As a strong, light weight and thermally conductive material aluminum is ideal for these applications. An often-overlooked source of aluminum waste is food packaging used on the International Space Station. Reusing this waste stream will reduce the cost and logistics of regular sparing. In Space Manufacturing (ISM) will utilize this technology is such areas as sparing and outfitting. However, processing aluminum can present challenges, especially in the context of additive manufacturing and sintering, due to its high reactivity and tendency to form a tenacious oxide layer. Identifying appropriate binders and sintering profiles can overcome these challenges. Herein we present our work on obtaining aluminum powder derived from food packaging, binder selection for aluminum feedstock, and a demonstration of bound metal deposition printing.
Monitoring Depolymerization in Mesopores Using Dynamic Properties of Polymeric Melt Accessed via Dielectric Spectroscopy
Traditional design principles for heterogeneous catalysis guide the use of catalytic particles with mesosized (∼2–50 nm) pores to increase the number of surface-active sites by way of an increased surface area. However, the entry of long-chain polymers into such pores may be significantly limited by the size and entanglement of polymers in the melt state, thereby decreasing the number of accessible sites. Assessment of catalyst performance from traditional reactor-based studies averages over intrapore reaction events as well as reactions on the surface of a particle, resulting in an inability to distinguish between differences in site accessibility and activity. Techniques that assess the intrapore performance can inform the design of future heterogeneous catalysts for polymer upcycling. In this work, we demonstrate the use of broadband dielectric spectroscopy to monitor depolymerization of a polymer melt within mesopores via changes in the segmental relaxation time scale of amorphous polymer chains. In particular, we highlight the use of an anodic aluminum oxide (AAO) membrane as a readily available model for catalyst pores with a well-characterized pore morphology. The decrease in the segmental relaxation (α-relaxation) time of the melt with increasing chain scission emerges as a measure of the extent of polymer deconstruction inside mesopores. To demonstrate the utility of this technique, we demonstrate the decomposition of two commercial poly(propylene carbonate) polymers with different decomposition rates within mesopores. As the polymers depolymerize, their segmental relaxation time decreases as the molecular weight decreases (as predicted by the Fox–Flory equation). The BDS-measured change in segmental relaxation time mirrors the expected trend based on change in molecular weight measured by size exclusion chromatography.
Surface composition of solid-rocket exhausted aluminum oxide particles
Particulate samples of aluminum oxide were collected on Teflon filters from the exhaust plume of the Space Shuttle (STS-61A, October 30, 1985) over the altitude interval 4.6-7.6 km immediately after launch. These particles were analyzed using SEM, energy-dispersive X-ray analysis, electron spectroscopy for chemical analysis, X-ray fluorescent spectroscopy, and conventional wet-chemical techniques. The samples were 0.6-1.0 percent surface-chlorided (chlorided meaning predominantly aluminum chlorides and oxychlorides, possibly including other adsorbed forms of chloride) by weight. This level of chloriding is about one-third of the amount determined previously from laboratory-prepared alumina and surface site samples of solid-rocket-produced alumina (SRPA) after both had been exposed to moist HCl vapor at temperatures down to ambient. This level is equivalent to previous laboratory results with samples exposed to moist HCl at temperatures above the boiling point of water. It is suggested that the present lower chloriding levels, determined for samples from a 'dry' Shuttle exhaust cloud, underscore the importance of a liquid water/hydrochloric acid phase in governing the extent of surface chloriding of SRPA. The reduced chloriding is not trivial with respect to potential physical/chemical modification of the SRPA particle surfaces and their corresponding interaction with the atmosphere.
Thermal Insulation Strips Conserve Energy
Launching the space shuttle involves an interesting paradox: While the temperatures inside the shuttle s main engines climb higher than 6,000 F hot enough to boil iron for fuel, the engines use liquid hydrogen, the second coldest liquid on Earth after liquid helium. Maintained below 20 K (-423 F), the liquid hydrogen is contained in the shuttle s rust-colored external tank. The external tank also contains liquid oxygen (kept below a somewhat less chilly 90 K or -297 F) that combines with the hydrogen to create an explosive mixture that along with the shuttle s two, powdered aluminum-fueled solid rocket boosters allows the shuttle to escape Earth s gravity. The cryogenic temperatures of the main engines liquid fuel can cause ice, frost, or liquefied air to build up on the external tank and other parts of the numerous launch fueling systems, posing a possible debris risk when the ice breaks off during launch and causing difficulties in the transfer and control of these cryogenic liquid propellants. Keeping the fuel at the necessary ultra-cold temperatures while minimizing ice buildup and other safety hazards, as well as reducing the operational maintenance costs, has required NASA to explore innovative ways for providing superior thermal insulation systems. To address the challenge, the Agency turned to an insulating technology so effective that, even though it is mostly air, a thin sheet can prevent a blowtorch from igniting a match. Aerogels were invented in 1931 and demonstrate properties that make them the most extraordinary insulating materials known; a 1-inch-thick piece of aerogel provides the same insulation as layering 15 panes of glass with air pockets in between. Derived from silica, aluminum oxide, or carbon gels using a supercritical drying process - resulting in a composition of almost 99-percent air - aerogels are the world s lightest solid (among 15 other titles they hold in the Guinness World Records), can float indefinitely on water if treated to be hydrophobic, and can withstand extremely hot temperatures (from 1,100 F to 3,000 F depending on the type of aerogel) down to cryogenic levels, making this "frozen smoke" ideal for use in space. Because of its low weight and ability to withstand temperature extremes, an aerogel was even used as the space-based catcher s mitt to trap comet particles and space dust for NASA s Stardust mission, launched in 1999. All of this remarkable technology s characteristics were ideal for NASA s purposes except one: The aerogels were extremely brittle. Through a long-term partnership between Kennedy Space Center and Aspen Aerogels Inc., of Northborough, Massachusetts, researchers developed a flexible, durable form of aerogel that NASA has since used as cryogenic insulation for space shuttle launch systems. Through Aspen Aerogels, the technology has made oil pipeline insulation, extreme weather clothing, and infrared shielding for combat helicopters.