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At least 235 records · Page 13

Effects of Field Strength and Silver Nanowire Size on Plasmon-Enhanced N 2 Dissociation

Dissociation of the nitrogen molecule via plasmon-enhanced catalysis using noble metal nanoparticles has been investigated both experimentally and computationally in recent years. However, the mechanism of plasmon-enhanced nitrogen dissociation is still not very clear. In this work, we apply theoretical approaches to examine the dissociation of a nitrogen molecule on atomically-thin Ag n nanowires (n = 6, 8, 10, 12) and a Ag 19 + nanorod. Ehrenfest dynamics provides information about the motion of nuclei during the dynamics process and real-time TDDFT calculations show the electronic transitions and population of electrons over the first 10s of fs time scale. The activation and dissociation of nitrogen is typically enhanced when the electric field strength increases. However, the enhancement is not always monotonic with field strength. As the length of the Ag wire increases, nitrogen is typically easier to dissociate and thus requires lower field strengths, even though the plasmon frequency is lower. The Ag 19 + nanorod leads to faster dissociation of N 2 than the atomically-thin nanowires. Altogether, our detailed study yields insights into the mechanisms involved in plasmon-enhanced N 2 dissociation, as well as provides information about factors that can be used to improve adsorbate activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Permeation of oxygen through high purity, large grain silver

The permeation of high purity, large grain Ag membranes by oxygen has been studied over the temperature range 400 to 800 C. The permeability was found to be quite linear and repeatable, but the magnitude was 3.2 times smaller than that determined by past research. Since previous investigators studied substantially less pure Ag and conducted experiments within much poorer vacuum environments (which indicates that their grain boundary density was much greater), the data presented here suggest oxygen transport through the membrane is primarily by grain boundary diffusion. The diffusivity measurements were found to exhibit two distinct linear regions, one above and one below a critical temperature of 630 C. The high-temperature data have an activation energy (11.1 kcal/mole) similar to that reported by others, but the low-temperature data have a higher activation energy (15.3 kcal/mole), which can be explained by impurity trapping in the grain boundaries. Vacuum desorption of the oxygen-saturated Ag was found to occur at a threshold of 630 C, which is consistent with the onset of increased mobility within the grain boundaries.

Outlaw, R. A.↗

Preliminary findings of the LDEF Materials Special Investigation Group

The retrieval of NASA's LDEF from low Earth orbit provided an opportunity for the study of long duration space environmental effects on materials. The five year, nine month flight of the LDEF greatly enhanced the potential value of most LDEF materials. NASA recognized this potential by forming the LDEF Space Environmental Effects on Materials Special Investigation Group (MSIG). Its goal is to explore the expanded materials analysis opportunities available in the LDEF structure and on experiment trays. The charter and scope of MSIG activities is presented, followed by an overview of the preliminary MSIG observations. These observations of low Earth orbit environmental effects on materials were made in-space during LDEF retrieval and during LDEF tray disintegration. Also presented are initial findings of lab analyses of LDEF materials. Included are effects of individual environmental parameters: atomic oxygen, ultraviolet radiation, meteoroid and debris impacts, thermal cycling, vacuum, and contamination, plus combined effects of these parameters. Materials considered include anodized aluminum, polymer matrix composites, polymer films, silvered Teflon thermal blankets, and a white thermal control paint.

Stein, Bland A.↗

Direct Electrolytic Deposition of Mats of Mn(x)O(y) Nanowires

Mats of free-standing manganese oxide (MnxOy) nanowires have been fabricated as experimental electrode materials for rechargeable electrochemical power cells and capacitors. Because they are free-standing, the wires in these mats are electrochemically accessible. The advantage of the mat-of-nanowires configuration, relative to other configurations of electrode materials, arises from the combination of narrowness and high areal number density of the wires. This combination offers both high surface areas for contact with electrolytes and short paths for diffusion of ions into and out of the electrodes, thereby making it possible to charge and discharge at rates higher than would otherwise be possible and, consequently, to achieve greater power densities. The nanowires are fabricated in an electrolytic process in which there is no need for an electrode binder material. Moreover, there is no need to incorporate an electrically conductive additive into the electrode material; the only electrically conductive material that must be added is a thin substrate contact film at the anchored ends of the nanowires. Hence, the mass fraction of active electrode material is close to 100 percent, as compared with about 85 percent in conventional electrodes made from a slurry of active electrode material, binder, and conductive additive pressed onto a metal foil. The locations and sizes of the nanowires are defined by holes in templates in the form of commercially available porous alumina membranes. In experiments to demonstrate the present process, alumina membranes of various pore sizes and degrees of porosity were used. First, a film of Au was sputtered onto one side of each membrane. The membranes were then attached, variously, to carbon tape or a gold substrate by use of silver or carbon paste. Once thus attached, the membranes were immersed in a plating solution comprising 0.01 M MnSO4 + 0.03 M (NH4)2SO4. The pH of the solution was kept constant at 8 by addition of H2SO4 or NH4OH as needed. Mn(x)O(y) nanowires were potentiostatically electrodeposited in the pores in the alumina templates. Depending on the anodic deposition potentials, Mn(x)O(y) was deposited in various oxidation states [divalent (Mn3O4), trivalent (Mn2O3), or tetravalent (MnO2)]. The Mn(x)O(y) wires were made free-standing (see figure) by dissolving the alumina templates, variously, in KOH or NaOH at a concentration of 20 volume percent.

Myung, Nosang↗

Surface Chemistry and Reactions for Bimetallic Au Catalysis (Final Report)

Gold-based catalysts offer tremendous opportunities for developing new technologies for selective oxidation reactions that directly use gas-phase oxygen as a benign reagent and produce either no byproducts or water as the only byproduct. These processes are urgently needed and critical for achieving the sustainable production of chemicals. While recent studies demonstrate that the catalytic properties of gold can be significantly enhanced by addition of other metals, the development of these catalysts with sufficient performance for commercialization is hindered by a lack of fundamental understanding of how the catalytic properties of gold can be controlled and tailored. This project addressed this need by synergistically combining experimental and computational studies to establish fundamental composition-structure-activity relationships for gold-based catalysts for several industrially important reactions. Results from surface spectroscopy, atomic imaging and thermal desorption experiments were combined with molecular models and reaction mechanisms from quantum chemical calculations to link observable reaction rates to the structure and composition of surfaces at the molecular level. The results were used to develop improved catalyst formulations and identify optimized reaction conditions for gold-based catalysts. For broader impacts, the developed methodology was extended to other metallic catalysts, such as silver, platinum-molybdenum and nickel-tin, for improved catalytic efficiency and sustainable production of specialty and commodity chemicals.

36 MATERIALS SCIENCE↗

Microbial Characterization of Internal Active Thermal Control System (IATCS) Hardware Surfaces after Five Years of Operation in the International Space Station

A flex hose assembly containing aqueous coolant from the International Space Station (ISS) Internal Active Thermal Control System (IATCS) consisting of a 2 foot section of Teflon hose and quick disconnects (QDs) and a Special Performance Checkout Unit (SPCU) heat exchanger containing separate channels of IATCS coolant and iodinated water used to cool spacesuits and Extravehicular Mobility Units (EMUS) were returned for destructive analyses on Shuttle return to flight mission STS-114. The original aqueous IATCS coolant used in Node 1, the Laboratory Module, and the Airlock consisted of water, borate (pH buffer), phosphate (corrosion control), and silver sulfate (microbiological control) at a pH of 9.5 +/- 0.5. Chemical changes occurred after on-orbit implementation including a decrease to pH 8.4 due to the diffusion of carbon dioxide through the Teflon hoses, an increase in nickel ions due to general corrosion of heat exchanger braze coatings, a decrease in phosphate concentration due to precipitation of nickel phosphate, and the rapid disappearance of silver ions due to deposition on hardware surfaces. Also associated with the coolant chemistry changes was an increase in planktonic microorganisms from less than 100 colony forming units (CFU) per 100 ml to approximately 1 million CFU per 100 ml. Attachment and growth of microorganisms to the system surfaces (biofilm) was suspected due to the levels of planktonic microorganisms in the coolant. Biofilms can reduce coolant flow, reduce heat transfer, amplify degradation of system materials initiated by chemical corrosion, and enhance mineral scale formation.

Roman, Monsi C.↗

National Aeronautics and Space Administration Twenty-Fifth Anniversary, 1958-1983

This year marks a major milestone for the National Aeronautics and Space Administration: its silver anniversary. It seems appropriate, on this occasion, to sum up how NASA has responded to the legislative charter that established the agency. Among the responsibilities the Congress assigned NASA in the National Aeronautics and Space Act of 1958 were these: preservation of U.S. leadership in aerospace science and technology; cooperation with other nations in the peaceful application of technology; expansion of human knowledge of phenomena in the atmosphere and in space; pursuit of the practical benefits to be gained from aeronautical and space activities. There can be no doubt that NASA's quarter century of effort has preserved the nation's leadership role and strengthened its posture in aerospace science and technology. As for international cooperation. NASA has - since its inception - fostered the concept that the fruits of civil space research are to be shared with all mankind. The agency has provided technical assistance to scores of nations and has actively promoted cooperative ventures; indeed, virtually every major NASA space project today boasts some degree of foreign participation. In the last 25 years, man has teamed more about his planet, the near-Earth environment, and the universe than in all the prior years of history. NASA's space science program has spearheaded this great expansion of human knowledge. And, from the beginning, NASA has vigorously pursued the practical benefits that aerospace research offers. The agency pioneered in weather, communications and Earth resources survey satellites, the prime examples of space technology applied for Earth benefit, and it has built a broad base for expanding into new applications, some of which promise direct benefits of exceptional order. In aeronautical research, NASA has contributed in substantial degree to safer, better performing, more efficient, more environmentally acceptable aircraft.

Source record↗

A Bifunctional Ionic Liquid for Capture and Electrochemical Conversion of CO 2 to CO over Silver

Electrochemical conversion of CO 2 requires selective catalysts and high solubility of CO 2 in the electrolyte to reduce the energy requirement and increase the current efficiency. In this study, the CO 2 reduction reaction (CO 2 RR) over Ag electrodes in acetonitrile-based electrolytes containing 0.1 M [EMIM][2-CNpyr] (1-ethyl-3-methylimidazolium 2-cyanopyrolide), a reactive ionic liquid (IL), is shown to selectively (>94%) convert CO 2 to CO with a stable current density (6 mA·cm –2 ) for at least 12 h. The linear sweep voltammetry experiments show the onset potential of CO 2 reduction in acetonitrile shifts positively by 240 mV when [EMIM][2-CNpyr] is added. This is attributed to the pre-activation of CO 2 through the carboxylate formation via the carbene intermediate of the [EMIM] + cation and the carbamate formation via binding to the nucleophilic [2-CNpyr] – anion. The analysis of the electrode–electrolyte interface by surface-enhanced Raman spectroscopy (SERS) confirms the catalytic role of the functionalized IL where the accumulation of the IL-CO 2 adduct between –1.7 and –2.3 V vs Ag/Ag + and the simultaneous CO formation are captured. Furthermore, this study reveals the electrode surface species and the role of the functionalized ions in lowering the energy requirement of CO 2 RR for the design of multifunctional electrolytes for the integrated capture and conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of hydration on plasma volume and endocrine responses to water immersion

The effect of hydration status on early endocrine responses and on osmotic and intravascular volume changes during immersion was determined in humans undergoing successive periods of dehydration, immersion, rehydration, and immersion. Immersion caused an isotonic expansion of plasma volume, as well as suppression of plasma renin activity and aldosterone, which all occurred independently of hydration status. On the other hand, the concentration of plasma vasopressin (PVP) was found to decrease during dehydrated immersion, but not during rehydrated immersion. It is concluded that plasma tonicity is not a factor influencing PVP suppression during water immersion.

Harrison, M. H.↗

Electrodynamic Dust Shield (EDS) Preparation for MISSE-11 Launch

The dusty surfaces of the Moon, Mars, and various asteroids present a significant challenge to NASA’s manned and unmanned space exploration efforts. The fine, electrostatically charged dust is difficult to remove and has resulted in vision obscuration, false instrument readings, contamination, elevated temperatures, performance reduction, and equipment failure. To alleviate these problems, NASA KSC’s Electrostatics and Surface Physics Laboratory (ESPL) is developing active dust mitigation systems for solar system exploration and in situ resource utilization (ISRU). Part of KSC’s Swamp Works system, the lab emphasizes fast-paced, hands-on, cost-effective, and collaborative innovation. The Electrodynamic Dust Shield (EDS) is an ESPL technology being developed to prevent dust accumulation on space components. It consists of a dielectric substrate embedded with parallel electrodes which, when applied with high voltage out-of-phase waveforms, produce a traveling electric field wave that scatters dust particles from its surface via dielectrophoretic and electrostatic forces. The EDS is currently fully functional and has been tested for scalability and endurance in reduced gravity/pressure flight. Next, it will be part of the May 2019 Materials International Space Station Experiment-11 (MISSE-11) payload, which will test small shield samples for performance durability with exposure to the harsh space environment. The summer objective was to test EDS functionality before active and passive dust shield samples launch on MISSE-11, in order to screen for good flight/control samples as well as to compare pre-flight and post-flight clearing efficiencies. I imaged glass and Kapton shields of 2-phase and 3-phase electrode configurations with the Keyence VHX-5000 digital microscope to check for damage before and after all testing for a qualitative pre-flight baseline; helped with vacuum testing of high-voltage shield breakdown; assembled shields and wires using Electrobond 004 silver epoxy; and helped with vacuum and cryogenic dust clearance testing of assembled EDS systems. I learned CAD (computer-aided design) and 3D printing skills to create parts for a shaker table/motor assembly, which will allow for repeatable experiments by evening out EDS dust distribution in a consistent manner prior to dust scattering testing. I will also be improving the interfacing with Alpha Space’s prototype Data Communications Unit (DCU), a payload component to control power to the EDS and store data, by mapping the DCU structure upon power-up and writing shell scripts to improve various processes. Finally, I also CADed and 3D-printed plastic supports for three different geometries of the Electrostatic Precipitator (ESP), a project that aims to use high voltage electrodes to charge and filter out dust from the Martian atmosphere drawn for ISRU devices. This work on dust mitigation technologies will help to support future robotic and human space exploration missions, including NASA’s Journey to Mars; the EDS has especially significant applications to spacecraft solar panels, thermal radiators, viewports, and astronaut visors. This opportunity has also allowed me to become more familiar with various lab equipment and hardware testing, develop key modeling skills in SolidWorks, explore past and present components critical to America’s space program, work with inspiring peers and mentors, and ascertain my dream of working permanently for NASA.

space↗

Atomic oxygen dosimetry measurements made on STS-46 by CONCAP 2

With increasing flight duration and the possibility of a permanent facility in space, long-term monitoring of material degradation due to atomic oxygen is increasing in importance. Reliance on models to determine the fluence of atomic oxygen is not only necessarily complex but also imprecise due to the strong dependence of oxygen concentration on day/night, latitude and solar activity. Mass-spectroscopy, the traditional method for determining the gas phase species densities at low pressure, is not only expensive but is limited in the area that it can monitor. Our group has developed a simple and inexpensive dosimeter to measure the atomic oxygen fluence via the change in resistance as the sensor element is gradually oxidized. The sensors consisted of thin-film circuit elements deposited on a suitable substrate. Four-point resistance measurements were used to monitor the change in resistance. Results obtained using silver and carbon dosimeters flown on STS-46 (CONCAP 2-01) will be discussed.

Gregory, J. C.↗

Local Intensity Enhancements in Spherical Microcavities: Implications for Photonic Chemical and Biological Sensors

In this report, we summarize recent findings regarding the use spherical microcavities in the amplification of light that is inelastically scattered by either fluorescent or Raman-active molecules. This discussion will focus on Raman scattering, with the understanding that analogous processes apply to fluorescence. Raman spectra can be generated through the use of a very strong light source that stimulates inelastic light scattering by molecules, with the scattering occurring at wavelengths shifted from that of the source and being most prominent at shifts associated with the molecules natural vibrational frequencies. The Raman signal can be greatly enhanced by exposing a molecule to the intense electric fields that arise near surfaces (typically of gold or silver) exhibiting nanoscale roughness. This is known as surface-enhanced Raman scattering (SERS). SERS typically produces gain factors of 103 - 106, but under special conditions, factors of 1010 - 1014 have been achieved.

Fuller, Kirk A.↗

Stoichiometric metal nitration based novel green synthesis of mesoporous metal oxides and their enhanced heterogeneity

Here, in this work, a general and novel method for the green synthesis of mesoporous metal oxides via stoichiometric metal nitration has been demonstrated. Pluronic surfactants and their effect on synthesis procedures in terms of surface area have been experimentally studied in detail. Contrary to the traditional synthesis procedure, water has been utilized as the solvent and in several cases, such as tin oxide, manganese oxide, aluminum oxide, antimony oxide, zinc oxide, cobalt oxide, copper oxide, yttrium oxide, lanthanum oxide, and silver either the highest or comparable surface areas have been successfully synthesized. Through XRD, and TEM, all materials were observed to be crystalline except silver and magnesium oxide. SEM shows that with an increase in surfactant molar mass agglomeration decreases. Ammonia chemisorption on acidic materials gives quantitative amounts of ammonia chemical bonding with catalysts, whereas carbon dioxide chemisorption gives a quantitative value of CO 2 chemical binding with basic sites. As high as 1901.8 μmol/g and 994.6 μmol/g ammonia chemisorption values for oxides of vanadium and tin were achieved. Amphoteric materials give both acidic and basic enhanced adsorption. Finally, all synthesized materials are studied under organic catalytic transformations. Benzyl bromide is theoretically more active compared with benzylamine and benzyl alcohol which was also experimentally shown through the conversion.

36 MATERIALS SCIENCE↗

Pioneer 10 at Silver Au Describes Sun's atmosphere

Almost 4 billion kilometers from the Sun, Pioneer 10's findings paint a detailed picture of the solar atmosphere. The heliosphere is now believed to be a huge magnetic bubble created by the solar wind and gets its tear-shape from streamlining due to the motion of the solar system through the interstellar gas. The skin of the bubble, the region between stellar and interstellar gas, is believed to lie between 50 and 100 AU from the Sun. The solar wind drags the Sun's magnetic field with it. The bubble, probably extends far beyond Pluto, and is believed to breathe, expanding and contracting like a giant cosmic lung with each 11 year cycle. The most recent findings show that as storms on the Sun build up toward maximum solar activity, they send out shock waves throughout the bubble which cause ripples. This long lived solar storm turbulence accelerates low energy cosmic ray particles coming in from the galaxy, deflecting them out of the solar system, and shielding the planets. As distance from the Sun increases, more and more cosmic ray particles penetrate the heliosphere.

Source record↗

Synthesis of Thick Hg x Cd 1– x Se Nanoplatelets by Cation Exchange Catalyzed by Silver Ions, Showing Amplified Spontaneous Emission

II-VI semiconductor nanoplatelets have emerged as promising candidates for various applications, owing to their tunable optical properties dictated by their thickness and compositions. In the realm of infrared technology, mercury chalcogenides stand out as particularly promising materials for optoelectronic applications. However, the direct synthesis of 2D particles in this category remains challenging, thus prompting the exploration of alternative methods such as cation exchange. Here, we demonstrate that the cation exchange process from cadmium to mercury can be effectively catalyzed by monovalent Ag + cations. Further, this catalysis facilitates the formation of alloyed Hg x Cd 1-x Se nanoplatelets with tunable optical properties, with the photoluminescence peak ranging from 1.23 eV for the thinnest three-monolayer (ML) nanoplatelets to 0.92 eV for the thickest 7 ML nanoplatelets. The Ag + ions reduce the activation energy of the cation exchange process by a factor of 2, enabling enhanced penetration of mercury atoms deep into the native CdSe nanoplatelets. Moreover, these nanoplatelets exhibit optical gain in the infrared spectrum, including the 1.3 μm telecommunication band, with a fluence threshold at 80 K of 50 μJ∙cm -2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of suspension hypokinesia on rat soleus muscle

Hindlimb hypokinesia was induced in rats by the Morey method to characterize the response of the soleus muscle. Rats suspended for 1-4 wk exhibited continuous and significant declines in soleus mass, function, and contractile duration. Soleus speeding was in part explained by an alteration in fiber type. The normal incidence of 70-90 percent type I fibers in the soleus muscle was reduced after 4 wk of suspension to 50 percent or less in 9 of 11 rats. A significant decline in type I myosin isozyme content occurred without a change in that of type II. Other observed histochemical changes were characteristic of denervation. Consistent with soleus atrophy, there was a significant increase in lysosomal (acid) protease activity. One week of recovery after a 2-wk suspension was characterized by a return to values not significantly different from control for muscle wet weights, peak contraction force, one-half relaxation time, and type I myosin. Persistent differences from control were observed in maximal rate of tension development, contraction time, and denervation-like changes.

Templeton, G. H.↗

Cryogenic Selective Surfaces

There are many challenges involved in deep-space exploration, but several of these can be mitigated, or even solved, by the development of a coating that reflects most of the Sun’s energy, yet still provides far-infrared heat emission. Such a coating would allow non-heat-generating objects in space to reach cryogenic temperatures without using an active cooling system. This would benefit deep-space sensors that require low temperatures, such as the James Webb Telescope focal plane array. It would also allow the use of superconductors in deep space, which could lead to magnetic energy storage rings, lossless power delivery, or perhaps a large-volume magnetic shield against galactic cosmic radiation. However, perhaps the most significant enablement achieved from such a coating would be the long-term, deep space storage of cryogenic liquids, such as liquid oxygen (LOX). In our Phase I NIAC study, we realized that a combination of scattering particles and a silver backing could yield a highly effective, very broadband, reflector that could potentially reflect more than 99.9% of the Sun’s irradiant power. We developed a sophisticated model of this reflector and theoretically showed that cryogenic temperatures could be achieved in deep space at one astronomical unit (1 AU) from the Sun. We showed how this new reflector could minimize heat conduction into the cryogenic tanks by coating the tank support struts. We then modelled a strawman architecture for a mission to Mars, using a coated LOX tank, coated struts, and infrared shields, to show that with our new coating it would be possible to maintain liquid oxygen passively. As a result of this work a patent application was generated and a paper published in Optics Letters. Our Phase II NIAC study had two primary goals, to develop a rigid version of the cryogenic selective surface proposed in Phase I and to test its performance in a simulated deep space environment. During the first year of the project the work concentrated on developing rigid tiles of BaF2, leading to tiles as large as 4 inches in diameter that transmitted very little visible light. In addition, during the first year a simulated deep space environment was created using a vacuum chamber and cryocooler. Using this facility, we showed that our BaF2 tiles absorbed less than ¼% of 375 nm radiation, a significant milestone for the work. During the second year of the project, we continued to develop the BaF2 tiles and we put significant effort into the construction of a deep space environment where we could project simulated solar radiation onto a sample. In the spring of 2018, we conducted our first solar simulator test with BaF2 and saw about 3.6% absorption. This is better than the state-of-the-art, but disappointing since predictions were for much lower absorption. We, erroneously, attributed this absorption to water retention by the BaF2, and decided to change materials. We considered several oxides and settled on yttrium oxide (Y2O3) for further development, because it is broadband, lightweight, has high index, and is hydrophobic. In July 2018 we conducted our first test of a rigid tile of Y2O3 in the simulated deep space environment and saw significant absorption again. We then realized that the issue was not water, but mid-wave radiation passing through the tile and being absorbed by the temperature sensor and the varnish used to hold it in place. We wrapped the sensor in silver foil, re-ran the test, and saw much lower absorption; only 1.1%. We then re-ran the BaF2 tile and saw 1.4% absorption. These values are almost adequate to maintain LOX in deep space, but we suspect that there are still issues in our test apparatus; we suspect thermocouple wires may be absorbing radiation. Further, post-NIAC, testing will better determine the performance of our new solar reflector. In order to restrict the size of this report, we will only briefly describe topics that we have previously published, allowing us to devote more time to new material. So minimal material will be devoted to modeling the material and deep space cryogenic storage, while longer sections will cover our material development, simulated deep space testing, and new applications. The Launch Service Program (LSP) requested that we explore ways to use this new coating to maintain LOX in low Earth Orbit and that work is described. In addition, the Nuclear Thermal Propulsion (NTP) Program asked us to explore ways to reduce the heat load for liquid hydrogen, resulting in the development of a spray-on version of the coating that should significantly improve in-space multi-layer insulation performance.

Robert C. Youngquist,↗