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At least 1,459 records · Page 81

Understanding the TiH (2-x) /TiO y System at Elevated Temperature: A Literature Review

Titanium hydride of varying TiH stoichiometry is used in pyrotechnic compositions. In order to yield consistent performance, manufacturing processes must be developed to ensure precise and reproducible material properties, including composition and morphology. Legacy synthesis protocols are not comprehensive nor are the required apparatuses still available. To guide the development of novel production procedures, this report reviews literature on relevant chemical reactions and diffusion events occurring at elevated temperature in the TiH (2-x) /TiO y system. Titanium hydride exposed to air spontaneously forms a passivating oxide layer. Upon heating, significant hydrogen release, which is accompanied by changes to the surface oxide layer, is noted by 375–400°C. At higher temperatures (above about 500°C) the oxide layer is reported to be essentially nonexistent as a result of oxide-layer dissolution processes and, potentially, oxide-layer reduction due to water formation. Based on the reviewed literature, we hypothesize that, by 500°C, the surface layer consists of an oxyhydride phase, which is a solid solution of oxygen in titanium hydride. We believe that hydrogen release from titanium hydride is controlled by the kinetics of molecular hydrogen desorption on the oxyhydride surface. No literature data is available for corresponding activation energies of the dynamic desorption process, and the equilibrium phase diagram of this three-component system remains largely unexplored as well. These gaps in knowledge might be addressed through coordinated computational modeling and experimental efforts.

36 MATERIALS SCIENCE↗

A Ge/Li/ spectrometer for gamma ray astronomy

A space-borne instrument to measure the spectral and temporal characteristics of astronomical gamma rays in the .05 to 10 Mev energy range is described. The spectrometer consists of four 60 cc Ge(Li) detectors with an energy resolution of 2.5 Kev (FWHM) at 1.33 Mev. The Ge(Li) detectors are actively shielded with CsI(Na) for angular collimation and background reduction. Cooling of the Ge(Li) detectors to 88 K for orbital lifetimes of up to two years is provided by a two-stage solid subliming refrigerator.

Hicks, D. B.↗

Space Shuttle Program progress report

A status report devoted to progress of design, manufacturing and test activities for each element of the Space Shuttle is presented. In particular, attention is given to system engineering and integration, the orbiter and its subsystems, the carrier aircraft, the main engine, the external tank, the solid rocket booster, the launch and landing facilities, and ground and orbital flight tests.

Thompson, R. F.↗

The application of Fourier transform spectroscopy to the remote identification of solids in the solar system

The techniques of Fourier transform spectroscopy combined with large aperture telescopes and advances in detector technology now permit infrared (at a wavelength greater than 1 micron) observations of the surfaces of small solar system objects such as asteroids and satellites. The results demonstrate that this activity can produce important new compositional information related to the origin and evolution of the solar system. The detection of water ice in Saturn's rings and on some of the satellites of Jupiter and Saturn confirm expectations that ices are important mineralogical components in the chemistry of the outer solar system. More recent studies of the mineralogical composition of the surfaces of asteroids provide a new observational link to the origin of meteorites and the early thermal history of the solar system. These results have been dependent upon supporting laboratory studies of the spectral behavior of ices and minerals to define the potential, and limitations, of the method. Since many of the astronomical observations have been exploratory in nature, prospects are good that continued refinement of the techniques will lead to additional insights.

Larson, H. P.↗

Measurements of cloud nuclei in the effluents from launches of liquid- and solid-fueled rockets

Airborne measurements of two types of cloud nuclei, cloud condensation nuclei (CCN) and ice nuclei (IN), were conducted in the stabilized ground clouds which resulted from the launches of a liquid-fueled ATLAS/Centaur rocket and a solid-fueled TITAN III rocket. Results show that the concentrations of CCN in both types of clouds were greater than ambient values for the 2 hours duration of the measurements. The initial production of CCN active at 0.5% supersaturation in the ATLAS and TITAN clouds was found to be equivalent to a 20 and 700 sec emission, respectively, by the city of Denver, Colorado. After the initial production, the clouds continued to generate CCN at a rate of about 1/cu cm sec. However, concentrations of IN in the ATLAS cloud were greater than ambient values for only a short period after launch, and it appears that the nuclei resulted from entrained launch pad and ground debris. The concentrations of IN in the TITAN cloud were found to be at or below ambient levels until about 2 hours after launch when they increased substantially above ambient values.

Hindman, E. E.↗

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

Ceramic Aerogel Composite Materials and Characterization

Aerogels a.k.a "Solid Smoke" are gels with the liquid phase replaced by gas, leaving behind a highly porous material with a nanoscale framework. Due to the porous, nanoscale structure, aerogels have the lowest known density and conductivity of solids. Aerogels have the potential for being a breakthrough material because of their extremely light weight and unique properties. In this paper, we address overcoming their most profound weaknesses: mechanical fragility and very high surface activity, which leads to a lowered sintering temperature. A matrix of ceramic aerogel composite materials was produced to investigate their properties and functionality. Mechanical property measurements and Scanning Electron Micrographs are used to identify trends and structure of these ceramic composite materials. Thermal cycling was used to identify the sintering points of the materials.

White, Susan↗

Ka-Band Beam Steering Reflectarray Study

A one-meter diameter, 32 GHz active microstrip reflectarray capable of electronic beam steering has been studied. The 15_500 element array consists of rnicrostrip patch antennas, microstrip phase shifters, and dc bias lines. Specifically, the study focused on the solid-state devices and dc bias layouts for scanning the beam linearly 45 from boresight using 2-bit phase shifters. Three configurations are recommended for the reflectarray with integrated 2-bit phase shifters where the total substrate and cladding mass varies from 8 kg to 14 kg. Additionally, dc power requirements for p-i-n diodes in 1-bit, 2-bit and 3-bit phase shifting circuits are approximately 19 W, 19 W, and 39 W, respectively. The dc power requirement for phase shifters using passive MESFETs is much less than 1 W.

McSpadden, James O.↗

Assessment of Lithium-based Battery Electrolytes Developed under the NASA PERS Program

Recently, NASA formally completed the Polymer Energy Rechargeable System (PERS) Program, which was established in 2000 in collaboration with the Air Force Research Laboratory (AFRL) to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The goal of this program was to ultimately develop an advanced, space-qualified battery technology, which embodied a solid polymer electrolyte (SPE) and complementary components, with improved performance characteristics that would address future aerospace battery requirements. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. A variety of cell and polymeric electrolyte concepts were pursued as part of the development efforts undertaken at numerous governmental, industrial and academic laboratories. Numerous candidate electrolyte materials were developed, synthesized and optimized for evaluation. Utilizing the component screening facility and the "standardized" test procedures developed at the NASA Glenn Research Center, electrochemical screening and performance evaluations of promising candidate materials were completed. This overview summarizes test results for a variety of candidate electrolyte materials that were developed under the PERS Program. Electrolyte properties are contrasted and compared to the original project goals, and the strengths and weaknesses of the electrolyte chemistries are discussed. Limited cycling data for full-cells using lithium metal and vanadium oxide electrodes are also presented. Based on measured electrolyte properties, the projected performance characteristics and temperature limitations of batteries utilizing the advanced electrolytes and components have been estimated. Limitations for the achievement of practical performance levels are also discussed, as well as needs for future research and development.

Bennett, William R.↗

Growing the First Stage of the Ares Launch Vehicles

In accordance with the U.S. Vision for Space Exploration, NASA has been tasked to send human beings to the moon, Mars, and beyond. The Firs t Stage of NASA's new Ares I Crew Launch Vehicle, which will loft the Orion Crew Exploration Vehicle into low-Earth orbit early next decade, will consist of a Space Shuttle-derived five-segment Reusable Solid Rocket Booster (RSRB); a pair of similar RSRBs also will be used on the Ares V cargo launch vehicle. This paper will discuss the basis for choosing the First Stage propulsion system; describe the activities the Exploration Launch Projects (ELP) Office is conducting to develop the First Stage; and offer a preview of future development activities including the Ares I-X test flight planned for 2009.

Priskos, Alex↗

Direct Observation of Modulated Radical Spin States in Metal–Organic Frameworks by Controlled Flexibility

Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique to a variety of fields. When incorporated in solid state materials, generation of organic radicals proves challenging due to aggregation. Metal–organic frameworks (MOFs) are promising candidates for immobilization and stabilization of organic radicals because of the tunable spatial arrangement of organic linkers and metal nodes, which sequesters the reactive species. Herein, a flexible, redox-active tetracarboxylic acid linker bearing two imidazole units was chosen to construct a new Zr 6 -MOF, NU-910, with scu topology. By exploiting the structural flexibility of NU-910, we successfully modulate the dynamics between an isolated organic radical species and an organic radical π-dimer species in the MOF system. Single-crystal X-ray diffraction analysis reveals that through solvent exchange from N,N-diethylformamide to acetone, NU-910 undergoes a structural contraction with interlinker distances decreasing from 8.32 Å to 3.20 Å at 100 K. Organic radical species on the bridging linkers are generated via UV light irradiation. Direct observation of temperature-induced spin switches from an isolated radical species to a magnetically silent radical π-dimer in NU-910 after irradiation in the solid state was achieved via variable-temperature single-crystal X-ray diffraction and variable-temperature electron paramagnetic resonance spectroscopy. Ultraviolet–visible–near infrared spectroscopy and density functional theory calculations further substantiated the formation of a radical cation π-dimer upon irradiation. As a result, this work demonstrates the potential of using flexible MOFs as a platform to modulate radical spin states in the solid phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Increasing temperature and flow management alter mercury dynamics in East Fork Poplar Creek

East Fork Poplar Creek (EFPC) is a mercury (Hg) contaminated creek in east Tennessee, USA. Stream restoration activities included the initiation of a flow management programme in 1996 in which water from a nearby lake was pumped to the head of the creek. We conducted regular water sampling for 2 years along the length of EFPC during active flow management and for 5 years after flow management stopped. Total Hg and total monomethylmercury (MMHg) concentration and flux decreased in the uppermost reaches of EFPC that were closest to the point of water addition. Most water quality parameters, including DOC concentration, remained unchanged after flow management termination. Nevertheless, SUVA 254 , a measure of dissolved organic matter (DOM) composition, increased and coincided with increased dissolved Hg (Hg D ) concentration and flux and decreased Hg solid-water partitioning coefficients throughout EFPC. Higher SUVA 254 and Hg D concentration have potential implications for bioavailability and MMHg production. Total and dissolved MMHg concentrations increased in lower reaches of EFPC after the end of flow management and these increases were most pronounced during spring and early summer when biota are more susceptible to exposure and uptake. A general warming trend in the creek after active flow management ended likely acted in concert with higher Hg D concentration to promote higher MMHg concentration. Total and dissolved MMHg concentrations were positively correlated with water temperature above a threshold value of 10°C. Concentration changes for Hg and MMHg could not be accounted for by changes in creek discharge that accompanied the cessation of flow management. In addition to the changing DOM composition in-stream, other watershed-scale factors likely contributed to the observed patterns, as these changes occurred over months rather than instantaneously after flow management stopped. Nevertheless, similar changes in MMHg have not been observed in a tributary to EFPC.

54 ENVIRONMENTAL SCIENCES↗

Stabilization of Ni-YSZ Anodes in Solid Oxide Fuel Cells using an ALD-Grown Aluminum Titanate Interlayer

The effect of an Al 2 TiO 5 (ALT) interlayer between Ni and YSZ on enhancing the thermal stability of Ni-YSZ solid oxide fuel cell was examined. Atomic layer deposition (ALD) was used to provide precise control of the structure and thickness of the ALT interlayer. The study's findings demonstrate that a 2 nm thick ALT interlayer deposited by ALD does not adversely affect the cell's ohmic resistance and effectively prevents Ni sintering and the loss of active area during high-temperature heat treatments. ALT layers thicker than 2 nm, although they enhanced Ni stability, were found to impede oxygen ion transport in the electrode and significantly increase the ohmic resistance of the cell, leading to a decline in performance.

25 ENERGY STORAGE↗

Highly Selective Carbon-Supported Boron for Oxidative Dehydrogenation of Propane

Bulk boron materials, such as hexagonal boron nitride (h-BN), are highly selective catalysts for the oxidative dehydrogenation of propane (ODHP). Previous attempts to improve the productivity of these systems involved the immobilization of boron on silica and resulted in less selective catalysts. Here, we report that acid-treated, activated carbon-supported boron prepared via incipient wetness impregnation with boric acid (B/OAC) exhibits equal propylene selectivity and improved productivity (kg propylene kg cat -1 hr -1 ) as compared to h-BN. Characterization of the fresh and spent catalysts with infrared, Raman, X-ray photoelectron, and solid-state NMR spectroscopies reveals the presence of oxidized/hydrolyzed boron that is clustered on the surface of the support.

03 NATURAL GAS↗

Simulation of 100-300 GHz solid-state harmonic sources

Accurate and efficient simulations of the large-signal time-dependent characteristics of second-harmonic Transferred Electron Oscillators (TEO's) and Heterostructure Barrier Varactor (HBV) frequency triplers have been obtained. This is accomplished by using a novel and efficient harmonic-balance circuit analysis technique which facilitates the integration of physics-based hydrodynamic device simulators. The integrated hydrodynamic device/harmonic-balance circuit simulators allow TEO and HBV circuits to be co-designed from both a device and a circuit point of view. Comparisons have been made with published experimental data for both TEO's and HBV's. For TEO's, excellent correlation has been obtained at 140 GHz and 188 GHz in second-harmonic operation. Excellent correlation has also been obtained for HBV frequency triplers operating near 200 GHz. For HBV's, both a lumped quasi-static equivalent circuit model and the hydrodynamic device simulator have been linked to the harmonic-balance circuit simulator. This comparison illustrates the importance of representing active devices with physics-based numerical device models rather than analytical device models.

NONLINEAR CIRCUITS↗

Electrochemical Imaging of Precisely‐Defined Redox and Reactive Interfaces

Abstract Understanding the diverse electrochemical reactions occurring at electrode‐electrolyte interfaces (EEIs) is a critical challenge to developing more efficient energy conversion and storage technologies. Establishing a predictive molecular‐level understanding of solid electrolyte interphases (SEIs) is challenging due to the presence of multiple intertwined chemical and electrochemical processes occurring at battery electrodes. Similarly, chemical conversions in reactive electrochemical systems are often influenced by the heterogeneous distribution of active sites, surface defects, and catalyst particle sizes. In this mini review, we highlight an emerging field of interfacial science that isolates the impact of specific chemical species by preparing precisely‐defined EEIs and visualizing the reactivity of their individual components using single‐entity characterization techniques. We highlight the broad applicability and versatility of these methods, along with current state‐of‐the‐art instrumentation and future opportunities for these approaches to address key scientific challenges related to batteries, chemical separations, and fuel cells. We establish that controlled preparation of well‐defined electrodes combined with single entity characterization will be crucial to filling key knowledge gaps and advancing the theories used to describe and predict chemical and physical processes occurring at EEIs and accelerating new materials discovery for energy applications.

Edgecomb, Joseph↗

Electrochemical Imaging of Precisely‐Defined Redox and Reactive Interfaces

Abstract Understanding the diverse electrochemical reactions occurring at electrode‐electrolyte interfaces (EEIs) is a critical challenge to developing more efficient energy conversion and storage technologies. Establishing a predictive molecular‐level understanding of solid electrolyte interphases (SEIs) is challenging due to the presence of multiple intertwined chemical and electrochemical processes occurring at battery electrodes. Similarly, chemical conversions in reactive electrochemical systems are often influenced by the heterogeneous distribution of active sites, surface defects, and catalyst particle sizes. In this mini review, we highlight an emerging field of interfacial science that isolates the impact of specific chemical species by preparing precisely‐defined EEIs and visualizing the reactivity of their individual components using single‐entity characterization techniques. We highlight the broad applicability and versatility of these methods, along with current state‐of‐the‐art instrumentation and future opportunities for these approaches to address key scientific challenges related to batteries, chemical separations, and fuel cells. We establish that controlled preparation of well‐defined electrodes combined with single entity characterization will be crucial to filling key knowledge gaps and advancing the theories used to describe and predict chemical and physical processes occurring at EEIs and accelerating new materials discovery for energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗