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At least 1,639 records · Page 91

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.

Cofer, Wesley R., III↗

Regeneration of Active Surface Alloys during Cyclic Oxidation and Reduction: Oxidation of H 2 on Pd/Ag(111)

The surface morphology and composition of a catalyst during excursions between oxidizing and reducing conditions can change substantially, especially in bimetallic alloys. Both thermodynamic and kinetic factors play a role in determining the properties of alloy surfaces where the active phase may be a metastable state. Previously, Ag oxide reduction was shown to be dramatically enhanced when Pd is on the surface; however, Pd is more stable when dissolved in Ag, raising the question as to whether a highly active Pd surface state will persist over multiple reaction cycles—a requirement for catalytic function. Experiments herein demonstrate that the enhanced chemical functionality due to the presence of Pd on the surface is retained, based on the enhanced rate of silver oxide reduction over multiple oxidation/reduction cycles for a Pd/Ag(111) model. Repeated oxidation and reduction promote PdAg alloying and reversible structural and compositional changes are detected using X-ray photoelectron spectroscopy. Furthermore, this study establishes that metastable phases can persist in reactive processes on surfaces, indicating their potential in heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design of a high-temperature cell for cobalt-60 irradiations of aqueous solutions with in situ UV–visible spectroscopy

To understand the speciation of solutes in aqueous solutions in high temperature radiation environments, we report the design and fabrication of a custom-built, high temperature (≤300 °C) titanium irradiation cell with in situ optical spectroscopy capabilities, as afforded by coupled fiber optic cables. The wetted surfaces of the 8-inch tall cylindrical cell with 3.5 in. diameter are entirely made of titanium, sapphire, and gold, which are chemically and radiolytically inert. The initial benchmarking results are reported, including the baseline spectrum of deionized water as a function of temperature, the stability of a spectrum over 4 h at 100 °C, and an irradiated Fricke dosimetry solution under ambient irradiator temperature conditions (27.0 ± 0.5 °C). Further, the average gamma radiation dose rate in the cell in its current configuration is 26.1 ± 1.3 Gy min -1 . This cell has application in studying several processes throughout the nuclear fuel cycle, including the reactor coolant behavior.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Using Neutron Spectroscopy to Constrain the Composition and Provenance of Phobos and Deimos

The origin of the Martian moons Phobos and Deimos is obscure and enigmatic. Hypotheses include the capture of asteroids originally from the outer main belt or beyond, residual material left over from Mars' formation, and accreted ejecta from a large impact on Mars, among others. Measurements of reflectance spectra indicate a similarity to dark, red D-type asteroids, but could indicate a highly space-weathered veneer. Here we suggest a way of constraining the near-surface composition of the two moons, for comparison to known meteoritic compositions. Neutron spectroscopy, particularly the thermal and epithermal neutron flux, distinguishes clearly between various classes of meteorites and varying hydrogen (water) abundances. Perhaps most surprising of all, a rendezvous with Phobos or Deimos is not necessary to achieve this. A low-cost mission based on the LADEE spacecraft design in an eccentric orbit around Mars can encounter Phobos every 2 weeks. As few as five flyby encounters at speeds of 2.3 kilometers per second and closest-approach distance of 3 kilometers provide sufficient data to distinguish between ordinary chondrite, water-bearing carbonaceous chondrite, ureilite, Mars surface, and aubrite compositions. A one-Earth year mission design includes many more flybys at lower speeds and closer approach distances, as well as similar multiple flybys at Deimos in the second mission phase, as described in the Phobos And Deimos Mars Environment (PADME) mission concept. This presentation will describe the expected thermal and epithermal neutron fluxes based on MCNP6 (Monte Carlo N (i.e. Neutron)-Particle transport code (version 6) simulations of different meteorite compositions and their uncertainties.

thtermal and epithermal neutron fluxes↗

Morphological stability and fluid dynamics of vapor crystal growth

Progress is reported in establishing the capabilities of thermal deflection spectroscopy for measurements of the concentration field around a growing crystal. Work was completed on the inclusion of the next nearest neighbor interaction into a surface roughness model and the resulting formalism was applied to copper, zinc, and lead. Other work in mass spectroscopy and vapor transport is discussed.

Rosenberger, F. E.↗

Spatially resolved ballistic electron spectroscopy of subsurface interfaces

Buried interfaces have traditionally been inaccessible to direct investigation by surface-sensitive techniques. A unique and novel electronic probe, which is sensitive to subsurface electronic structure, has been utilized to probe Schottky barrier interfaces. The method, ballistic electron emission microscopy (BEEM), is based on scanning tunnelling microscopy (STM) techniques. A theoretical treatment has been developed to describe the ballistic electron spectra obtained by BEEM and this treatment is applied to data obtained on the Au-Si Schottky barrier interface system. Excellent agreement between experiment and theory is obtained. In addition, the treatment predicts nanometer spatial resolution for interface imaging by BEEM.

Bell, L. D.↗

Spectroscopy of galaxies in distant clusters. IV - A catalog of photometry and spectroscopy for galaxies in seven clusters with z in the range of 0.35 to 0.55

Photometry and spectroscopy for seven deep fields containing distant clusters of galaxies with z in the range of 0.35 to 0.55 are presented. Positions and photometric parameters, including r-magnitudes g - r and r - i colors, surface brightnesses, and photometric profile types are given for about 2000 galaxies. Low-resolution spectroscopy is obtained from which redshifts are determined for 289 objects, of which 190 are cluster members. These are classified according to dominant spectral features, and examples are plotted in each cluster. Color-magnitude and color-color diagrams are formed which show trends in the cluster populations, and maps are made of the cluster field using the color-color relations to increase the contrast of cluster over field. Galaxies with spectra typical of old stellar populations cluster most strongly, with active galaxies, those with recent or ongoing star formation, or an active nucleus, distributed more diffusely. The g - r color is well correlated with active star formation as judged from spectral features.

Dressler, Alan↗

Microwave spectroscopy

Microwave spectroscopy - electric field effects in nuclear magnetic resonance of fluids, expansion of velocity surfaces in spherical harmonics, and electron cross relaxation in dilute ruby

CROSS RELAXATION↗

The Influence of Cr-Additives on the Polarization Resistance of Praseodymium-Doped Ceria Cathodes for Solid Oxide Fuel Cells

While Cr poisoning of the oxygen reduction reaction (ORR) at SOFC cathodes is widely agreed to involve deactivation of oxygen exchange sites, the degradation mechanism remains ambiguous. Here, we selected an alternative cathode material Pr 0.1 Ce 0.9 O 2− δ , free of Sr segregation, to systematically investigate the effect of Cr-induced degradation in ORR. We expand on our previous studies in which the acidity/basicity of binary additives was found to be a strong indicator of the rate of oxygen surface exchange, by electrochemically investigating the ORR activity of the PCO cathode by impedance spectroscopy. Serial infiltration with acidic Cr-based oxides was found to degrade ORR activity as reflected in a 20-fold increase in area specific resistance (ASR) without corresponding changes in activation energy, with the opposite trend obtained with Ca-based oxides. Detected changes in total capacitance, attributed to changes in surface capacitance, also suggest depressed/enhanced PCO surface redox behavior with Cr/Ca-based infiltrants. Taken together, these results point to a more universal source of ORR poisoning/activation, based on acidity/basicity, rather than physical blocking of active sites. With this improved understanding, one can expect progress to be made in the coming years in optimizing means for protecting catalytic surfaces from degradation and/or improving their performance.

25 ENERGY STORAGE↗

Effect of the Chemical States of Copper on Methanol Decomposition and Oxidation

Here, the decomposition and oxidation reactions of CH 3 OH over metallic Cu(100) and Cu 2 O-covered Cu(100) surfaces are studied using a combination of in-situ ambient-pressure X-ray photoelectron spectroscopy, Auger electron spectroscopy, and density functional theory calculations. We identify the sequential chemical transformation pathways from bond cleavage to the formation of intermediates and final products under operational conditions. Accumulative surface adsorption of CH 3 O species on metallic Cu(100) impedes the decomposition of CH 3 OH. Co-dosing on metallic Cu(100) with low pressures of 1·10 -4 Torr CH 3 OH + 1·10 -4 Torr O 2 results in partial oxidation of CH 3 OH, where the chemisorbed O ads reduces surface sites available for CH 3 O adsorption, decreasing the surface activity for CH 3 OH decomposition. In contrast, the Cu 2 O overlayer formed under the elevated pressures of 0.33 Torr CH 3 OH + 0.66 Torr O 2 promotes the total oxidation of CH 3 OH into the final products of CO 2 and H 2 O, arising from the active reaction 2 between lattice O within Cu 2 O and intermediates of CH 3 O, CH 2 O, HCOO, and CO. Despite the more favorable O-H bond scission, C-O bond scission also occurs to result in surface accumulation of CH x on metallic Cu(100), blocking active sites for decomposition reactions of CH 3 OH and CH 3 O. By comparison, the CH x species on the Cu 2 O-covered Cu(100) undergo oxidation into CO 2 and H 2 O with lattice O in the Cu 2 O overlayer, thereby freeing active sites for the total oxidation of CH 3 OH. These results highlight the distinct roles of metallic Cu and Cu 2 O in the pathways of CH 3 OH decomposition and oxidation reactions, offering practical insights for the design of Cu-based catalysts with tailored reactivity and selectivity.

36 MATERIALS SCIENCE↗

Infrared nanoimaging and nanospectroscopy of electrochemical energy storage materials and interfaces

Electrochemical interfaces are central to the function and performance of energy storage devices. Thus, the development of new methods to characterize these interfaces, in conjunction with electrochemical performance, is essential for bridging the existing knowledge gaps and accelerating the development of energy storage technologies. Of particular need is the ability to characterize surfaces or interfaces in a non-destructive way with adequate resolution to discern individual structural and chemical building blocks. To this end, sub-diffraction-limit low-energy infrared optical probes that exploit near-field interactions within atomic force microscopy platforms, such as pseudoheterodyne nanoimaging, photothermal nanoimaging and nanospectroscopy, and nanoscale Fourier transform infrared spectroscopy, are all powerful emerging techniques. These are capable of non-destructive surface probing and imaging at nanometer resolution. This review outlines recent efforts to characterize ex situ, in situ, and operando electrode materials and electrochemical interfaces in rechargeable batteries with these advanced infrared near-field probes.

25 ENERGY STORAGE↗

pH-dependent reactivity of water at MgO(100) and MgO(111) surfaces

Facet-dependent surface charging of metal oxides in water dominates the ion transport behavior across the interface, in turn impacting many natural and industrial processes such as adsorption, the formation and stabilization of nanoparticle suspensions, corrosion, and heterogeneous catalysis. Here we investigated the pH-dependent surface chemistry of two low-index MgO single crystal surfaces, namely MgO(100) and MgO(111), using vibrational sum frequency generation (vSFG) spectroscopy. This allowed us to evaluate facet-dependent pH effects on the hydration and hydroxylation at the solid/aqueous interface and point-of-zero charge (PZC) values. The MgO system is complicated by its thermodynamic instability with respect to Mg(OH) 2 in water at ambient conditions. Here, for both hydroxylated MgO(100) and MgO(111) surfaces, the PZC is found to be around pH ∼ 12, which compares well with reported values for MgO single crystal and nanoparticle surfaces. However, structure specific differences in the molecular water hydrogen bonding network near the surface are evident at mildly acidic pH. To our knowledge, this is the first account of the PZC values for the MgO(111) single-crystal surface, an electrostatically unstable MgO termination that is prone to reconstruction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ex Situ Photoelectron Emission Microscopy of Polycrystalline Bismuth and Antimony Telluride Surfaces Exposed to Ambient Oxidation

The surfaces of textured polycrystalline N-type bismuth telluride and P-type antimony telluride materials were investigated using ex situ photoelectron emission microscopy (PEEM). PEEM enabled imaging of the work function for different oxidation times due to exposure to air across sample surfaces. The spatially averaged work function was also tracked as a function of air exposure time. N-type bismuth telluride showed an increase in the work function around grain boundaries relative to grain interiors during the early stages of air exposure-driven oxidation. At longer time exposure to air, the surface became homogenous after a ~5 nm-thick oxide formed. X-ray photoemission spectroscopy was used to correlate changes in PEEM imaging in real space and work function evolution to the progressive growth of an oxide layer. The observed work function contrast is consistent with the pinning of electronic surface states due to the defects at a grain boundary.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Room temperature colossal superparamagnetic order in aminoferrocene–graphene molecular magnets

Intensive studies are published for graphene-based molecular magnets due to their remarkable electric, thermal, and mechanical properties. However, to date, most of all produced molecular magnets are ligand based and subject to challenges regarding the stability of the ligand(s). The lack of long-range coupling limits high operating temperature and leads to a short-range magnetic order. Herein, we introduce an aminoferrocene-based graphene system with room temperature superparamagnetic behavior in the long-range magnetic order that exhibits colossal magnetocrystalline anisotropy of 8 × 10 5 and 3 × 10 7 J/m 3 in aminoferrocene and graphene-based aminoferrocene, respectively. These values are comparable to and even two orders of magnitude larger than pure iron metal. Aminoferrocene [C 10 H 11 FeN] + is synthesized by an electrophilic substitution reaction. It was then reacted with graphene oxide that was prepared by the modified Hammers method. The phase structure and functionalization of surface groups were characterized and confirmed by XRD, FT-IR, and Raman spectroscopy. To model the behavior of the aminoferrocene between two sheets of hydroxylated graphene, we have used density functional theory by placing the aminoferrocene molecule between two highly ordered hydroxylated sheets and allowing the structure to relax. Here, the strong bowing of the isolated graphene sheets suggests that the charge transfer and resulting magnetization could be strongly influenced by pressure effects. In contrast to strategies based on ligands surface attachment, our present work that uses interlayer intercalated aminoferrocene opens routes for future molecular magnets as well as the design of qubit arrays and quantum systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Physiological response to submaximal isometric contractions of the paravertebral muscles

STUDY DESIGN: Brief (30-second) isometric trunk extensions at 5%, 20%, 40%, 60%, and 80% of maximal voluntary contraction (MVC) and 3 minutes of prolonged trunk extension (20% MVC) in erect position were studied in nine healthy male subjects. OBJECTIVES: To investigate the intercorrelation between intramuscular pressure and tissue oxygenation of the paravertebral muscles during submaximal isometric contractions and further, to evaluate paravertebral electromyogram and intramuscular pressure as indicators of force development. SUMMARY OF BACKGROUND DATA: Local physiologic responses to muscle contraction are incompletely understood. METHODS: Relative oxygenation was monitored with noninvasive near-infrared spectroscopy, intramuscular pressure was measured with a transducer-tipped catheter, and surface electromyogram was monitored at three recording sites. RESULTS: The root mean square amplitudes of the paravertebral electromyogram (L4, left and right; T12, right) and intramuscular pressure measured in the lumbar multifidus muscle at L4 increased with greater force development in a curvilinear manner. A significant decrease in the oxygenation of the lumbar paravertebral muscle in response to muscle contraction was found at an initial contraction level of 20% MVC. This corresponded to a paravertebral intramuscular pressure of 30-40 mm Hg. However, during prolonged trunk extension, no further decrease in tissue oxygenation was found compared with the tissue oxygenation level at the end of the brief contractions, indicating that homeostatic adjustments (mean blood pressure and heart rate) over time were sufficient to maintain paravertebral muscle oxygen levels. CONCLUSION: At a threshold intramuscular pressure of 30-40 mm Hg during muscle contraction, oxygenation in the paravertebral muscles is significantly reduced. The effect of further increase in intramuscular pressure on tissue oxygenation over time may be compensated for by an increase in blood pressure and heart rate. Surface electromyogram amplitudes and intramuscular pressure can be used as indicators of paravertebral muscle force.

NASA Center ARC↗

Probing nanoparticle substrate interactions with synchrotron infrared nanospectroscopy: Coupling gold nanorod Fabry-Pérot resonances with SiO 2 and $h$-BN phonons

Spectroscopic interrogation of materials in the midinfrared with nanometer spatial resolution is inherently difficult due to the long wavelengths involved, reduced detector efficiencies, and limited availability of spectrally bright, coherent light sources. Technological advances are driving techniques that overcome these challenges, enabling material characterization in this relatively unexplored spectral regime. Synchrotron infrared nanospectroscopy (SINS) is an imaging technique that provides local sample information of nanoscale target specimens in an experimental energy window between 330 and 5000 cm -1 . Here, using SINS, we analyzed a series of individual gold nanorods patterned on a SiO 2 substrate and on a flake of hexagonal boron nitride. The SINS spectra reveal interactions between the nanorod photonic Fabry-Pérot resonances and the surface phonon polaritons of each substrate, which are characterized as avoided crossings. A coupled oscillator model of the hybrid system provides a deeper understanding of the coupling and provides a theoretical framework for future exploration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Characterization of Candidate Materials for Remote Recession Measurements of Ablative Heat Shield Materials

A method of remotely measuring surface recession of a material sample in a plasma flow through emission spectroscopy of the post shock layer was characterized through experiments in the NASA Langley HYMETS arc jet facility. Different methods for delivering the seed products into the Phenolic Impregnated Carbon Ablator (PICA) material samples were investigated. Three samples were produced by seeding the PICA material with combinations of Al, Si, HfO2, VB2, Al2O3, SiO2, TiC, HfC, NaCl, and MgCl2 through infusing seed materials into a core of PICA, or through encapsulating seed material in an epoxy disk, mechanically bonding the disk to a PICA sample. The PICA samples seeded with the candidate tracers were then tested at surface temperatures near 2400 K under low pressure air plasma. The emission of Al, Ti, V, Na, and Mg in the post-shock layer was observed in the UV with a high resolution imaging spectrometer viewing the whole stagnation line from the side, and from UV to NIR with a fiber-coupled miniaturized spectrometer observing the sample surface in the wavelength range from 200 nm to 1,100 nm from the front through a collimator. Al, Na, and Mg were found to be emitting in the post-shock spectra even before the recession reached the seeding depth - therefore possibly characterizing the pyrolysis process rather than the recession itself. The appearance of Ti and V emission in the spectra was well correlated with the actual recession which was monitored through a video of the front surface of the sample. The applicability of a seed material as an indicator for recession appears to be related to the melting temperature of the seed material. Future parametric studies will be carried out in low power plasma facilities at the University of Kentucky.

Butler, Bradley D.↗

Estimation of Supraglacial Dust and Debris Geochemical Composition via Satellite Reflectance and Emissivity

We demonstrate spectral estimation of supraglacial dust, debris, ash and tephra geochemical composition from glaciers and ice fields in Iceland, Nepal, New Zealand and Switzerland. Surface glacier material was collected and analyzed via X-ray fluorescence spectroscopy (XRF) and X-ray diffraction (XRD) for geochemical composition and mineralogy. In situ data was used as ground truth for comparison with satellite derived geochemical results. Supraglacial debris spectral response patterns and emissivity-derived silica weight percent are presented. Qualitative spectral response patterns agreed well with XRF elemental abundances. Quantitative emissivity estimates of supraglacial SiO2 in continental areas were 67% (Switzerland) and 68% (Nepal), while volcanic supraglacial SiO2 averages were 58% (Iceland) and 56% (New Zealand), yielding general agreement. Ablation season supraglacial temperature variation due to differing dust and debris type and coverage was also investigated, with surface debris temperatures ranging from 5.9 to 26.6 C in the study regions. Applications of the supraglacial geochemical reflective and emissive characterization methods include glacier areal extent mapping, debris source identification, glacier kinematics and glacier energy balance considerations.

Casey, Kimberly Ann↗