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At least 1,459 records · Page 81

Elucidating the mechanism of photochemical CO 2 reduction to CO using a cyanide-bridged di-manganese complex

The complex, [{[Mn(bpy)(CO) 3 ] 2 }(μ-CN)] + (Mn 2 CN + ), has previously been shown to photochemically reduce CO 2 to CO. The detailed mechanism behind its reactivity was not elucidated. In this work, the photoevolution of this reaction is studied in acetonitrile (MeCN) using IR and UV-vis spectroscopy. Samples were excited into the Mn I → π* bpy metal-to-ligand charge transfer (MLCT) absorption band triggering CO loss, and rapid MeCN solvent ligation at the open coordination site. It is concluded that this process occurs selectively at the Mn axial ligation site that is trans to the C-end of the bridging cyanide. Upon further photolysis, the metal–metal bonded dimeric species, [(CO) 3 (bpy)Mn–Mn(bpy)(CO) 3 ] (Mn–Mn) is observed to form under anaerobic conditions. The presence of this dimeric species coincides with the observation of CO production. When oxygen is present, CO 2 photoreduction does not occur, which is attributed to the inability of Mn 2 CN + to convert to the metal–metal bonded dimer. Photolysis experiments, where the Mn–Mn dimer is formed photochemically under argon first and then exposed to CO 2 , reveal that it is the radical species, [Mn(bpy)(CO) 3 ˙] (Mn˙), that interacts with the CO 2 . Since the presence of Mn–Mn and light is required for CO production, [Mn(bpy)(CO) 3 ˙] is proposed to be a photochemical reagent for the transformation of CO 2 to CO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The sunspot chromosphere-corona transition region

Data from simultaneous readings of the line intensities, Doppler shifts, and line widths of a sunspot ion emission lines between 1170-1700 A are reported. Subsonic and supersonic flows were observed in the same line of sight above the umbra. A reduction of coronal plasma over sunspots with an electron temperature exceeding 1,000,000 K was confirmed, concurrent with enhanced emission from the transition region plasma in the temperature range 200,000-1,000,000 K. The differential emission measure is noted to have been caused to shift because of the enhancement of the transition region plasma emission, where radiative losses dominated the energy balance. Calculations of the energy balance also indicated that a detected divergence in the enthalpy flux for the umbral downflows could balance the radiative losses in the electron temperature range 30,000-200,000 K.

Nicolas, K. R.↗

Load cell verification of the uprated high pressure oxygen turbopump for the Space Shuttle Main Engine

The high pressure turbomachinery of the Space Shuttle Main Engine has the highest power-to-weight ratio of any operational machine known. Subsynchronous rotor whirl of the high pressure oxygen turbopump occurred in development testing at full-power level (109 percent thrust). The means by which the turbopump was successfully uprated is presented herein. The subsynchronous motion was determined to be driven by impeller destabilizing forces in combination with low net damping and bearing degradation. The degradation resulted from ball wear due primarily to an excessive loading condition of operating too near the lightly damped rotor second critical speed while under a large static load and, secondarily, from reverse bearing loading or loss of internal clearance and coolant during simulated flight conditions. The rotor response was reduced by stiffening the shaft and supports, optimizing the stiffness and damping of annular seals, and increasing the bearing deadband. The uprated oxygen turbopump configuration was verified by converting the pump and bearing support into a load cell for the purpose of systematically quantifying the load reduction benefits relative to baseline turbopumps. The damped second critical speed margin and the load sharing have been substantially improved which has resulted in reduced bearing loads for improved service life of the machine at full-power level.

Beatty, R. F.↗

Computerized Analysis Of Thermal-Diffusivity Data

Improved data-acquisition and data-analysis system for thermal-diffusivity measurements using flash method incorporates digital oscilloscope and microcomputer for rapid reduction of experimental data. In thermal-diffusivity apparatus thin specimen heated on one face by pulsed xenon flashlamp, subsequent temperature rise on opposite face monitored by infrared detector. Thermal diffusivity estimated from thickness of specimen and from time after initial pulse during which temperature rise reaches half maximum value. Accuracy of estimate improved by correcting temperature measurements for radiative loss of heat from specimen and for finite duration and specific waveform of flashlamp pulse. System devised for use in high-temperature measurements of thermoelectric materials.

Chmielewski, Artur B.↗

Laboratory test and acoustic analysis of cabin treatment for propfan test assessment aircraft

An aircraft cabin acoustic enclosure, built in support of the Propfan Test Assessment (PTA) program, is described. Helmholtz resonators were attached to the cabin trim panels to increase the sidewall transmission loss (TL). Resonators (448) were located between the trim panels and fuselage shell. In addition, 152 resonators were placed between the enclosure and aircraft floors. The 600 resonators were each tuned to a 235 Hz resonance frequency. After flight testing on the PTA aircraft, the enclosure was tested in the Kelly Johnson R and D Center Acoustics Lab. Laboratory noise reduction (NR) test results are discussed. The enclosure was placed in a Gulfstream 2 fuselage section. Broadband (138 dB overall SPL) and tonal (149 dB overall SPL) excitations were used in the lab. Tonal excitation simulated the propfan flight test excitation. The fundamental tone was stepped in 2 Hz intervals from 225 through 245 Hz. The resonators increase the NR of the cabin walls around the resonance frequency of the resonator array. The effects of flanking, sidewall absorption, cabin adsorption, resonator loading of trim panels, and panel vibrations are presented. Increases in NR of up to 11 dB were measured.

Kuntz, H. L.↗

Overlapping Conditions in IMPACT

Introduction The IMPACT 1.0 model assumes independence of 119 different medical conditions. That is, it is assumed that one medical event maps to a single medical condition. However, it is often the case that a single medical event may lead to several different concurrent conditions (e.g., a single accident resulting in multiple fractures, chest/abdominal trauma, and sepsis). There is a significant overlap between many of the conditions in ICL 1.0. For example, depression and anxiety are two separate conditions but often co-exist. This overlap may lead to an overestimation in the incidence calculation. In future iterations of the model, we plan to address progression of medical conditions. Methods There are two possible methods to approach progression of a medical condition. The first is to take any medical condition in ICL, calculate its incidence and determine its outcomes no matter what sequelae occur. For example, calculate the incidence of prostatitis and determine its metrics (e.g., loss of crew life, risk of medical evacuation or task time affected) no matter what the sequelae might be (sepsis, hydronephrosis, renal failure, etc.). The second approach is to take any medical condition in the ICL and calculate the outcomes based on transitions to any other condition. For example, calculate the incidence of nephrolithiasis and determine the incidence of each possible transition (e.g., hydronephrosis, renal failure, UTI, pyelonephritis, sepsis) and then determine its metrics. With perfectly informative evidence, the answers should be the same using either method. The question is which approach best reduces the opportunity for overlapping. Results The team identified 31 conditions that were the most likely to transition to a secondary condition such as sepsis and respiratory failure. It was felt that the first approach, as described above, would be the easiest to implement and would have the greatest reduction in overlapping conditions. The identified conditions were primarily infectious conditions, like UTI and pneumonia (which could lead to both respiratory failure and sepsis), toxic inhalations, cardiac arrest, seizures, and trauma. Once these conditions were identified, the conditions were divided between the four clinicians on the team to identify those that were not consistent with the others in way they were approached. There were 13 conditions that were found to be problematic. Some condition definitions needed to be changed to eliminate references to transitions or to update them in cases where the definitions were out of date. Some conditions required new evidence to correct the loss of crew life, and one condition was felt to have so much overlap that it was recommended for elimination. A second effort required modification of the sepsis incidence calculation to prevent double counting of the conditions, such as prostatitis, that could progress to sepsis. Conclusion The team made significant progress in clarifying the method for dealing with transitions from one medical condition to another. In addition, errors were found and corrected in definitions, incidence, and loss of crew life as well as a condition in which reference was made to a CLiFF that was no longer included. These modifications will provide greater fidelity in the IMPACT model and reduce overlap.

Arian Anderson↗

Evaluation of probabilistic photometric redshift estimation approaches for The Rubin Observatory Legacy Survey of Space and Time (LSST)

Many scientific investigations of photometric galaxy surveys require redshift estimates, whose uncertainty properties are best encapsulated by photometric redshift (photo-z) posterior probability density functions (PDFs). A plethora of photo-z PDF estimation methodologies abound, producing discrepant results with no consensus on a preferred approach. We present the results of a comprehensive experiment comparing twelve photo-z algorithms applied to mock data produced forLarge Synoptic Survey Telescope The Rubin Observatory Legacy Survey of Space and Time (lsst) Dark Energy Science Collaboration (desc). By supplying perfect prior information, in the form of the complete template library and a representative training set as inputs to each code, we demonstrate the impact of the assumptions underlying each technique on the output photo-z PDFs. In the absence of a notion of true, unbiased photo-z PDFs, we evaluate and interpret multiple metrics of the ensemble properties of the derived photo-z PDFs as well as traditional reductions to photo-z point estimates. Additionally, we report systematic biases and overall over/under-breadth of the photo-z PDFs of many popular codes, which may indicate avenues for improvement in the algorithms or implementations. Furthermore, we raise attention to the limitations of established metrics for assessing photo-z PDF accuracy; though we identify the conditional density estimate (CDE) loss as a promising metric of photo-z PDF performance in the case where true redshifts are available but true photo-z PDFs are not, we emphasize the need for science-specific performance metrics.

79 ASTRONOMY AND ASTROPHYSICS↗

Segmented vortex flaps

Segmented vortex flaps were suggested as a means of delaying the vortex spill-over causing thrust loss over the outboard region of single-panel flaps. Also proposed was hinge-line setback for exploiting leading-edge suction in conjunction with vortex flaps to improve the overall thrust per unit flap area. These two concepts in combination were tested on a 60-deg cropped delta wing model. Significant improvement in flap efficiency was indicated by a reduction of the flap/wing area from 11.4% of single-panel flap to 6.3% of a two segment delta flap design, with no lift/drag penalty at lift coefficients between 0.5 and 0.7. The more efficient vortex flap arrangement of this study should benefit the performance attainable with flaps of given area on wings of moderate leading-edge sweep.

Rao, D. M.↗

Dye laser traveling wave amplifier

Injection locking was applied to a cavity-dumped coaxial flashlamp pumped dye laser in an effort to obtain nanosecond duration pulses which have both high energy and narrow-linewidth. In the absence of an injected laser pulse, the cavity-dumped dye laser was capable of generating high energy (approx. 60mJ) nanosecond duration output pulses. These pulses, however, had a fixed center wavelength and were extremely broadband (approx. 6nm FWHM). Experimental investigations were performed to determine if the spectral properties of these outputs could be improved through the use of injection-locking techniques. A parametric study to determine the specific conditions under which the laser could be injection-locked was also carried out. Significant linewidth reduction to 0.0015nm) of the outputs was obtained through injection-locking but only at wavelengths near the peak lasing wavelength of the dye. It was found, however; that by inserting weakly dispersive tuning elements in the laser cavity, these narrow-linewidth outputs could be obtained over a wide (24nm) tuning range. Since the tuning elements had low insertion losses, the tunability of the output was obtained without sacrificing output pulse energy.

Davidson, F.↗

Magnetic suspension and balance system (MSBS) advanced study.I - System design

A magnetic suspension and balance system is designed to support models of aircraft or other objects in wind tunnels by means of magnetic forces. Major design improvements have been achieved, resulting in reductions of the system size, weight, and cost. These improvements are due to: (1) the use of holmium in the model core to increase its magnetic moment, (2) the use of a powerful new permanent magnet material in the model wings, (3) a new arrangement for the roll coils, and (4) the use of a nonmetallic structure to eliminate eddy current losses. The conceptual design of the holmium core superconductive solenoid and of the new permanent magnet wing assembly is described in detail. The discussion includes comparisons of the pole strengths for different model core magnets, the design of a superconducting solenoid and cryostat, and the analysis of model wing magnetic requirements.

Boom, Roger W.↗

An investigation of passive control methods for shock-induced separation at hypersonic speeds

The effectiveness of several passive control techniques on shock-induced boundary-layer separation at hypersonic speed was investigated. Two approaches for alleviating the turbulent separation losses were examined: porous surface mass transfer and surface grooving. A total of four perforated surfaces with varying porosities were evaluated, and three groove orientations with respect to the freestream direction were studied. A comparison of the results from passive control techniques with those from an 'uncontrolled' shock impingement showed that the porous surface with the greatest porosity provided the greatest reduction in the pressure rise across the oblique shock wave. The grooved surface tested were found to be not effective; each of the grooved configurations examined increased the peak pressure value.

Rallo, R.↗

Electromagnetic Design of a Magnetically-Coupled Spatial Power Combiner

The design of a two-dimensional beam-combining network employing a parallel-plate superconducting waveguide with a mono-crystalline silicon dielectric is presented. This novel beam-combining network structure employs an array of magnetically coupled antenna elements to achieve high coupling efficiency and full sampling of the intensity distribution while avoiding diffractive losses in the multi-mode region defined by the parallel-plate waveguide. These attributes enable the structures use in realizing compact far-infrared spectrometers for astrophysical and instrumentation applications. When configured with a suitable corporate-feed power-combiner, this fully sampled array can be used to realize a low-sidelobe apodized response without incurring a reduction in coupling efficiency. To control undesired reflections over a wide range of angles in the finite-sized parallel-plate waveguide region, a wideband meta-material electromagnetic absorber structure is implemented. This adiabatic structure absorbs greater than 99 of the power over the 1.7:1 operational band at angles ranging from normal (0 degree) to near parallel (180 degree) incidence. Design, simulations, and application of the device will be presented.

Bulcha, B.↗

Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions

The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. Here, this report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum–iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ~24% Pt are shown to exhibit the highest mass activity (3.4 A/mg Pt , ~20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40000 cycles and <30% loss after 120000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)-body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions. Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.

25 ENERGY STORAGE↗

Convenient Syntheses of Trivalent Uranium Halide Starting Materials without Uranium Metal

Low-valent uranium coordination chemistry continues to rely heavily on access to trivalent starting materials, but these reagents are typically prepared from uranium turnings, which are becoming increasingly difficult to acquire. Here we report convenient syntheses of UI 3 (THF) 4 (THF = tetrahydrofuran) and UBr 3 (THF) 4 from UCl 4 , a more accessible uranium starting material that can be prepared from commercially available uranium oxides. UCl 3 (THF) 2 (1), UBr 3 (THF) 4 (2), and UI 3 (THF) 4 (3) were prepared by single-pot reductions from UCl 4 using KH and KC 8 and converted to 2 or 3 by halide exchange with the corresponding Me 3 SiX (where X = Br or I). Reduction of UI 4 (Et 2 O) 2 (4; Et 2 O = diethyl ether) and UI 4 (1,4-dioxane) 2 (5) was also shown to cleanly yield 3. Complex 1 was also synthesized separately by the addition of anhydrous HCl to U(BH 4 ) 3 (THF) 2 , which was prepared by thermal reduction of U(BH 4 ) 4 . All three trivalent uranium halide complexes were isolated in high crystalline yields (typically 85–99%) and their formulations were confirmed by single-crystal X-ray diffraction, elemental analysis, and 1 H NMR and IR spectroscopy. Elemental analysis conducted on triplicate samples of 1–3 exposed to vacuum for different time intervals revealed significant THF loss for all three complexes in as little as 15 min. Altogether, these results offer expedient entry into low-valent uranium chemistry for researchers lacking access to uranium turnings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design Rules for Carboborothermic Reduction Synthesis of High Uranium Density UB 4 –UBC Composites

Uranium borides are promising candidate fuel forms for use in advanced nuclear reactors due to their high thermal conductivity and potential for dual use as both fuel and burnable absorber. In this work, uranium tetraboride () and uranium monoboroncarbide (UBC) composite were synthesized by using industrially scalable carboborothermic reduction method. The final uranium boride phase composition is sensitive to the sample holding crucibles ( and graphite) such that graphite supply excess carbon, promoting the formation of a predominant UBC phase. The high‐temperature in situ synchrotron X‐ray diffraction of pristine –UBC show persistence , UBC, and phases while preoxidized –UBC leads to predominant and formation due to progressive oxidation and boron loss at high temperature. The oxidation behavior was further characterized using thermogravimetric analysis, allowing direct comparison with other potential accident tolerant fuels such as , , UC, and UN. The –UBC shows higher uranium loading than monolithic and demonstrates promising oxidation behavior at high temperature, pointing to its potential as an improved uranium boride‐based fuel form.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Effect of reducing rotor blade inlet diameter on the performance of a 11.66-Centimeter radial-inflow turbine

The effect of increased rotor blade loading on turbine performance was investigated by reducing rotor blade inlet diameter. The reduction was made in four stages. Each modification was tested with the same stator using cold air as the working fluid. Results are presented in terms of equivalent mass flow and efficiency at equivalent design rotative speed and over a range of pressure ratios. Internal flow characteristics are shown in terms of stator exit static pressure and the radial variation of local loss and rotor-exit flow angle with radius ratio. Included are velocity diagrams calculated from the experimental results.

Kofskey, M. G.↗

Direct EPP Affects on the Middle Atmosphere

Energetic precipitating particles (EPPs) can cause significant direct constituent changes in the mesosphere and stratosphere (middle atmosphere) during certain periods. Both protons and electrons can influence the polar middle atmosphere through ionization and dissociation processes. EPPs can enhance HOx (H, OH, HO2) through the formation of positive ions followed by complex ion chemistry and NOx (N, NO, NO2) through the dissociation of molecular nitrogen. The HOx increases result in direct ozone destruction in the mesosphere and upper stratosphere via several catalytic loss cycles. Such middle atmospheric HOx-caused ozone loss is rather short-lived due to the relatively short lifetime (hours) of the HOx constituents. The NOx family has a considerably longer lifetime than the HOx family and can also lead to catalytic ozone destruction. EPP-caused enhancements of the NOx family can affect ozone directly, if produced in the stratosphere. Ozone decreases from the EPPs lead to a reduction in atmospheric heating and, subsequent atmospheric cooling. Conversely, EPPs can cause direct atmospheric heating through Joule heating. Measured HOx constituents OH and HO2 showed increases due to solar protons. Observed NOx constituents NO and NO2 were enhanced due to both solar protons and precipitating electrons. Other hydrogen- and nitrogen-ocntaining constituents were also measured to be directly influenced by EPPs, including N2O, HNO3, HO2NO2, N2OS, H2O2, ClONO2, HCl, and HOCl. Observed constituents ClO and CO were directly affected by EPPs as well. Many measurements indicated significant direct ozone decreases. A significant number of satellites housed instruments, which observed direct EPP-caused atmospheric effects, including Nimbus 4 (BUV), Nimbus 7 (SBUV), several NOAA platforms (SBUV/2), SME, UARS (HALOE, CLAES), SCISAT-1 (ACE-FTS), Odin (OSIRIS), Envisat-l (GOMOS, MIPAS, SCIAMACHY), and Aura (MLS). Measurements by rockets and ground-based radar also indicated EPP direct impacts. Atmospheric models have been used with some success in predicting the direct EPP impacts on the mesosphere and stratosphere. A review of the observed direct effects of EPP on the middle atmosphere will be given in this presentation.

Jackman, Charles H.↗

Shuttle Shortfalls and Lessons Learned for the Sustainment of Human Space Exploration

Much debate and national soul searching has taken place over the value of the Space Shuttle which first flew in 1981 and which is currently scheduled to be retired in 2010. Originally developed post-Saturn Apollo to emphasize affordability and safety, the reusable Space Shuttle instead came to be perceived as economically unsustainable and lacking the technology maturity to assure safe, routine access to low earth orbit (LEO). After the loss of two crews, aboard Challenger and Columbia, followed by the decision to retire the system in 2010, it is critical that this three decades worth of human space flight experience be well understood. Understanding of the past is imperative to further those goals for which the Space Shuttle was a stepping-stone in the advancement of knowledge. There was significant reduction in life cycle costs between the Saturn Apollo and the Space Shuttle. However, the advancement in life cycle cost reduction from Saturn Apollo to the Space Shuttle fell far short of its goal. This paper will explore the reasons for this shortfall. Shortfalls and lessons learned can be categorized as related to design factors, at the architecture, element and sub-system levels, as well as to programmatic factors, in terms of goals, requirements, management and organization. Additionally, no review of the Space Shuttle program and attempt to take away key lessons would be complete without a strategic review. That is, how do national space goals drive future space transportation development strategies? The lessons of the Space Shuttle are invaluable in all respects - technical, as in design, program-wise, as in organizational approach and goal setting, and strategically, within the context of the generational march toward an expanded human presence in space. Beyond lessons though (and the innumerable papers, anecdotes and opinions published on this topic) this paper traces tangible, achievable steps, derived from the Space Shuttle program experience, that must be a part of any 2l century initiatives furthering a growing human presence beyond earth.

Zapata, Edgar↗