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At least 1,621 records · Page 90

Resonance stabilization effects on ketone autoxidation: Isomer-specific cyclic ether and ketohydroperoxide formation in the low-temperature (400–625 K) oxidation of diethyl ketone

Here, the pulsed photolytic chlorine-initiated oxidation of diethyl ketone [DEK; (CH 3 CH 2 ) 2 C=O], 2,2,4,4- d 4 -DEK [ d 4 -DEK; (CH 3 CD 2 ) 2 C=O], and 1,1,1,5,5,5-d 6 -DEK [ d 6 -DEK; (CD 3 CH 2 ) 2 C=O] is studied at 8 torr and 1–2 atm and from 400–625 K. Cl atoms produced by laser photolysis react with diethyl ketone to form either primary (3-pentan-on-1-yl, R P ) or secondary (3-pentan-on-2-yl, R S ) radicals, which in turn react with O 2 . Multiplexed time-of-flight mass spectrometry, coupled to either a hydrogen discharge lamp or tunable synchrotron photoionizing radiation, is used to detect products as a function of mass, time, and photon energy. At 8 torr, the nature of the chain propagating cyclic ether + OH channel changes as a function of temperature. At 450 K, the production of OH is mainly in conjunction with formation of 2,4-dimethyloxetan-3-one, resulting from reaction of the resonance-stabilized secondary R S with O 2 . In contrast, at 550 K and 8 torr, 2-methyl-tetrahydrofuran-3-one, originating from oxidation of the primary radical (RP), is observed as the dominant cyclic ether product. Formation of both of these cyclic ether production channels proceeds via a resonance-stabilized hydroperoxy alkyl (QOOH) intermediate. Little or no ketohydroperoxide (KHP) is observed under the low-pressure conditions. At higher O 2 concentrations and higher pressures (1–2 atm), a strong KHP signal appears as the temperature is increased above 450 K. Definitive isomeric identification from measurements on the deuterated DEK isotopologues indicates the favored pathway produces a γ-KHP via resonance-stabilized alkyl, QOOH, and HOOPOOH radicals. Time-resolved measurements reveal the KHP formation becomes faster and signal more intense upon increasing temperature from 450 to 575 K before intensity drops significantly at 625 K. The KHP time profile also shows a peak followed by a gradual depletion for the extent of experiment. Several tertiary products exhibit a slow accumulation in coincidence with the observed KHP decay. These products can be associated with decomposition of KHP by β-scission pathways or via isomerization of a γ-KHP into a cyclic peroxide intermediate (Korcek mechanism). The oxidation of d 4 -DEK, where kinetic isotope effects disfavor γ-KHP formation, shows greatly reduced KHP formation and associated signatures from KHP decomposition products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determining hexavalent chromium transport properties in alkaline nuclear waste using nuclear magnetic resonance spectroscopy

This study focuses on the transport properties of hexavalent chromium, specifically the chromate anion, to improve predictive models and environmental remediation strategies for Cr(VI) migration. Using 53 Cr Nuclear Magnetic Resonance (NMR) spectroscopy, the research quantifies chromate in multicomponent electrolytes replicating nuclear waste conditions at the Hanford Site in Washington State. The consistency of the 53 Cr NMR signal integral with chromate concentration, despite varying matrix compositions, establishes it as a reliable concentration indicator. The transport properties of chromate in an alkaline solution were assessed using relaxation-based measurements via saturation recovery and Carr-Purcell-Meiboom-Gill experiments, determining spin-lattice and spin-spin relaxation times. These measurements, combined with the Bloembergen-Purcell-Pound equation, helped estimate the rotational correlation time and the 53 Cr self-diffusion coefficient using Stokes-Einstein-Debye and Stokes-Einstein equations. Direct measurements were obtained through pulsed field gradient stimulated echo 53 Cr NMR spectroscopy. Monte Carlo simulations further estimated uncertainty propagation. The results enhance comprehension of chromate transport and highlight prospects for identifying transport properties of NMR-active nuclei, traditionally considered unreachable.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ultrafast Annealing Improves SNR and Long-Term Stability of a Highly Multiplexed Line-by-Line FBG Array Inscribed by Femtosecond Laser in a Coreless Fiber for Extreme-Temperature Applications

This study reports the fabrication of a fourth-order line-by-line fiber Bragg grating (FBG) array using femtosecond laser inscription within a highly multimode coreless optical fiber, with a particular focus on achieving substantial multiplexing capabilities. An ultrafast annealing procedure is employed, resulting in an impressive enhancement of the FBG sensor’s fringe visibility by approximately 13 dB, signifying a notable improvement of approximately ~4 dB. This substantial enhancement contributes to the long-term stability and performance of the multiplexed FBG array in extreme-temperature conditions. The systematic fabrication approach employed for the multiplexed FBG array guarantees a high signal-to-noise ratio (SNR) for each individual FBG within the array. This FBG array is intended for extreme-temperature applications, addressing limitations associated with traditional FBGs based on doped optical fibers, including SNR degradation and temperature-induced fringe drift. Testing at temperatures up to 1120 °C demonstrates the FBG array’s stability without fluctuations in readings. Furthermore, it endures seven heat cycles, spanning from 500 °C to 1120 °C, over 60 h, exhibiting outstanding thermal stability. Furthermore, this highly multiplexed FBG array with an ultrafast annealing approach holds promise for extreme-temperature environments, such as steelmaking, where precise and reliable distributed temperature monitoring is imperative.

47 OTHER INSTRUMENTATION↗

Standoff Detection of Oil and Powder Mixtures at 12 Meters Using a Tunable Quantum Cascade Laser-Based System with a Close Focus Telescope and Uncooled Infrared Detector

We have designed and demonstrated a quantum cascade laser (QCL) based standoff system that utilizes an uncooled mercury cadmium telluride (MCT) detector with lock-in signal processing for chemical identification at a distance of 12.5 meters in indoor ambient light conditions. In the system, a tunable quad-QCL operating (1 MHz) in quasi-continuous wave mode between 8.45 and 10.03 μm (~1182 to 1000 cm –1 ) serves as the active mid-infrared source for remotely interrogating mineral, powder, and thin film oil samples including powder mixtures (6, 12.5, 25, and 50%) of crystalline quartz (SiO 2 ) in KBr. Light as reflected from a given sample is collected using a 10-inch (25.4 cm) Dall Kirkham telescope and coupled with ZnSe optics to an uncooled MCT detector. Furthermore, the mixture dependence of the highly transparent KBr and strongly absorbing quartz was found to fit a modified version of the Schatz reflectance model for compacted powder mixtures. All reflectance spectra reported are relative to an Au-coated diffuse reflector. A NIST traceable polystyrene standard reflector was also used to determine the QCL wavelength tuning range and calibration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Testing of Performance of Optical Fibers Under Irradiation in Intense Radiation Fields, When Subjected to Very High Temperatures

The primary objective of this project is to measure and model the performance of optical fibers in intense radiation fields when subjected to very high temperatures. This research will pave the way for fiber optic and optically based sensors under conditions expected in future high-temperature gas-cooled reactors. Sensor life and signal-to-noise ratios are susceptible to attenuation of the light signal due to scattering and absorbance in the fibers. This project will provide an experimental and theoretical study of the darkening of optical fibers in high-radiation and high-temperature environments. Although optical fibers have been studied for moderate radiation fluence and flux levels, the results of irradiation at very high temperatures have not been published for extended in-core exposures. Several previous multi-scale modeling efforts have studied irradiation effects on the mechanical properties of materials. However, model-based prediction of irradiation-induced changes in silica's optical transport properties has only recently started to receive attention due to possible applications as optical transmission components in fusion reactors. Nearly all damage-modeling studies have been performed in the molecular-dynamics domain, limited to very short times and small systems. Extended-time modeling, however, is crucial to predicting the long-term effects of irradiation at high temperatures, since the experimental testing may not encompass the displacement rate that the fibers will encounter if they are deployed in the VHTR. The project team will pursue such extended-time modeling, including the effects of the ambient and recrystallization. The process will be based on kinetic MC modeling using the concept of amorphous material consisting of building blocks of defect-pairs or clusters, which has been successfully applied to kinetic modeling in amorphized and recrystallized silicon. Using this procedure, the team will model compensation for rate effects, and the interplay of rate effects with the effects of annealing, to accurately predict the fibers' reliability and expected lifetime

36 MATERIALS SCIENCE↗

Application of Advanced Wide Area Early Warning Systems with Adaptive Protection

Recent blackouts of power systems in North America and throughout the world have shown how critical a reliable power system is to modern societies, and the enormous economic and societal damage a blackout can cause. It has been noted that unanticipated operation of protection systems can contribute to cascading phenomena and, ultimately, blackouts. This project developed and field-tested two methods of Adaptive Protection systems utilizing synchrophasor data. One method detects conditions of system stress that can lead to unintended relay operation, and initiates a supervisory signal to modify relay response in real time to avoid false trips. The second method detects the possibility of false trips of impedance relays as stable system swings “encroach” on the relays’ impedance zones, and produces an early warning so that relay engineers can re-evaluate relay settings. In addition, real-time synchrophasor data produced by this project was used to develop advanced visualization techniques for display of synchrophasor data to utility operators and engineers.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Power Solitons in Inverter-based Electric Energy Systems: Observation, Analysis and Implications

The discovery of an unfamiliar class of nonlinear energy waves in electric energy systems with dominating coupled inverter-based energy resources has been reported in a recent research project. Whenever there are slight but persistent differences among the reference signals used by inverters in pulse-width modulation, i.e., a weak group modulation instability condition, the unfamiliar energy waves appear, which contain not only the familiar frequency components present in electric power systems but also self-organized components in the ultra-high frequency region of the energy spectrum. These components are found to be exploding solitary waves with concentrated energy masses, hence we call them power solitons. This paper explains the work of the discovery reported, and the implications of the presence of power solitons for grid integration of inverter-based resources and power system protection.

14 SOLAR ENERGY↗

Diagnostics of low-temperature structural stability

The failure of materials at low temperatures is studied. The acoustic signals emitted in the extension of steel 45 at low temperature are analyzed. In this conditions, the yield point and strength increase, while the relative elongation declines.

42 ENGINEERING↗

Analog device simulates physiological waveforms

An analog physiological simulator generates representative waveforms for a wide range of physiological conditions. Direct comparison of these waveforms with those from telemetric inputs permits quick detection of signal parameter degradation.

Hickman, D. M.↗

Investigation of factors affecting the heater wire method of calibrating fine wire thermocouples

An analytical investigation was made of a transient method of calibrating fine wire thermocouples. The system consisted of a 10 mil diameter standard thermocouple (Pt, Pt-13% Rh) and an 0.8 mil diameter chromel-alumel thermocouple attached to a 20 mil diameter electrically heated platinum wire. The calibration procedure consisted of electrically heating the wire to approximately 2500 F within about a seven-second period in an environment approximating atmospheric conditions at 120,000 feet. Rapid periodic readout of the standard and fine wire thermocouple signals permitted a comparison of the two temperature indications. An analysis was performed which indicated that the temperature distortion at the heater wire produced by the thermocouple junctions appears to be of negligible magnitude. Consequently, the calibration technique appears to be basically sound, although several practical changes which appear desirable are presented and discussed. Additional investigation is warranted to evaluate radiation effects and transient response characteristics.

Keshock, E. G.↗

Dynamic response of Mach 2.5 axisymmetric inlet with 40 percent supersonic internal area contraction

Results of experimental tests conducted on a supersonic, mixed compression, axisymmetric inlet are presented. The inlet is designed for operation at Mach 2.5 with a turbofan engine (TF-30). The inlet was terminated with either a choked-orifice plate or a long pipe with variable area choked exit plug. Frequency responses were obtained for selected static pressures in the diffuser. These pressures were selected as potential control signals for terminal shock control. Frequency responses were obtained for the Mach 2 and 2.5 conditions for different terminations. Responses also were obtained with and without cowl bleed. Internal disturbances were produced by sinusoidally varying the inlet overboard bypass doors at frequencies out to 100 hertz.

Baumbick, R. J.↗

System design of a rudder coordination system

The application of the parameter optimization computer program to the design of a rudder coordination system for the F-8 airplane is summarized. The flight condition was Mach 0.56 at 20,000 feet altitude. The system configuration selected consisted of signal paths that fed yaw rate and aileron signals to the rudder. The two signal paths were summed and then modified by a high pass filter to eliminate any steady state bias signal. The input axis of the yaw gyro was perpendicular to the aircraft zero lift line and the trim angle of attack was 7.75 degrees. The parameter optimization was used to design the complete system first, and then a root locus analysis of the individual component effects was made. The results are presented.

Whitaker, H. P.↗

A monolithic SAW-charge transfer device

Surface acoustic waves excited in a Si-SiO2-ZnO layered structure can produce a traveling electric field in the silicon substrate. Charges stored in the traveling potential wells can be transferred at high speed and density and with less complexity. The monolithic structure under investigation for the SAW-charge transfer device consists of a silicon substrate, a thin silicon dioxide insulating layer on top of which a ZnO piezoelectric film is deposited by sputtering. The surface acoustic waves are excited by interdigital transducers. The signal charge is injected into traveling potential wells that travel with the velocity of sound. Conditions for the transfer of the charges by the traveling wells are analyzed. A surface acoustic wave program was used to determine the optimum structure dimensions and transducer configuration which will produce the highest coupling in the excitation of the piezoelectric waves.

Papanicolaou, N. A.↗

Drift mirror mode waves in the distant (about 200 earth radii) magnetosheath

The physical mechanisms which produced large magnetic field magnitude changes beyond 60 earth radii during ISEE-3 passage are discussed in relation to interplanetary conditions. The ISEE-3 data were taken close to the time that IMP-8 data signaled an interplanetary shock and the crossing of the terrestrial magnetosheath. The ISEE detected decreases (10-50 percent) in field magnitude that the IMP did not. The electron temperature and density and magnetic field data made by the ISEE indicated the presence of drift mirror mode waves. The instabilities would have been triggered in the magnetosheath plasma by arrival of the driver gas of the solar wind detected by the IMP-8. The waves were especially prominent due to the relative quiescence of the usually turbulent magnetosheath when the shock arrived.

Tsurutani, B. T.↗

Observations of OH in comet Levy with the Nancay radio telescope

Due to extremely favorable excitation conditions, comet Levy (1990c) exhibited in August-September 1990 the strongest OH 18-cm signal ever recorded in a comet at the Nancay radio telescope. This unique opportunity was used to measure the OH satellite lines at 1612 and 1721 MHz, to perform extensive mapping of the OH radio emission and to make a sensitive evaluation of the cometary magnetic field, of the H2O outflow velocity and of the OH production rate.

Bockelee-Morvan, Dominique↗

Parameter trade-offs for imaging spectroscopy systems

With the advent of the EOS era and of configurable sensors, users of these instruments are faced with the twin problems of specifying data acquisition parameters and extracting desired information from the voluminous data. An application of a system model is made to explore system parameter trade-offs for a model sensor based on the High Resolution Imaging Spectrometer. Radiometric performance was studied, along with the effect on classification accuracy of several system parameters. Using a model scene based on typical agricultural reflectance and atmospheric conditions, the atmosphere and sensor are seen to have significant effects on the mean received signal and noise performance. The effect of random uncorrelated errors in the radiometric calibration of the detector array is seen to degrade system performance, especially in the spectral bands below 1 micron. Accurate pixel-to-pixel relative radiometric calibration and the use of the Image Motion Compensation option are seen to improve classification accuracy, especially at high solar zenith angles. Feature sets chosen from characteristics of the scene performed best overall, but ones chosen based on signal-to-noise ratios were seen to be more robust.

Kerekes, John P.↗

Providing hydrogen maser timing stability to orbiting VLBI radio telescope observations by post-measurement compensation of linked frequency standard imperfections

Orbiting VLBI (OVLBI) astronomical observations are based upon measurements acquired simultaneously from ground-based and earth-orbiting radio telescopes. By the mid-1990s, two orbiting VLBI observatories, Russia's Radioastron and Japan's VSOP, will augment the worldwide VLBI network, providing baselines to earth radio telescopes as large as 80,000 km. The challenge for OVLBI is to effectuate space to ground radio telescope data cross-correlation (the observation) to a level of integrity currently achieved between ground radio telescopes. VLBI radio telescopes require ultrastable frequency and timing references in order that long term observations may be made without serious cross-correlation loss due to frequency source drift and phase noise. For this reason, such instruments make use of hydrogen maser frequency standards. Unfortunately, space-qualified hydrogen maser oscillators are currently not available for use on OVLBI satellites. Thus, the necessary long-term stability needed by the orbiting radio telescope may only be obtained by microwave uplinking a ground-based hydrogen maser derived frequency to the satellite. Although the idea of uplinking the frequency standard intrinsically seems simple, there are many 'contaminations' which degrade both the long and short term stability of the transmitted reference. Factors which corrupt frequency and timing accuracy include additive radio and electronic circuit thermal noise, slow or systematic phase migration due to changes of electronic circuit temporal operating conditions (especially temperature), ionosphere and troposphere induced scintillations, residual Doppler-incited components, and microwave signal multipath propagation. What is important, though, is to realize that ultimate stability does not have to be achieved in real-time. Instead, information needed to produce a high degree of coherence in the subsequent cross-correlation operation may be derived from a two-way coherent radio link, recorded and later introduced as compensations adjunct to the VLBI correlation process. Accordingly, this paper examines the technique for stable frequency/time transfer within the OVLBI system, together with a critique of the types of link degradation components which must be compensated, and the figures of merit known as coherence factors.

Springett, James C.↗

Unsteady Flow Field in a Multistage Axial Flow Compressor

The flow field in a multistage compressor is three-dimensional, unsteady, and turbulent with substantial viscous effects. Some of the specific phenomena that has eluded designers include the effects of rotor-stator and rotor-rotor interactions and the physics of mixing of velocity, pressure, temperature and velocity fields. An attempt was made, to resolve experimentally, the unsteady pressure and temperature fields downstream of the second stator of a multistage axial flow compressor which will provide information on rotor-stator interaction effects and the nature of the unsteadiness in an embedded stator of a three stage axial flow compressor. Detailed area traverse measurements using pneumatic five hole probe, thermocouple probe, semi-conductor total pressure probe (Kulite) and an aspirating probe downstream of the second stator were conducted at the peak efficiency operating condition. The unsteady data was then reduced through an ensemble averaging technique which splits the signal into deterministic and unresolved components. Auto and cross correlation techniques were used to correlate the deterministic total temperature and velocity components (acquired using a slanted hot-film probe at the same measurement locations) and the gradients, distributions and relative weights of each of the terms of the average passage equation were then determined. Based on these measurements it was observed that the stator wakes, hub leakage flow region, casing endwall suction surface corner region, and the casing endwall region away from the blade surfaces were the regions of highest losses in total pressure, lowest efficiency and highest levels of unresolved unsteadiness. The deterministic unsteadiness was found to be high in the hub and casing endwall regions as well as on the pressure side of the stator wake. The spectral distribution of hot-wire and kulite voltages shows that at least eight harmonics of all three rotor blade passing frequencies are present at this measurement location. In addition to the basic three rotor blade passing frequencies (R1, R2 and R3) and their harmonics, various difference frequencies such as (2R1 -R2) and (2R3-R2) and their harmonics are also observed. These difference frequencies are due to viscous and potential interactions between rotors 1, 2 and 3 which are sensed by both the total pressure and aspirating probes at this location. Significant changes occur to the stator exit flow features with passage of the rotor upstream of the stator. Because of higher convection speeds of the rotor wake on the suction surface of the downstream stator than on the pressure side, the chopped rotor wake was found to be arriving at different times on either side of the stator wake. As the rotor passes across the stator.

Suryavamshi, N.↗