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At least 829 records · Page 46

HJ-aggregates of donor–acceptor–donor oligomers and polymers

A vibronic exciton model is developed to account for the spectral signatures of HJ-aggregates of oligomers and polymers containing donor–acceptor–donor (DAD) repeat units. In (DAD) N π-stacks, J-aggregate-promoting intrachain interactions compete with H-aggregate promoting interchain interactions. The latter includes Coulombic coupling, which arises from “side-by-side” fragment transition dipole moments as well as intermolecular charge transfer (ICT), which is enhanced in geometries with substantial overlap between donors on one chain and acceptors on a neighboring chain. J-behavior is dominant in single (DAD)N chains with enhanced intrachain order as evidenced by an increased red-shift in the low-energy absorption band along with a heightened A 1 /A 2 peak ratio, where A 1 and A 2 are the oscillator strengths of the first two vibronic peaks in the progression sourced by the symmetric quinoidal–aromatic vibration. By contrast, the positive H-promoting interchain Coulomb interactions operative in aggregates cause the vibronic ratio to attenuate, similar to what has been established in H-aggregates of homopolymers such as P3HT. An attenuated A 1 /A 2 ratio can also be caused by H-promoting ICT which occurs when the electron and hole transfer integrals are out-of-phase. In this case, the A 1 peak is red-shifted, in contrast to conventional Kasha H-aggregates. With slight modifications, the ratio formula derived previously for P3HT aggregates is shown to apply to (DAD) N aggregates as well, allowing one to determine the effective free-exciton interchain coupling from the A 1 /A 2 ratio. Applications are made to polymers based on 2T-DPP-2T and 2T-BT-2T repeat units, where the importance of the admixture of the excited acceptor state in the lowest energy band is emphasized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contact Resistance of Carbon–Li x (Ni,Mn,Co)O 2 Interfaces

Abstract Electronic resistance in lithium‐ion battery positive electrodes is typically attributed to the bulk resistance of the active material and the network resistance of the carbon additive. Expected overpotentials from these bulk components are minimal relative to that from charge‐transfer resistance. However, literature reports show that cell overpotentials are often much more sensitive to conductive additives than the expected level from bulk or percolating‐network transport. This discrepancy motivated a detailed examination of the contact resistance between the active material and conductive additive. The contact and bulk resistances are simultaneously measured using dense bar samples of lithium‐layered oxides (Li x Ni 1 /3 Mn 1/3 Co 1/3 O 2 and Li x Ni 0.5 Mn 0.3 Co 0.2 O 2 ) in contact with carbon black. It is found that the contact resistance dominates the overall electronic resistance when the length scale is smaller than millimeters; after correcting for contact effects, bulk conductivity of layered oxides is determined to be orders‐of‐magnitude higher than previously reported. In porous electrodes, it is found from three‐electrode electrochemical impedance spectroscopy that the carbon content most heavily influences the low‐frequency regime (≈0.01 Hz), as opposed to the high frequency (>10 3 Hz) regime expected from electronic percolating properties. Constriction effects within the layered oxide are identified as the dominant mechanism for contact resistance and its implication is investigated for porous electrodes.

Kuo, Jimmy Jiahong↗

Improvement of a geodetic triangulation through control points established by means of satellite or precision traversing

Whether any significant increment to accuracy could be transferred from a super-control continental net (continental satellite net or super-transcontinental traverse) to the fundamental geodetic net (first-order triangulation) is discussed. This objective was accomplished by evaluating the positional accuracy improvement for a triangulation station, which is near the middle of the investigated geodetic triangulation net, by using various station constraints over its geodetic position. This investigation on a 1858 kilometer long triangulation chain shows that the super-control net can provide a useful constraint to the investigated geodetic triangulation net, and thus can improve it only when the accuracy of super-control net is at least 1 part in 500,000.

Saxena, N. K.↗

Electric propulsion - Past history and future prospects

Studies of feasibility and flight mechanics of electric propulsion systems began around 1946. Conceptual systems design started in 1954, experimental developments in 1958; flight tests in 1964 and 1970 proved the functioning of electric thrusters in space. Further development of ion thruster systems has concentrated on bombardment ionization in the U.S., and on radiofrequency, bombardment, and surface contact ionization in West Germany, Great Britain, France and Russia. Electrothermal, plasma, and colloid thruster development has been pursued in many contries. Electric thrusters were used successfully during past years for satellite attitude control, and for prime propulsion of the Russian spacecraft Yantar. Further applications for attitude and position control of satellites are planned. Studies are presently underway for solar electric missions to planets, planetary moons, comets, asteroids, and toward the sun, and also for missions in near-earth space involving transfer, servicing, and repair of orbiting spacecraft.

Stuhlinger, E.↗

Three-dimensional structure of Escherichia coli initiator tRNA/f//Met/

The crystal structure of Escherichia coli tRNA(f)(Met), an initiator transfer RNA, has been determined. While grossly similar to that of the chain-elongating yeast tRNA(Phe), there are three major differences. One involves the folding of the anticodon loop; in particular, the position of the constant uridine, U33. This difference was unexpected and may be of functional significance.

Woo, N. H.↗

SSSFD manipulator engineering using statistical experiment design techniques

The Satellite Servicer System Flight Demonstration (SSSFD) program is a series of Shuttle flights designed to verify major on-orbit satellite servicing capabilities, such as rendezvous and docking of free flyers, Orbital Replacement Unit (ORU) exchange, and fluid transfer. A major part of this system is the manipulator system that will perform the ORU exchange. The manipulator must possess adequate toolplate dexterity to maneuver a variety of EVA-type tools into position to interface with ORU fasteners, connectors, latches, and handles on the satellite, and to move workpieces and ORUs through 6 degree of freedom (dof) space from the Target Vehicle (TV) to the Support Module (SM) and back. Two cost efficient tools were combined to perform a study of robot manipulator design parameters. These tools are graphical computer simulations and Taguchi Design of Experiment methods. Using a graphics platform, an off-the-shelf robot simulation software package, and an experiment designed with Taguchi's approach, the sensitivities of various manipulator kinematic design parameters to performance characteristics are determined with minimal cost.

Barnes, John↗

A plan for spacecraft automated rendezvous

An automated rendezvous approach has been developed that utilizes advances in technology to reduce real-time/near real-time flight operations support personnel to an acceptable level that is near the minimum without jeopardizing the success of the mission. The on-board flight targeting uses a rule-based system to select the pursuit vehicle phasing orbits and uses precise navigation updates from the pursuit/target spacecraft made possible by the global positioning system receivers/processors on both spacecraft to adjust the phasing orbits and achieve rendezvous. The ascent-to-orbit targeting for the pursuit vehicle has been successfully decoupled from the on-orbit orbit transfer phasing targeting. Typical launch window data have been developed for the heavy lift launch vehicle and cargo transfer vehicle for a Space Station Freedom rendezvous mission.

Deaton, A. W.↗

Delay Banking for Managing Air Traffic

Delay banking has been invented to enhance air-traffic management in a way that would increase the degree of fairness in assigning arrival, departure, and en-route delays and trajectory deviations to aircraft impacted by congestion in the national airspace system. In delay banking, an aircraft operator (airline, military, general aviation, etc.) would be assigned a numerical credit when any of their flights are delayed because of an air-traffic flow restriction. The operator could subsequently bid against other operators competing for access to congested airspace to utilize part or all of its accumulated credit. Operators utilize credits to obtain higher priority for the same flight, or other flights operating at the same time, or later, in the same airspace, or elsewhere. Operators could also trade delay credits, according to market rules that would be determined by stakeholders in the national airspace system. Delay banking would be administered by an independent third party who would use delay banking automation to continually monitor flights, allocate delay credits, maintain accounts of delay credits for participating airlines, mediate bidding and the consumption of credits of winning bidders, analyze potential transfers of credits within and between operators, implement accepted transfers, and ensure fair treatment of all participating operators. A flow restriction can manifest itself in the form of a delay in assigned takeoff time, a reduction in assigned airspeed, a change in the position for the aircraft in a queue of all aircraft in a common stream of traffic (e.g., similar route), a change in the planned altitude profile for an aircraft, or change in the planned route for the aircraft. Flow restrictions are typically imposed to mitigate traffic congestion at an airport or in a region of airspace, particularly congestion due to inclement weather, or the unavailability of a runway or region of airspace. A delay credit would be allocated to an operator of a flight that has accepted, or upon which was imposed, a flow restriction. The amount of the credit would increase with the amount of delay caused by the flow restriction, the exact amount depending on which of several candidate formulas is eventually chosen. For example, according to one formula, there would be no credit for a delay smaller than some threshold value (e.g., 30 seconds) and the amount of the credit for a longer delay would be set at the amount of the delay minus the threshold value. Optionally, the value of a delay credit could be made to decay with time according to a suitable formula (e.g., an exponential decay). Also, optionally, a transaction charge could be assessed against the value of a delay credit that an operator used on a flight different from the one for which the delay originated or that was traded with a different operator. The delay credits accumulated by a given airline could be utilized in various ways. For example, an operator could enter a bid for priority handling in a new flow restriction that impacts one or more of the operator s flights; if the bid were unsuccessful, all or a portion of the credit would be returned to the bidder. If the bid pertained to a single aircraft that was in a queue, delay credits could be consumed in moving the aircraft to an earlier position within the queue. In the case of a flow restriction involving a choice of alternate routes, planned altitude profile, aircraft spacing, or other non-queue flow restrictions, delay credits could be used to bid for an alternative assignment.

Green, Steve↗

Performance Requirements for Emergency Responder Interoperable and Compatible Electronic Safety Equipment

Firefighters and other emergency response personnel are presented with an increasing array of technologies to improve their health and safety. This includes real-time bidirectional communication, navigation and positional information, data on physiological and metabolic functions, as well as data on their surrounding environment. The emerging challenge is to integrate these elements into a practical system, addressing such features as power, data transfer, and inter-element coordination and communication. In many respects, NASA has addressed these aspects in the context of Extra Vehicular Activity (EVA). The EVA environment shares many common attributes with that of emergency response scenarios. A similar situation exists in terms of the need for interoperability among the various system sub-elements. A brief overview is presented on the similarities and differences in these two applications, as well as the technical approach adopted by NASA in terms of system design philosophy.

Greenberg, Paul S.↗

Pathfinder Lander Rover Recharge System, and MARCO POLO Controls and ACME Regolith Feed System Controls and Integration

This project stems from the Exploration, Research, and Technology Directorate (UB) Projects Division, and one of their main initiatives is the "Journey to Mars". Landing on the surface of Mars which is millions of miles away is an incredibly large challenge. The terrain is covered in boulders, deep canyons, volcanic mountains, and spotted with sand dunes. The robotic lander is a kind of spacecraft with multiple purposes. One purpose is to be the protective shell for the Martian rover and absorb the impact from the landing forces; another purpose is to be a place where the rovers can come back to, actively communicate with, and recharge their batteries from. Rovers have been instrumental to the Journey to Mars initiative. They have been performing key research on the terrain of the red planet, trying to unlock the mysteries of the land for over a decade. The rovers that will need charging will not all have the same kind of internal battery either. RASSOR batteries may differ from the PbAC batteries inside Red Rover's chassis. NASA has invested heavily in the exploration of the surface of Mars. A driving force behind further exploration is the need for a more efficient operation of Martian rovers. One way is to reduce the weight as much as possible to reduce power consumption given the same mission parameters. In order to reduce the mass of the rovers, power generation, communication, and sample analysis systems currently onboard Martian rovers can be moved to a stationary lander deck. Positioning these systems from the rover to the Lander deck allows a taskforce of smaller, lighter rovers to perform the same tasks currently performed by or planned for larger rovers. A major task in transferring these systems to a stationary lander deck is ensuring that power can be transferred to the rovers.

Internship↗

Optimization of energy transfer in microwave electrothermal thrusters

Results are presented from preliminary tests conducted to evaluate the performance of a prototype microwave electrothermal thruster. The primary component of the device is a microwave resonant cavity. The device produces stable axial plasmas within a pressurized section of the cavity with the plasma positioned in the inlet region of the nozzle. Plasma stability is enhanced by axial power coupling, an optimal distribution of electric power density within the cavity, and a propellant gas flow which has a large vortical velocity component. The thruster has been operated with a number of propellant gases: helium, nitrogen, ammonia, and hydrogen. Plasmas can be formed in a reliable manner at cavity pressures of 1 kPa and incident power levels ranging from 50 W to 350 W, depending on the gas used, and can be operated at pressures up to 300 kPa at power levels up to 2200 W. Ideal performance results of vacuum Isp and thermal efficiency vs. specific power are presented for each gas. Representative results of this preliminary work are: He - Isp = 625 s, eta-thermal = 90 percent; N2 - Isp = 270 s, eta-thermal = 41 percent; NH3 - Isp = 475 s, eta-thermal= 55 percent; H2 - Isp = 1040 s, eta-thermal = 53 percent.

Sullivan, D. J.↗

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Determination and characterization of the Hubble Space Telescope pointing stability

The Hubble Space Telescope (HST) was designed to maintian a pointing stability (jitter) of 0.007 arc seconds rms throughout every observing period, which can last from a few seconds to several orbits. On-orbit measurements indicate that the hardware excitation induced by the reaction wheels. gyros, high gain antennae, science instrument mechanisms and tape recorders are well within specifications. Unexpectedly, the solar arrays because the dominant source of jitter. Every passage through an orbital terminator produces vibrations which emanate from the solar arrays due to thermal effects, which affect the relative positional stability. Broadband frequencies centered about 0.11 and 0.65 Hz were detected in the frequency content of the vehicle jitter. On-board modifications to the control law have attenuated the disturbance torques and reduced the vehicle jitter close to specification. Replacement of the solar arrays in December, 1993, should eliminate the torque distubances. Astrometric science observations are extremely susceptible to corruption from vehicle jitter. The removal of vehicle jitter from astrometric Transfer function scans of binary stars is explained in detail. A binary star separation of 16 milli-seconds of arc has been achieved, a separation resolution of 10 to 12 milli-seconds of arc appears feasible, with a binary star magnitude of 9 m(sub V). The achievement of this resolution is in part due to vehicle jitter removal. Comparison of vehicle jitter measurements from the position path of the vehicle control law, or from the guiding Fine Guidance Sensors (FGS), are shown to be equivalent to approximately 0.001 arc second.

Bradley, A. J.↗

The Dark Energy Spectrographic Instrument (DESI) Optical Fiber System

The specific research of the DESI project is to study in detail the expansion history of the Universe over the past 10 billion years. In order to do this, the project designed, fabricated, tested and commissioned the DESI instrument which has been deployed at the Mayall Telescope at the Kitt Peak National Observatory near Tucson, Arizona. The DESI project was conducted by approximately 30 US and foreign national laboratories. The complete instrument includes a prime focus corrector assembly, a focal plane with 5,000 optical fibers whose position can be set by robotic positioners, and ten spectrographs. Each spectrograph can accommodate the light from 500 fibers and include three color channels that are illuminated by a common collimator mirror and other planar transfer optics. In order for this entire system to work, optical fibers are required to connect each positioner to the spectrographs. Our CRADA with Durham University in the UK provided the 10 crucial fiber cables required to connect the DESI focal plane to the 10 spectrographs. The key major goals of this CRADA were achieved. Survey planning was another key component to the Durham contribution. Drs. Frenk, Baugh, Cole, Edge, Lacey, Li, Lucey, Massey, Metcalfe, Norberg and Shanks were all important contributors to the working groups to which they were assigned. Their work to implement emission lines and QSO in lightcone mocks, mocks for non-standard cosmologies/modified gravity, optimization of completeness of BGS in crowded regions and extended source photometry have been vital in the early planning for targets during commissioning. The major role in the project involved Dr. Ray Sharples and his team. They provided a significant portion of the design, fabrication and testing of the optical fiber system. In particular, they were responsible for the design, production of engineering drawings, component procurements, and fabrication of the 10 DESI Science fiber cables. Working in close collaboration with Dr. Claire Poppett, they also designed and fabricated the slit assemblies, the specialized termination of the groups of 500 fibers which plug into the spectrographs.

47 OTHER INSTRUMENTATION↗

Determination of Scale Bar for AGHCF Metallography Data

The DOE Nuclear Energy Advanced Reactor Technologies (ART) Fast Reactor Program (FRP) has supported the development of several databases containing information on the safety performance of fast reactors, components, and fuels. This growing collection of legacy experimental data, operating data, and analysis is available online to registered users. Metallography data represents one of the most critical types of post-irradiation examination (PIE) data being collected, organized, and archived in several ART Fast Reactor Databases (https://frdb.ne.anl.gov), including the Metallic Fuels Irradiation & Physics Database (FIPD), Out-of-Pile Transient Database (OPTD), and TREAT (the Transient Reactor Test Facility) Experimental Relational Database (TREXR). These databases contain three principal sets of metallography data. The first set comprises metallography data from Experimental Breeder Reactor-II (EBR-II) and Fast Flux Test Facility (FFTF) irradiated fuel pins examined in the Hot Fuel Examination Facility (HFEF). The second set consists of metallography data from EBR-II irradiated fuel pins examined in the Alpha-Gamma Hot Cell Facility (AGHCF). The third set includes metallography data from transient-tested fuel pins (including both out-of-pile furnace tests and TREAT tests) examined in AGHCF. Since both the second and third sets were generated in AGHCF, they are governed by identical specifications. The metallography data in the databases consist of digital images scanned from either positive or negative photographic films. To analyze the microstructure of a fuel pin, a series of preparatory steps are required, including sectioning, epoxy mounting, mechanical grinding and polishing, and etching. Following sample preparation, specimens are transferred for metallographic examination. The AGHCF and HFEF metallography data were generated using optical microscopes manufactured by Leitz and Bausch and Lomb (B&L). Images were recorded on Polaroid film at preset magnifications. Magnification verification for the Leitz and B&L metallographs was conducted every two months prior to 1989 and at least every six months from 1989 through the conclusion of the IFR program. Magnifications determined from imaging of microslide standards were compared to the instrument settings for magnifications ranging from 50× to 500×. If the magnifications determined from standards deviated from the instrument settings, adjustments were made to the bellows extension until agreement was achieved. The specifications for AGHCF and HFEF legacy metallography data have been established based on available hard-copy and digital records, most of which have been incorporated into the data repositories associated with FIPD, OPTD, and TREXR. Detailed specifications including hard-copy records, digitized records, cutting diagrams and sectioning schemes, high-magnification photographs, photomosaics (composites), information tags, scale bars, and magnification verification procedures can be found in a separate report.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Apparatus for remote handling of materials

Apparatus for remote handling of materials are described. A closed housing is provided with first and second containers and first and second reservoirs for holding materials to be mixed. The materials are transferable from the reservoirs to the first container where they are mixed. The mixed materials are then conveyed from the first container to the second container preferably by dumping the mixed materials into a funnel positioned over the second container. The second container is then moved to a second position for analysis of the mixed materials. For example, the materials may be ignited and the flame analyzed. Access, such as a sight port, is provided in the housing at the analysis position. The device provides a simple and inexpensive apparatus for safely mixing a pyrophoric material and an oxidizer which together form a thermite type mixture that burns to produce a large quantity of heat and light.

Kimball, R. B.↗

Development of the Equatorial Infrared Catalogue from satellite data

More than 40,000 infrared measurements of stellar sources have been obtained since November, 1976 during the ongoing process of compiling an Equatorial Infrared Catalogue. Because of the problem of eliminating spurious sources, which has affected earlier space surveys, an extensive effort is being made to verify the sources by means of (1) repetitive observations by satellite sensors, (2) cross correlation with a large data base developed from ground-based and space surveys at other wavelengths, and (3) investigation of a significant subset of the sources with a ground-based infrared telescope. As sources are verified, they are transferred from a working list to a screened preliminary version of the catalogue. The catalogue comprises the only survey of a significant area of the sky that has been accomplished (or is presently planned) with positional accuracies of a few arc seconds at a wavelength of not less than 2 microns.

Heinsheimer, T. F.↗

The use of differential pressure feedback in an automatic flight control system

A feasibility study has been performed to evaluate the performance of a system whereby a control surface is positioned with differential pressure as the feedback variable. Analogous to a position command system, the control surface is commanded to move until a certain differential pressure is achieved at a given point on the surface. Frequency response tests and theoretical considerations indicate that the pressure feedback transfer function is first order, with a break frequency up to 50 rad/sec. There exist applications to the outer loops of flight control systems as well. Stability augmentation, gust alleviation, and stall prevention appear to be possible by feeding back differential pressure across lifting and control surfaces.

Levy, D. W.↗