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At least 451 records · Page 25

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DOE OSTI2023

Fluorescent aggregate structure revealed in bisphenol F epoxy thermoset

Bisphenol F (BPF) epoxy resin is a prepolymer component of thermosets used in construction of reinforced carbon fiber composites (RCFC). The fluorescence of this resin can provide information about chemical and structural alterations of the thermoset from thermal or mechanical damage. While some work has investigated the fluorescence spectra of bisphenol A epoxy resin, a structural analog of BPF, none have studied BPF. The purpose of this study is to investigate the baseline fluorescence spectra of the BPF epoxy resin for features that could be utilized for monitoring damage and structural alterations. Bisphenol F epoxy resin was found to have two emission peaks with a broad peak centered at 410 nm and a sharp peak centered at 550 nm. The broad emission peak was identified as the fluorescence from BPF epoxy monomer while the sharp emission peak was found to be from an aggregate structure present in the epoxy resin. It is hypothesized that this structure is an H-aggregate based on the emission features and structural stability of the aggregate compared to the alternative J-aggregate which was determined via density functional theory calculations. The H-aggregate was found to persist into one of the cured thermoset formulations evaluated but was lost when exposed to elevated temperatures below thermal degradation of the thermoset. This loss of aggregate structure was due to polymer network rearrangement. This new fluorescence signature can be used as an indicator of polymer network rearrangement from thermal exposure which may alter the expected material performance and precede thermal degradation.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Exploring the Role of Neutral 4-Amino-1,2,4-triazole in the Formation of Hexanuclear f-Element Hydrolysis Products

Our recent observations of an unexpected Ce(III) hydrolysis product from the reaction of 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz) with CeCl 3 ·7H 2 O, [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 2 (μ 3 -Cl) 2 (Cl) 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ]·7H 2 O, the first high-nuclearity lanthanide complex where all Ln atoms are connected pairwise through 12 N-donor ligands or 12 neutral bridging ligands of any type, prompted us to explore the utility of this ligand in trapping additional f-element examples. Reactions of LnCl 3 ·6H 2 O (Ln = Nd, Eu, Ho) with a large excess of 4-NH 2 -1,2,4-Triaz (20 equiv) and with the addition of small amounts of water to help solubilize the metal salts led to the isolation of the unique hydrolysis products [Nd 6 (μ 3 -OH) 8 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ][Cl 4 ]·2H 2 O, [Eu 6 (μ 6 -Cl) 0.23 (μ 3 -O 0.77 ) 4 (μ 3 -O) 2.6 (μ 3 -Cl) 0.4 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ], and [Ho 6 (μ 6 -Cl) 0.21 (μ 3 -O 0.79 ) 4 (μ 3 -OH) 2 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ][Cl] 3.4 . Here, we also report a Ce(III) analogue prepared in glassware contaminated with Pb(OAc) 2 , namely, [Ce 6 (μ 3 -OH) 8 (BrPbBr 5 )(μ 2 -4-NH 2 -1,2,4-Triaz) 11.5 (OH 2 ) 6 ][Pb 0.84 Br 4.2 ][Br] 3.8 ·2(4-NH 2 -1,2,4-Triaz)·3.6H 2 O. The Nd(III) complex is the structurally most ordered with a clear [Nd 6 (μ 3 -OH) 8 ] cluster core, while the Eu(III) and Ho(III) compounds contain partial occupancy of a μ 6 position and thus result in an incomplete Ln 6 O 9 cluster core formation. The crystallographic results suggest that the 4-NH 2 -1,2,4-Triaz ligand brings Ln(III) ions together, followed by the formation of an Ln 6 O 8 or Ln 6 O 9 core with whatever remaining anions or ligands can be incorporated. Given the complexity of the hydrolysis products of nuclear waste, we expect to continue to find a myriad of closely related complex structures of these types for the f-elements.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2022

Atomic isotropic hyperfine properties for first row elements (B–F) revisited

Benchmark quality isotropic hyperfine properties have been obtained for first row elements (B–F) using a systematic composite approach consisting of a sequence of core/valence correlation consistent basis sets, up through aug-cc-pCV8Z, along with configuration interaction and coupled cluster theory methods. The best nonrelativistic final values (in MHz) are 10.64 (B), 20.22 (C), 10.59 (N), –31.74 (O), and 318.30 (F) and are in very good agreement with available experimental values for these difficult-to-describe properties. Agreement is especially close in the case of N, which has the most accurate experimental value. The spin densities derived from the best composite level of theory were found to closely follow a simple quadratic scaling with the atomic number, Z. Finally, observed convergence rates in the 1-particle and n-particle expansions obtained here may be useful in judging likely accuracy that can be expected in studies of molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Inhibition mechanisms of AcrF9, AcrF8, and AcrF6 against type I-F CRISPR–Cas complex revealed by cryo-EM

Prokaryotes and viruses have fought a long battle against each other. Prokaryotes use CRISPR–Cas-mediated adaptive immunity, while conversely, viruses evolve multiple anti-CRISPR (Acr) proteins to defeat these CRISPR–Cas systems. The type I-F CRISPR–Cas system in Pseudomonas aeruginosa requires the crRNA-guided surveillance complex (Csy complex) to recognize the invading DNA. Although some Acr proteins against the Csy complex have been reported, other relevant Acr proteins still need studies to understand their mechanisms. As such, here, we obtain three structures of previously unresolved Acr proteins (AcrF9, AcrF8, and AcrF6) bound to the Csy complex using electron cryo-microscopy (cryo-EM), with resolution at 2.57 Å, 3.42 Å, and 3.15 Å, respectively. The 2.57-Å structure reveals fine details for each molecular component within the Csy complex as well as the direct and water-mediated interactions between proteins and CRISPR RNA (crRNA). Our structures also show unambiguously how these Acr proteins bind differently to the Csy complex. AcrF9 binds to key DNA-binding sites on the Csy spiral backbone. AcrF6 binds at the junction between Cas7.6f and Cas8f, which is critical for DNA duplex splitting. AcrF8 binds to a distinct position on the Csy spiral backbone and forms interactions with crRNA, which has not been seen in other Acr proteins against the Csy complex. Our structure-guided mutagenesis and biochemistry experiments further support the anti-CRISPR mechanisms of these Acr proteins. Our findings support the convergent consequence of inhibiting degradation of invading DNA by these Acr proteins, albeit with different modes of interactions with the type I-F CRISPR–Cas system.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Spin-parities of subthreshold resonances in the 18 F(p, α) 15 reaction

The 18 F(p,α) 15 O reaction is key to determining the 18 F abundance in classical novae. However, the cross section for this reaction has large uncertainties at low energies largely caused by interference effects. In this work, we resolve a longstanding issue with unknown spin-parities of subthreshold states in 19 Ne that reduces these uncertainties. The 20 Ne( 3 He, 4 He) 19 Ne neutron pick-up reaction was used to populate 19 Ne excited states, focusing on the energy region of astrophysical interest (≈ 6 – 7 MeV). The experiment was performed at the Triangle Universities Nuclear Laboratory using the high resolution Enge split-pole magnetic spectrograph. Spins and parities were found for states in the astrophysical energy range. In particular, the state at 6.133 MeV ($E^{cm}_{r}$ = –277 keV) was found to have spin and parity of 3/2 + and we confirm the existence of an unresolved doublet close to 6.288 MeV ($E^{cm}_{r}$ = –120 keV) with J π = 1/2 + and a high-spin state. Using these results, we demonstrate a significant factor of two decrease in the reaction rate uncertainties at nova temperatures.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2022

Sesame Equation of State for Kel F-800

I describe the construction of new equations of state for Kel F-800, as both linear and quadratic fits to shock data and Sesame 97200. This is the first SESAME table for Kel F-800 of which I’m aware. The SESAME table recovers shock data by construction and does reasonably well with thermal data, but differs with Brillouin scattering results for sound speed and density under static compression.

42 ENGINEERING↗

DOE OSTI2021

Nondetection of Helium in the Upper Atmospheres of TRAPPIST-1b, e, and f

We obtained high-resolution spectra of the ultracool M-dwarf TRAPPIST-1 during the transit of its planet “b” using two high-dispersion near-infrared spectrographs, the Infrared Doppler (IRD) instrument on the Subaru 8.2m telescope, and the Habitable Zone Planet Finder (HPF) instrument on the 10 m Hobby–Eberly Telescope. These spectroscopic observations are complemented by a photometric transit observation for planet “b” using the APO/ARCTIC, which assisted us in capturing the correct transit times for our transit spectroscopy. Using the data obtained by the new IRD and HPF observations, as well as the prior transit observations of planets “b,” “e” and “f” from IRD, we attempt to constrain the atmospheric escape of the planet using the He i triplet 10830 Å absorption line. We do not detect evidence for any primordial extended H-He atmospheres in all three planets. To limit any planet-related absorption, we place an upper limit on the equivalent widths of <7.754 mÅ for planet “b,” <10.458 mÅ for planet “e,” <4.143 mÅ for planet “f” at 95% confidence from the IRD data, and <3.467 mÅ for planet “b” at 95% confidence from HPF data. Using these limits along with a solar-like composition isothermal Parker wind model, we attempt to constrain the mass-loss rates for the three planets. For TRAPPIST-1b, our models exclude the highest possible energy-limited rate for a wind temperature <5000 K. This nondetection of extended atmospheres with low mean-molecular weights in all three planets aids in further constraining their atmospheric composition by steering the focus toward the search of high-molecular-weight species in their atmospheres.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1972

OGO-F-02 data analysis

The OGO-VI satellite, which was launched on June 5, 1969 carried a complement of twenty-six experiments. One of those instruments, the F-02 package, was a cylindrical Langmuir probe experiment whose primary purpose was to measure ionospheric electron temperatures and densities. This report briefly describes the F-02 experiment itself, outlines the computer programs developed to analyze the raw data, and gives a summary of the scientific information obtained, with the aid of this experiment.

Nagy, A. F.↗

NASA NTRS1973

Steady-state and dynamic pressure phenomena in the propulsion system of an F-111A airplane

Flight tests were conducted with two F-111A airplanes to study the effects of steady-state and dynamic pressure phenomena on the propulsion system. Analysis of over 100 engine compressor stalls revealed that the stalls were caused by high levels of instantaneous distortion. In 73 percent of these stalls, the instantaneous circumferential distortion parameter, k sub theta, exhibited a peak just prior to stall higher than any previous peak. The K sub theta parameter was a better indicator of stall than the distortion factor, k sub d, and the maximum-minus-minimum distortion parameter, d, was poor indicator of stall. Inlet duct resonance occurred in both F-111A airplanes and is believed to have been caused by oscillations of the normal shock wave from an internal to an external position. The inlet performance of the two airplanes was similar in terms of pressure recovery, distortion, and turbulence, and there was good agreement between flight and wind-tunnel data up to a Mach number of approximately 1.8.

Burcham, F. W.↗

NASA NTRS1972

The ATS-F/Nimbus-E tracking experiment.

The objective of the ATS-F/Nimbus-E tracking experiment, the first of its kind, is presented. Specifically, this experiment has a twofold purpose: first, to gain experience in the practical use of satellite-to-satellite range and range rate data for very accurate orbit determination (this was its original intent); and second, to evaluate the real usefulness of such a technique for geodetic studies despite the fact that the 1000-km Nimbus orbit is not ideally suited for such a purpose. The accuracies of the tracking systems of the satellite-to-satellite and satellite-to-ground link (ATS-F to the Rosman, N.C. ground station) will be about 0.035 cm/sec in range rate and about 1 m in range - utilizing a 10 sec integration time. With these values it is possible to obtain, based upon performed error analyses, orbit height errors of the order of 0.1 to 0.3 m for the near earth orbiting Nimbus spacecraft. This experiment will therefore hopefully prove to be a significant first step for future earth applications spacecraft carrying altimeters systems for measuring ocean height variations.

Von Bun, F. O.↗

NASA NTRS1973

Measurement of ion thruster exhaust characteristics and interaction with simulated ATS-F spacecraft

The ATS-F ion engine was mounted on a simulated spacecraft and was operated in a 22 by 35 foot vacuum chamber, using the same neutralizer control point as in earlier small chamber tests. The control point was in the middle of a range of 16 steps and, thus, the range should be adequate for transition to space flight. Measurement of the near- and far-field ions showed that the ion beam was well defined in a cone of 18-degrees half-angle. The material deposition experiment indicated that the ATS-F solar array would accumulate less than 0.2 A of aluminum per thousand hours of thruster operation, so that the corresponding power loss could be considered negligible. An interesting result was that the coupling between the beam and spacecraft was strong enough to require relatively large increases in the beam potential as the neutralizer bias was increased.

Worlock, R.↗

NASA NTRS1974

The ATS-F/Nimbus-F tracking and orbit determination experiment

The experiment described was conducted to demonstrate a procedure for tracking a near-earth satellite via a geostationary satellite without the aid of multiple ground station tracking. Another objective of the experiment was connected with the utilization of the broad tracking coverage provided by the geostationary satellite to obtain an improved geopotential solution. Questions of overall experiment implementation are discussed along with details regarding ground equipment, the ATS-F transponder, and the Nimbus-F transponder. Aspects of measurement evaluation are also examined, taking into account basic measurements, measurement interpretation, and approaches for orbit computation.

Schmid, P. E.↗

NASA NTRS1976

The F-12 series aircraft approach to design for control system reliability

The F-12 series aircraft control system design philosophy is reviewed as it pertains to functional reliability. The basic control system, i.e., cables, mixer, feel system, trim devices, and hydraulic systems are described and discussed. In addition, the implementation of the redundant stability augmentation system in the F-12 aircraft is described. Finally, the functional reliability record that has been achieved is presented.

Schenk, F. L.↗

NASA NTRS1976

Flight experience with a digital integrated propulsion control system on an F-111E airplane

A digital integrated propulsion control system (IPCS) installed in the left side of an F-111 E aircraft was tested in flight. The F-111 aircraft was selected for the IPCS program because it incorporated a variable geometry inlet and an afterburning turbofan engine and had two engines, one of which could remain in the normal configuration to ensure flight safety. Flight data were compared with results of tests run in an altitude test chamber. The digital system was found to be capable of duplicating the standard engine and inlet control systems. Instabilities such as inlet buzz and afterburner rumble were detected and controlled. The usefulness of an altitude chamber for developing a software and testing hardware was proven. The flexibility of IPCS was demonstrated when an autothrottle, an in-flight thrust calculation, and a coannular noise study capability were added at the end of the flight tests.

Burcham, F. W., Jr.↗

NASA NTRS1977

Semiclassical dynamics on multiple electronic surfaces - Three-dimensional treatment of reactive F + H2

The role of electron transitions in collisions is studied for the F + H2 reaction by combining quasi-classical Monte Carlo trajectories with a semiclassical decoupling approximation for the electron transitions. Attention is directed at the reaction of excited state F atoms reacting to form ground state products; the reactants are initiated in either of two spin-orbit states of the atom with the diatom in the ground vibrational state and the lowest four rotational states, at relative translational energies of 0.1, 0.2 and 0.3 eV. Even if the reactants are initiated on the excited state surface, the reactive cross sections (which are classically forbidden) are significant. The major dynamical effects of the excited state reaction are the flow of reactant electronic energy into product internal energy.

Komornicki, A.↗

NASA NTRS1979

Semiclassical study of reactive scattering in a laser field - F + H2 + barred-h times omega times /1.06 microns/ system

Semiclassical calculations of collinear F+H2(nu = 0) reactive and inelastic scattering in an Nd-glass laser field of various intensities are described. The decoupling approximation developed for the Miller-George theory is used for nonadiabatic transitions between the electronic-field surfaces, and special attention is paid to the choice of a proper coordinate system for applying the decoupling approximation. An increase in the total reaction probability and population ratio of the nu = 3 over nu = 2 vibrational state of HF occurs suddenly as the field intensity increases beyond 10 TW/sq cm. It is found that in a laser field the H2 molecule can be vibrationally excited while the F atom is electronically excited.

Yuan, J.-M.↗

NASA NTRS1979

A comparison of intense electrostatic waves near f-UHR with linear instability theory

Intense electrostatic waves near the upper hybrid resonance frequency (f-UHR) have recently been detected near but beyond the plasmapause between + or -50 deg magnetic latitude at all local times. The paper shows that the electrostatic waves observed with the ISEE 1 plasma wave receiver near f-UHR are in qualitative agreement with linear theory of multicyclotron harmonic emissions. The peak amplitudes and bandwidths observed are similar to those calculated for maximum spatial growth rates. Measurements on Hawkeye of similar waves suggest that the electric field polarization is also consistent with theory. For a wide range of plasma parameters, nonconvective instability or large spatial growth rates occur within the cyclotron band encompassing the cold upper hybrid frequency.

Kurth, W. S.↗

NASA NTRS1982

Flight evaluation of a digital electronic engine control system in an F-15 airplane

Benefits provided by a full-authority digital engine control are related to improvements in engine efficiency, performance, and operations. An additional benefit is the capability of detecting and accommodating failures in real time and providing engine-health diagnostics. The digital electronic engine control (DEEC), is a full-authority digital engine control developed for the F100-PW-100 turbofan engine. The DEEC has been flight tested on an F-15 aircraft. The flight tests had the objective to evaluate the DEEC hardware and software over the F-15 flight envelope. A description is presented of the results of the flight tests, which consisted of nonaugmented and augmented throttle transients, airstarts, and backup control operations. The aircraft, engine, DEEC system, and data acquisition and reduction system are discussed.

Myers, L. P.↗