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At least 1,135 records · Page 63

Alkali Metal Cation Effects for Rapid C–H Activation by Iron(0) Complexes

C–H oxidative addition is a key reaction in organometallic catalysis, motivating efforts to accelerate it. Here, we examine an anionic beta-diketiminate-supported iron(0) species that was previously observed to activate C-H bonds with Na(15-crown-5), but not with K(18-crown-6) or Rb(18-crown-6). Though crown ethers are usually seen as beneficial due to their ability to solubilize alkali metal cations, we observe that removing the crown ether leads to rapid and complete oxidative addition of the C-H bond even by K, Rb, and Cs. The products are iron(II) phenyl hydride complexes that exist as dimers bridged by the alkali metals. Neutron crystallography of the cesium complex verifies the presence and location of the bridging hydrides. It is likely that the crown-free alkali metal cations have greater Lewis acidity that enables them to facilitate oxidative addition of the C-H bond. This system gives insight on how to control the rate and favorability of C-H activation through manipulation of the countercation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-State Transformation of an Additive Manufactured Inconel 625 Alloy at 700 °C

Inconel 625, a nickel-based superalloy, has drawn much attention in the emerging field of additive manufacturing (AM) because of its excellent weldability and resistance to hot cracking. The extreme processing condition of AM often introduces enormous residual stress (hundreds of MPa to GPa) in the as-fabricated parts, which requires stress-relief heat treatment to remove or reduce the internal stresses. Typical residual stress heat treatment for AM Inconel 625, conducted at 800 °C or 870 °C, introduces a substantial precipitation of the δ phase, a deleterious intermetallic phase. In this work, we used synchrotron-based in situ scattering and diffraction methods and ex situ electron microscopy to investigate the solid-state transformation of an AM Inconel 625 at 700 °C. Our results show that while the δ phase still precipitates from the matrix at this temperature, its precipitation rate and size at a given time are both smaller when compared with their counterparts during typical heat treatment temperatures of 800 °C and 870 °C. A comparison with thermodynamic modeling predictions elucidates these experimental findings. Our work provides the rigorous microstructural kinetics data required to explore the feasibility of a promising lower-temperature stress-relief heat treatment for AM Inconel 625. The combined methodology is readily extendable to investigate the solid-state transformation of other AM alloys.

36 MATERIALS SCIENCE↗

Nanosecond Breakdown Characteristics of C 4 F 7 N and Various Mixtures at Pressures Above 1 Atmosphere in Comparison with SF 6

This report evaluates the pulsed breakdown performance of C 4 F 7 N under a 6.8 kV/ns voltage excitation. The pulsed dielectric strength of C 4 F 7 N is compared to SF 6 in the same experimental setup, and it is found that C 4 F 7 N concentrations of 50% or greater are required to achieve a dielectric strength greater than or equal to SF 6 . Pure C 4 F 7 N demonstrated higher electric field hold-off for longer time periods and less statistical variance under pulsed conditions when compared to SF 6 . Mixtures of 50%C 4 F 7 N with N 2 or CO 2 as buffer gases showed no appreciable difference in pulsed dielectric strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Pentavalent HIV-1 Subtype C Vaccine Containing Computationally Selected gp120 Strains Improves the Breadth of V1V2 Region Responses

Background: HIV-1 envelope (Env) variable loops 1 and 2 (V1V2) directed non-neutralizing antibodies were a correlate of decreased transmission risk in the RV144 vaccine trial. Thus, the elicitation and breadth of antibody responses against the V1V2 of HIV-1 Env are important considerations for HIV-1 vaccine candidates. The V1V2 region’s highly variable nature and the extensive diversity of subtype C HIV-1 Envelopes (Envs) make the V1V2 response breadth a high priority for HIV-1 vaccine regimens aiming for V1V2-mediated protection in Southern Africa. Here, we determined whether the breadth of the anti-V1V2 vaccine response can be broadened by including HIV-1 Env strains computationally designed to enhance the coverage of subtype C V1V2 sequence diversity. Methods: Three subtype C Env strains were selected to maximize antibody binding coverage while complementing subtype C vaccine gp120s that were given in human clinical trials in South Africa, as well as to improve epitope accessibility. Humoral immunogenicity of a novel trivalent gp120 vaccine immunogen, a bivalent gp120 boost already in clinical trials (1086C and TV1), and a pentavalent (all five gp120s combined) were evaluated in a preclinical immunization study in guinea pigs. The pentavalent combination was further evaluated with alum versus glucopyranosyl lipid adjuvants formulated in squalene-in-water emulsion (GLA-SE) adjuvants in non-human primates. The breadth of the anti-V1V2 response was assessed using an array of cross-subtype variable loops 1&2 (V1V2) scaffold proteins and linear V2 peptides. Results: The breadth of the IgG response against V1V2 antigens of the trivalent and pentavalent groups was comparable, and both were greater than the breadth of the bivalent group. Linear epitope mapping showed that two linear epitopes in V2 were targeted by the vaccinated animals: the V2 hotspot focused at 169K that potentially correlated with decreased HIV-1 risk in RV144 and the V2.2 site (179LDV/I181) that is part of the integrin α4β7 binding site. The bivalent vaccine elicited a significantly higher magnitude of binding to the V2 hotspot compared to the trivalent vaccine whereas the trivalent vaccine elicited significantly higher binding to the V2.2 epitope compared to the bivalent vaccine, while the pentavalent recognized both regions. Conclusions: These results demonstrate that the three new computationally selected subtype C Envs successfully complemented 1086C and TV1 for broader V1V2 antibody responses, and, in concert with adjuvants that stimulate V1V2 responses, can be considered as part of a rationale immunogen design to improve V1V2 IgG coverage in future vaccine trials in South Africa.

Immunology↗

Revealing the Drag Instability in One-fluid Nonideal Magnetohydrodynamic Simulations of a 1D Isothermal C-shock

C-type shocks are believed to be ubiquitous in turbulent molecular clouds thanks to ambipolar diffusion. We investigate whether the drag instability in 1D isothermal C-shocks, inferred from the local linear theory of Gu & Chen, can appear in nonideal magnetohydrodynamic simulations. Two C-shock models (with narrow and broad steady-state shock widths) are considered to represent the typical environment of star-forming clouds. The ionization-recombination equilibrium is adopted for the one-fluid approach. In the 1D simulation, the inflow gas is continuously perturbed by a sinusoidal density fluctuation with a constant frequency. The perturbations clearly grow after entering the C-shock region until they start being damped at the transition to the post-shock region. We show that the profiles of a predominant Fourier mode extracted locally from the simulated growing perturbation match those of the growing mode derived from the linear analysis. Moreover, the local growth rate and wave frequency derived from the predominant mode generally agree with those from the linear theory. Therefore, we confirm the presence of the drag instability in simulated 1D isothermal C-shocks. We also explore the nonlinear behavior of the instability by imposing larger-amplitude perturbations to the simulation. We find that the drag instability is subject to wave steepening, leading to saturated perturbation growth. Issues concerning local analysis, nonlinear effects, one-fluid approach, and astrophysical applications are discussed.

79 ASTRONOMY AND ASTROPHYSICS↗

Global Corn Heat Stress: Mean and SD of Degree Days Above 29°C based on NEX-GDDP-CMIP6 Climate Projections

Description This global dataset provides the estimated mean and standard deviation (SD) of corn heat stress (degree days above 29°C) for a set of climate models in NEX-GDDP-CMIP6 at 0.25-degree resolution. The NEX-GDDP-CMIP6 dataset is comprised of global downscaled climate scenarios derived from the General Circulation Model (GCM) runs conducted under the Coupled Model Intercomparison Project Phase 6 (CMIP6). The current dataset includes: Long-Term Average Degree Days Above 29°C- Historical Long-Term Average Degree Days Above 29°C- SSP245 Long-Term Standard Deviation of Degree Days Above 29°C- Historical Long-Term Standard Deviation of Degree Days Above 29°C- SSP245 The mean and SD are calculated over 1985-2014 for the historical period and over 2035-2064 for future projections. A full description of methods, including growing season, daily temperature distribution, and statistical coefficients, can be found in Haqiqi (2024). The source climate data are obtained from https://ds.nccs.nasa.gov/thredds2/catalog/catalog.html and are described in Thrasher et al (2022). The codes used to create this dataset are available at https://github.com/ihaqiqi/dd29c_nex_cmip6. Acknowledgments This work was supported by the US Department of Energy, Office of Science, Biological and Environmental Research Program, Earth and Environmental Systems Modeling, MultiSector Dynamics under Cooperative Agreement DE-SC0022141. The data processing, computation, and storage were completed on Purdue Anvil supercomputer and cyberinfrastructure supported by the National Science Foundation HDR award # 2118329: "NSF Institute for Geospatial Understanding through an Integrative Discovery Environment (I-GUIDE)". References Haqiqi. I. (2024). Trade can buffer climate-induced risks and volatilities in crop supply. Environmental Research: Food Systems. https://doi.org/10.1088/2976-601X/ad7d12 Thrasher, B., Wang, W., Michaelis, A., Melton, F., Lee, T., & Nemani, R. (2022). NASA global daily downscaled projections, CMIP6. Scientific Data, 9(1), 262. https://doi.org/10.1038/s41597-022-01393-4

Climate Change↗

Hot hardness characteristics of ausformed AISI M-50, Matrix 2, WD-65, modified AISI 440-C, and Super Nitralloy

Short-term hot hardness studies were performed with ausformed AISI M-50, Matrix 2, WD-65, modified AISI 440-C (14-4-1) and case hardened Super Nitralloy. Hardness levels of each material were measured at elevated temperatures in an electric furnace with a low oxygen environment. Test temperatures ranged from 294 to 877 K. The hot hardness characteristics of the ausformed AISI-M-50, Matrix 2 WD-65, and modified AISI 440-C were the same as those determined for high-speed tool steels. Hot hardness for these steels can be predicted within one point Rockwell C. The hot hardness characteristics of both the case and core of Super Nitralloy were superior to AISI 52100 but inferior to the high-speed tool steels. The short-term Rockwell C hardness at temperature for the Super Nitralloy material between 294 and 769 K can be predicted within one point Rockwell C hardness.

Chevalier, J. L.↗

The effects of composition on mechanical properties of W-4Re-Hf-C alloys

Studies were made of the effects of alloy composition on the mechanical behavior of as-worked W-4Re-Hf-C alloys containing up to about 0.8 mol % Hfc. Extracted second-phase particles were analyzed and related to alloy composition and creep strength. While strengthening is attributed to HfC particles, the presence of excess hafnium or carbon (above the calculated amounts for stoichiometric HfC) in swaged W-4Re-Hf-C alloys generally causes a reduction of the high-temperature (1930 C) tensile strength; maximum creep strength is, however, indicated for alloys with a slight (about 0.05 to 0.1 at. %) excess of hafnium. Particle strengthening is reduced by WC in solid solution with HfC for allow compositions with an excess of carbon. The low-temperature ductility of worked W-4Re-Hf-C alloys appears to be far more dependent on the amount of excess C or Hf present than on the HfC particle content in the range studies.

Witzke, W. R.↗

All chain Loran-C time synchronization

A program is in progress to implement coordinated universal time (UTC) synchronization on all Loran-C transmissions. The present capability is limited to five Loran-C chains in which the tolerance is twenty-five microseconds with respect to UTC. Upon completion of the program, the transmissions of all Loran-C chains will be maintained within five microseconds of UTC. The improvement plan consists of equipping selected Loran-C transmitting stations for greater precision of frequency standard adjustment and improved monitoring capability. External time monitor stations will utilize television time transfer techniques with nearby SATCOM terminals where practicable, thus providing the requisite traceability to the Naval Observatory. The monitor equipment groups and the interrelationships with the ground station equipment are discussed. After a brief review of control doctrine, forth-coming improvements to transmitting stations and how the time monitor and navigation equipments will complement each other resulting in improved service to all users of the Loran-C system are described.

Sherman, H. T.↗

Stability and noise spectra of relative Loran-C frequency comparisons

Relative comparisons of Loran-C frequency transmissions between the master station of Catanzaro (Simeri Crichi) and the X, Z slave stations of Estartit (Spain) and Lampedusa (Italy) are carrying out by the GG LORSTA monitor station of the Mediterranean Sea Loran-C chain. These comparisons are able to emphasize the relative and, under certain conditions, the absolute rate of the emitting standard frequencies of the slave stations and some relevant statistical properties of the Loran-C Method for frequency transmission and time synchronization. The stability of each Loran-C frequency standard transmission is subject to perturbations, more or less known, due to the propagation medium and other causes. Following the Allan (1966) method for data processing, the performance of the relative rate of frequency of the transmissions of the X, Z slave stations are described calculating the standard deviation of a set of N frequency measurements from its mean averaged during sampling times. This standard deviation is designated as the measure of the stability of the Loran-C frequency transmission.

Proverbio, E.↗

The C-12/C-13 ratio in stellar atmospheres. VI - Five luminous cool stars

A simple curve-of-growth technique is described for extracting the C-12/C-13 ratio for M stars from high-resolution spectra of CO infrared vibration-rotation lines. The technique is applied to the CO lines at 1.6 and 2.3 microns in spectra of two M supergiants (Alpha Ori and Alpha Sco), two M giants (Alpha Her and Beta Peg), and a Mira-type variable (Chi Cyg). As a check on the CO analysis, the C-12/C-13 ratio is derived from the red CN system at 8000 A for Alpha Sco, Alpha Ori, and Beta Peg. The CO analysis is also applied to the K giant Alpha Boo as a check. The CN and CO results are found to be in general agreement, and the C-12/C-13 ratio in all the examined stars is shown to be considerably lower than the solar-system value. It is suggested that these stars were formed from clouds with a C-12/C-13 ratio of 40 to 89 and that their atmospheres now exhibit an enhancement of C-13 abundance due to internal production and mixing to the surface.

Hinkle, K. H.↗

Chemical vapor deposition of high T sub c superconductors

The results are reported of an investigation into the synthesis and properties of high temperature superconducting materials. A chemical vapor deposition apparatus was designed and built which is suitable for the preparation of multicomponent metal films This apparatus was used to prepare a series of high T sub c A-15 structure superconducting films in the binary system Nb-Ge. The effect on T sub c of a variety of substrate materials was investigated. An extensive series of ternary alloys were also prepared. Conditions allowing the brittle high T sub c (approximately 18 K) A-15 structure superconductor Nb3A1 to be prepared in a low T sub c but ductile form were found. Some of the ways that the ductile (bcc) form can be cold worked or machined are described. Measurements of rate of transformation of cold worked bcc material to the high T sub c A-15 structure with low temperature annealing are given. Preliminary measurements indicate that this material has attractive high field critical current densities.

Webb, G. W.↗

Development of surface coatings for air-lubricated, compliant journal bearings to 650 C

Surface coatings for an air-lubricated, compliant journal for an automotive gas turbine engine were tested to find those capable of withstanding temperatures of either 540 C (1000 F) or 650 C (1200 F). Also, the coatings have to be capable of surviving the start-stop sliding contact cycles prior to rotor lift-off and at touchdown. Selected coating combinations were tested in start-stop tests at 14 kPa (2 psi) loading for 2000 cycles at room and maximum temperatures. Specific coating recommendations are: Cdo and graphite on foil versus chrome carbide on journal up to 370 C (700 F); NASA PS-120 (Tribaloy 400, silver, and CaF2) on journal versus uncoated foil up to 540 C (1000 F); and chemically adherent Cr2O3 on journal and foil up to 650 C (1200 F). The chemically adherent Cr2O3 coating system was further tested successfully at 35 kPa (5 psi) loading for 2000 start-stop cycles.

Bhushan, B.↗

Improved boundary lubrication with formulated C-ethers

A comparison of five recently developed C-ether-formulated fluids with an advanced formulated MIL-L-27502 candidate ester is described. Steady state wear and friction measurements were made with a sliding pin on disk friction apparatus. Conditions included disk temperatures up to 260 C, dry air test atmosphere, 1 kilogram load, 50 rpm disk speed, and test times to 130 minutes. Based on wear rates and coefficients of friction, three of the C-ether formulations as well as the C-ether base fluid gave better boundary lubrication than the ester fluid under all test conditions. The susceptibility of C-ethers to selective additive treatment (phosphinic esters or acids and other antiwear additives) was demonstrated when two of the formulations gave somewhat improved lubrication over the base fluid. The increased operating potential for this fluid was shown in relationship to bulk oil temperature limits for MIL-L-23699 and MIL-L-27502 type esters.

Loomis, W. R.↗

Surface chemistry, microstructure and friction properties of some ferrous-base metallic glasses at temperatures to 750 C

X-ray photoelectron spectroscopy analysis, transmission electron microscopy, diffraction studies, and sliding friction experiments were conducted with ferrous-base metallic glasses in sliding contact with aluminum oxide at temperatures from room to 750 C in a vacuum of 30 nPa. The results indicate that there is a significant temperature influence on the friction properties, surface chemistry, and microstructure of metallic glasses. The relative concentrations of the various constituents at the surface of the sputtered specimens were very different from the normal bulk compositions. Contaminants can come from the bulk of the material to the surface upon heating and impart boric oxide and silicon oxide at 350 C and boron nitride above 500 C. The coefficient of friction increased with increasing temperature to 350 C. Above 500 C the coefficient of friction decreased rapidly. The segregation of contaminants may be responsible for the friction behavior.

Miyoshi, K.↗

The EMC of satellite power systems and DoD C-E systems

The solar power satellite (SPS) technical parameters that are needed to accurately assess the electromagnetic compatibility (EMC) between SPS systems and DoD communications-electronics (C-E) systems are identified and assessed. The type of electromagnetic interactions that could degrade the performance of C-E systems are described and the major military installations in the southwestern portions of CONUS where specially sensitive C-E systems are being used for combat training and evaluation are identified. Classes of C-E systems that are generally in the vicinity of these military installations are considered. The Technical parameters that govern the degree of compatibility of the SPS with these C-E systems, and some technical requirements that are necessary to ensure short-term and long-term EMC are identified.

Atkinson, J. H.↗

The temperature of C II emission-line formation regions in cool stars

An investigation has been conducted of the temperature of C II emission-line formation regions in the outer atmospheres of late-type giant and supergiant stars. A distinct dichotomy is seen in the C II lambda 2325/lambda 1335 ratio between coronal and noncoronal stars. It is found that C II emission from noncoronal giant and supergiant stars comes from regions with temperatures of 7000-9000 K, with the mean temperature being approximately 8500 K, whereas the C II emission from coronal stars likely comes from hotter regions. The C II ratio provides a powerful empirical tool for estimating the chromospheric temperatures of cool giants and supergiants.

Brown, A.↗

Rheological, processing, and 371 deg C mechanical properties of Celion 6000/N-phenylnadimide modified PMR composites

The rheology, processing, and chemistry of newly developed N-phenylnadimide modified PMR (PMR-PN) polyimide resins are reviewed. The 371 C performance of their composites reinforced with Celion 6000 graphite fibers is also reviewed, along with the state of the art Celion 6000/PMR-15 composite. The effects of the 371 C exposure in air for up to 300 hr on the composite glass transition temperature, weight loss characteristics, and dimensional stability are presented. The changes in the composite 371 C interlaminar shear and flexural properties are also presented. In addition, composite interfacial degradation at a function of exposure time at 371 C was followed by scanning electron microscopy. The results suggest that the composite materials can be used at 371 C for at least 100 hr.

Pater, R. H.↗