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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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24 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Chemistry and properties of blends of acetylene terminated materials

As part of a NASA program to develop new high temperature/high performance structural materials, the chemistry and properties of acetylene-containing materials and their cured resins are under investigation. The objective of this work is to develop materials that are readily processable (i.e., 200-300 C and about 1.4 MPa or less) and possess usable mechanical properties at temperatures as high as 177 C. An acetylene-terminated aspartimide (ATA) was blended with an equal weight of an acetylene-terminated arylene ether (ATAE) oligomer. The blend was subsequently thermally cured to yield a resin which was evaluated in the form of neat resin moldings, adhesive specimens, and laminates. Adhesive specimens and laminates gave good mechanical properties to temperatures as high as 177 C. In addition, preliminary laminate work is presented on the resin from a blend of a new N-methyl substituted ATA and an ATAE.

Connell, John W.↗
DOE OSTI2021

Influence of PRE-emergence herbicides on soybean development, root nodulation and symbiotic nitrogen fixation

We report widespread occurrence of herbicide-resistant weeds has further limited effective POST-emergence herbicide options in soybean (Glycine max (L.) Merr.) leading to an increased adoption of PRE-emergence herbicides. The objective of this study was to investigate the influence of 11 commonly used PRE herbicides on soybean development, root nodulation, and symbiotic N fixation. Soybean plants were grown under greenhouse conditions in pots (10 L; 4 plants per pot) filled with silt loam soil and treated one day after planting with a labeled field rate of imazethapyr, chlorimuron-ethyl, cloransulam-methyl, metribuzin, sulfentrazone, flumioxazin, saflufenacil, acetochlor, S-metolachlor, dimethenamid-P, pyroxasulfone and no herbicide (nontreated control). Sulfentrazone reduced soybean canopy at the VC growth stage but no canopy reduction was observed at the V2 growth stage from any of the herbicide treatments. At the R2 growth stage, herbicides had no effect on soybean development (root and shoot biomass), root nodulation (# nodule per plant, nodule diameter, and nodule biomass) and symbiotic N fixation (acetylene reduction assay and 15 N natural abundance). According to our findings, although PRE herbicides may slightly affect early-season soybean development, the impacts on plant growth, root nodulation, and symbiotic N fixation were negligible. Thus, when sprayed according to the label, the benefits of PRE herbicides for weed control likely outweigh any potential concern regarding soybean development, root nodulation, and N fixation.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1985

An improved processible acetylene-terminated polyimide for composites

The newest member of a family of thermosetting acetylene-substituted polyimide oligomers is HR600P. This oligomer is the isoimide version of the oligomer known as HR600P and Thermid 600. Although both types of material yield the same heat resistant end products after cure, HR600P has much superior processing characteristics. This attributed to its lower melting temperature (160 + or - 10 C, 320 + or - 20 F) in contrast to 202 C (396 F) for Thermid MC-600, its longer gel time at its processing temperature (16 to 30 minutes bvs 3 minutes), and its excellent solubility in low boiling solvents such as tetrahydrofuran, glymes, or 4:1 methyl ethyl ketone/toluene mixtures. These advantages provide more acceptable coating and impregnation procedures, allow for more complete removal at lower temperatures, provide a longer pot life or working time, and allow composite structure fabrication in conventional autoclaves used for epoxy composite curing. The excellent processing characteristics of HR600P allow its use in large area laminated structures, structural composites, and molding compositions.

Landis, A. L.↗
DOE OSTI2021

Transformation of an Embedded Five-Membered Ring in Polycyclic Aromatic Hydrocarbons via the Hydrogen-Abstraction–Acetylene-Addition Mechanism: A Theoretical Study

Five-membered rings are constituents of many polycyclic aromatic hydrocarbons (PAHs) and their presence on the edges of large PAHs has been repeatedly observed experimentally. However, modern kinetic combustion models often do not consider the growth of PAHs through the transformation of the five-membered rings. Here, in connection with the above, we carried out a theoretical study of the mechanism of Hydrogen-Abstraction-aCetylene-Addition (HACA) transformation of an embedded five-membered ring on the armchair PAH edge to a six-membered ring, considering cyclopenta[d,e,f]phenanthrene (4,5-methylenephenanthrene) as a prototype system for this process. The potential energy surface for the reactions of cyclopenta[d,e,f]phenanthrenyl radicals produced by direct H abstractions from cyclopenta[d,e,f]phenanthrene with acetylene has been compiled at the G3(MP2,CC)//B3LYP/6-311G(d,p) level of theory including zero-point vibrational energy corrections. The computed energies and molecular parameters were then used to solve the Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) in order to calculate reaction rate at various pressures and temperatures, which were fitted to modified Arrhenius equation for further kinetic modeling. The results show that the HACA transformation of the embedded five-membered ring to a six-membered ring is possible, albeit slow. The most viable reaction mechanism involves the R2 + C 2 H 2 reaction, where the acetylene molecules adds to a σ-radical in the six-membered ring adjacent to the five-membered ring via a low entrance barrier. The predominant product of R2 + C 2 H 2 is predicted to be 3 ethynyl 4H cyclopenta[def]phenanthrene Pr5 via immediate H elimination from the initial addition complex. Next, Pr5 undergoes H-assisted isomerization to 4aH-pentaleno[4,3,2,1-cdef]phenanthrene Pr4, and the latter adds an H atom eventually forming the 1-pyrenylmethyl radical Pr3: R2 + C 2 H 2 ⇌ 3 ethynyl 4H cyclopenta[def]phenanthrene (Pr5) + H ⇌ 4aH-pentaleno[4,3,2,1-cdef]phenanthrene (Pr4) + H Pr5 + H ⇌ Pr4 + H Pr4 + H → 1-pyrenylmethyl (Pr3) This HACA sequence may be competitive with the methyl radical addition to the R1 radical formed by H abstraction from the CH 2 group in the five-membered ring of cyclopenta[d,e,f]phenanthrene, which provides a pathway to pyrene following two H atom losses. Relative contributions of the two mechanisms of the five- to six-membered ring transformation would strongly depend on the branching ratios of the R1 and R2 radicals produced by the H abstractions and the available concentration of C 2 H 2 vs. CH 3 and hence differ in different flames.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Measurements of Intermediate Species in Fuel-Rich Oxidation of Ethylene, Toluene, and n -Decane

Polycyclic aromatic hydrocarbons (PAHs) are important precursors to the formation of soot and are also pollutant emissions from combustion devices, including internal combustion engines. To understand the formation of PAHs, the low-molecular-weight hydrocarbon chemistry leading to their formation needs to be understood. Toward this goal, fuel-rich oxidation of three different hydrocarbons, i.e., ethylene, toluene, and n-decane, has been investigated in an atmospheric pressure flow reactor at varying temperatures (1000–1350 K), equivalence ratios (φ = 3.0–12.0), and residence times of 0.25–1.5 s. The major C 1 to C 7 intermediates, such as methane, acetylene, ethylene, allene, propyne, propylene, vinylacetylene, 1,3-butadiene, cyclopentadiene, benzene, and toluene, were quantified using a gas chromatograph equipped with a flame ionization detector. The experimental tendency of intermediate species formation, e.g., the dependence of temperature, equivalence ratio, and residence time, was similar in ethylene oxidation and n-decane oxidation. The concentrations of intermediate species up to C 4 were higher in ethylene/n-decane oxidation than toluene oxidation, while a nearly equal or larger amount of C5–C7 species was produced in toluene oxidation. The experimental data were compared with modeling results using a detailed chemical kinetic mechanism. The calculated data using the kinetic model were in agreement with the experimental results. Additionally, a comprehensive kinetic analysis on the reaction pathways of each species was conducted to assess the differences in the oxidation chemistry with the change in the structure of hydrocarbons. In particular, in-depth analysis of benzene formation was performed, elucidating that two benzene formation pathways were important in ethylene and n-decane oxidation: (1) H elimination of the 2,4-cyclohexadienyl radical produced from the isomerization of the 2,4-cyclopentadienylmethyl radical, and (2) dehydrogenation of cyclohexadiene produced from reactions of vinyl radical with 1,3-butadiene. In toluene oxidation, it was found that benzene was primarily produced from toluene through the replacement of the methyl group with hydrogen.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS2007

Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3 yields C3H5 + CH3. This reaction occurs even at moderate pressures of approx.200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(exp -3) - 10(exp 5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3 +/- 0.1.

Fahr, Askar↗