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At least 919 records · Page 51

New Directions in Phthalocyanine Pigments

The objectives were the following: (1) investigation of the synthesis of new phthalocyanines; (2) characterization of the new phthalocyanines synthesized; (3) investigate the properties of the newly synthesized phthalocyanines with emphasis on UV protection of plastics and coatings; and (4) utilize quantum mechanics to evaluate the structural relationships with possible properties and synthetic approaches. The proposed research targeted the synthesis of phthalocyanines containing an aromatic bridge between two phthalocyanine rings. The goal was to synthesize pigments which would protect plastics when exposed to the photodegradation effects of the sun in space. The stability and extended conjugation of the phthalocyanines offer a unique opportunity for energy absorption and numerous radiative and non-radiative energy loss mechanisms. Although the original targeted phthalocyanines were changed early in the project, several new and unique phthalocyanine compounds were prepared. The basic goals of this work were met and some unique and unexpected outcomes of the work were the result of the integral use of quantum mechanics and molecular modeling with the synthetic effort.

Vandemark, Michael R.↗

Polyimides prepared from 3,5-diamino benzo trifluoride

High performance, thermooxidatively stable polyimides are prepared by reacting aromatic diamines with pendant trifluoromethyl groups and dianhydrides in an amide solvent to form a poly(amic acid), followed by cyclizing the poly(amic acid) to form the corresponding polyimide.

Gerber, Margaret K.↗

Hypervelocity impact survivability experiments for carbonaceous impactors

We performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, fullerenes, phthalic acid crystals, and Murchison meteorite) into Al plate at velocities between 4.2 and 6.1 km/s. These tests were made to do the following: (1) determine the survivability of carbon forms and organize molecules in low hypervelocity impact; (2) characterize carbonaceous impactor residues; and (3) determine whether or not fullerenes could form from carbonaceous impactors, under our experimental conditions, or survive as impactors. An analytical protocol of field emission SEM imagery, SEM-EDX, laser Raman spectroscopy, single and 2-stage laser mass spectrometry, and laser induced fluorescence (LIF) found the following: (1) diamonds did not survive impact at 4.8 km/s, but were transformed into various forms of disordered graphite; (2) intact, well-ordered graphite impactors did survive impact at 5.9 km/sec, but were only found in the crater bottom centers; the degree of impact-induced disorder in the graphite increases outward (walls, rims, ejecta); (3) phthalic acid crystals were destroyed on impact (at 4.2 km/s, although a large proportion of phthalic acid molecules did survive impact); (4) fullerenes did not form as products of carbonaceous impactors (5.9 - 6.1 km/s, fullerene impactor molecules mostly survived impact at 5.9 km/s; and (5) two Murchison meteorite samples (launched at 4.8 and 5.9 km/s) show preservation of some higher mass polycyclic aromatic hydrocarbons (PAHs) compared with the non-impacted sample. Each impactor type shows unique impactor residue morphologies produced at a given impact velocity. An expanded methodology is presented to announce relatively new analytical techniques together with innovative modifications to other methods that can be used to characterize small impact residues in LDEF craters, in addition to other acquired extraterrestrial samples.

Bunch, T. E.↗

Deviations of interstellar extinctions from the mean R-dependent extinction law

An analysis is conducted of the deviations from the mean extinction law A(lambda)/A(V) over UV wavelengths emphasizing sightlines through bright nebulosities vs dark clouds. The stellar sample is subdivided into sight lines with defined properties, and different behavior is noted for the deviations in the dark-cloud and bright-nebula sight lines. The deviations are correlated within the same wavenumber interval, but unique shapes for the FUV rise in the deviations are observed. Distributions of silicate grains are considered to account for the extinctions at certain wavenumbers that would explain the observations. The FUV rise in the extinctions is theorized to be related to the UV extinction of polycyclic aromatic hydrocarbons.

Mathis, John S.↗

Comets and the origins and evolution of life; Proceedings of the Conference, Univ. of Wisconsin, Eau Claire, Sept. 30-Oct. 2, 1991

Papers are presented on comets and the formation of biochemical compounds on the primitive earth; the cometary origin of carbon, nitrogen, and water on the earth; comets as a possible source of prebiotic molecules; comet impacts and chemical evolution on the bombarded earth; and cometary supply of terrestrial organics (lessons from the K/T and the present epoch). Other papers are on a computational study of radiation chemical processing in comet nuclei, the origin of the polycyclic aromatic hydrocarbons in meteorites, the fate of organic matter during planetary accretion (preliminary studies of the organic chemistry of experimentally shocked Murchison meteorite), recent observations of interstellar molecules (detection of CCO and a limit on H2C3O), terrestrial and extraterrestrial sources of molecular monochirality, and dark matter in the solar system (hydrogen cyanide polymers).

Thomas, Paul J.↗

The fate or organic matter during planetary accretion - Preliminary studies of the organic chemistry of experimentally shocked Murchison meteorite

The fate of organic matter in carbonaceous meteorites during hypervelocity (1-2 km/sec) impacts is investigated using results of experiments in which three samples of the Murchison (CM2) carbonaceous chondrite were shocked to 19, 20, and 36 GPa and analyzed by highly sensitive thermal-desorption photoionization mass spectrometry (SALI). The thermal-desorptive SALI mass spectra of unshocked CM2 material revealed presence of indigenous aliphatic, aromatic, sulfur, and organosulfur compounds, and samples shocked to about 20 GPa showed little or no loss of organic matter. On the other hand, samples shocked to 36 GPa exhibited about 70 percent loss of organic material and a lower alkene/alkane ratio than did the starting material. The results suggest that it is unlikely that the indigenous organic matter in carbonaceous chondritelike planetesimals could have survived the impact on the earth in the later stages of earth's accretion.

Tingle, Tracy N.↗

Simplified jet fuel reaction mechanism for lean burn combustion application

Successful modeling of combustion and emissions in gas turbine engine combustors requires an adequate description of the reaction mechanism. Detailed mechanisms contain a large number of chemical species participating simultaneously in many elementary kinetic steps. Current computational fluid dynamic models must include fuel vaporization, fuel-air mixing, chemical reactions, and complicated boundary geometries. A five-step Jet-A fuel mechanism which involves pyrolysis and subsequent oxidation of paraffin and aromatic compounds is presented. This mechanism is verified by comparing with Jet-A fuel ignition delay time experimental data, and species concentrations obtained from flametube experiments. This five-step mechanism appears to be better than the current one- and two-step mechanisms.

Lee, Chi-Ming↗

A search for C60 in carbonaceous chondrites

Analysis of interior samples of the Murchison meteorite by two routes yielded an upper limit of 2 ppb for its C60 content, as compared to parts per million levels for individual polycyclic aromatic hydrocarbons (PAHs ). Provided the samples contain an interstellar component, which is probable since Murchison hydrocarbons contain excess deuterium, this result argues against the ubiquitous presence of C60 in the interstellar medium. A possible explanation for the absence of C60 was found in experiments showing how PAHs replace fullerenes as stable end products when hydrogen is present during carbon condensation. As a secondary result we found high molecular weight PAHs in the Murchison and Allende meteorites. Coronene and its methyl derivatives are especially interesting since features in the coronene spectrum have been shown to match some of the unidentified interstellar infrared emission bands.

De Vries, M. S.↗

Electronic and vibrational spectra of matrix isolated anthracene radical cations - Experimental and theoretical aspects

The IR vibrational and visible/UV electronic absorption spectra of the anthracene cation, An(+), were studied experimentally, in argon matrices at 12 K, as well as theoretically, using ab initio calculations for the vibrational modes and enhanced semiempirical methods with configuration interaction for the electronic spectra. It was found that both approaches predicted well the observed photoelectron spectrum. The theoretical IR intensities showed some remarkable differences between neutral and ionized species (for example, the CH in-plane bending modes and CC in-plane stretching vibrations were predicted to increase by several orders of magnitude upon ionization). Likewise, estimated experimental IR intensities showed a significant increase in the cation band intensities over the neutrals. The implication of these findings for the hypothesis that polycyclic aromatic hydrocarbon cations are responsible for the unidentified IR emission bands from interstellar space is discussed.

Szczepanski, Jan↗

Measurement of volatile organic chemicals at selected sites in California

Urban air concentrations of 24 selected volatile organic chemicals that may be potentially hazardous to human health and environment were measured during field experiments conducted at two California locations, at Houston, and at Denver. Chemicals measured included chlorofluorocarbons, halomethanes, haloethanes, halopropanes, chloroethylenes, and aromatic hydrocarbons. With emphasis on California sites, data from these studies are analyzed and interpreted with respect to variabilities in ambient air concentrations, diurnal changes, relation to prevailing meteorology, sources and trends. Except in a few instances, mean concentrations are typically between 0 and 5 ppb. Significant variabilities in atmospheric concentrations associated with intense sources and adverse meteorological conditions are shown to exist. In addition to short-term variability, there is evidence of systematic diurnal and seasonal trends. In some instances it is possible to detect declining trends resulting from the effectiveness of control strategies.

Singh, Hanwant B.↗

Benzonorbornadiene end caps for PMR resins

Several ortho-disubstituted benzonorbornadiene derivatives are described. These molecules contain acid, ester, or anhydride functionality permitting their use as end caps in PMR (polymerization of monomer reactants) polyimide systems. The replacement of the currently used norbornenyl end caps with benzonorbornadienyl end caps affords resins of increased aromatic content. It also allows evaluation of some mechanistic aspects of PMR cross-linking. Initial testing of N-phenylimide model compounds and of actual resin formulations using the benzonorbornadienyl end cap reveals that they undergo efficient thermal crosslinking to give oligomers with physical properties and thermal stability comparable to commercial norbornene-end-capped PMR systems.

Panigot, Michael J.↗

Laboratory simulation of organic grain mantles

Laboratory simulations have been conducted of interstellar space conditions conducive to grain mantle evolution, including the photoproduction of a material which resembles the organic refractory mantle on interstellar grains. Upon analysis by various methods these organic refractory samples are noted to consist of a complex mixture of long, cross-linked chains, with a high probability of being aromatic carbon molecules.

Mendoza-Gomez, Celia X.↗

Hydrogen bonding in the benzene-ammonia dimer

High-resolution optical and microwave spectra of the gas-phase benzene-ammonia dimer were obtained, showing that the ammonia molecule resides above the benzene plane and undergoes free, or nearly free, internal rotation. To estimate the binding energy (De) and other global properties of the intermolecular potential, theoretical calculations were performed for the benzene-ammonia dimer, using the Gaussian 92 (Fritsch, 1992) program at the MP2/6-31G** level. The predicted De was found to be at the lowest end of the range commonly accepted for hydrogen bonding and considerably below that of C6H6-H2O, consistent with the gas-phase acidities of ammonia and water. The observed geometry greatly resembles the amino-aromatic interaction found naturally in proteins.

Rodham, David A.↗

Spectral imaging of the 3.3 and 11.3 micron emission bands in NGC 1333 - Discovery of spatially separate band emissions

Spectral images in the 3.3 and 11.3 micron IR emission band around the star SVS 3 in NGC 1333 indicate that the two bands have their origin in different locations, rendering them useless in estimates of the sizes of the molecules emitting the bands. This is in keeping with the emission bands' generation by a mixture of variously sized polycyclic aromatic hydrocarbons (PAHs) whose smallest species have been dehydrogenated in the vicinity of SVS 3. Hot bands and overtone/combination bands may account for the 3.4-micron band, rather than molecular side-groups of the PAHs.

Bregman, Jesse↗

Chemistry and adhesive properties of poly(arylene ether)s containing heterocyclic units

Novel poly(arylene ether)s containing heterocyclic units were prepared, characterized, and evaluated as adhesives and composite matrices. The polymers were prepared by reacting a heterocyclic bisphenol with an activated aromatic dihalide in a polar aprotic solvent, using potassium carbonate. The polymerizations were generally carried out in N,N-dimethylacetamide at 155 C. In some cases, where the polymers were semicrystalline, higher temperatures and thus higher boiling solvents were necessary to keep the polymers in solution. Heterocyclic rings incorporated into the poly(arylene ether) backbone include phenylquinoxaline, phenylimidazole, benzimidazole, benzoxazole, 1,3,4-oxadiazole, and 1,2,4-triazole. The polymers were characterized by differential scanning calorimetry, solution viscosity, X-ray diffraction, thin film, and adhesive and (in some cases) composite properties. The glass transition temperatures, crystalline melt temperature, solubility, and mechanical properties varied depending upon the heterocyclic ring. The chemistry and properties of these materials are discussed.

Connell, John W.↗

Infrared spectra of transition objects and the composition and evolution of carbon dust

We obtained IR (5-23 microns) spectra of five carbon-rich objects in transition from the asymptotic giant branch (AGB) to the planetary nebula stage of evolution. These spectra show a variety of IR emission features due to circumstellar materials. In particular, all sources show the 6.2 and '7.7' micron bands, commonly observed in PNs and ascribed to polycyclic aromatic hydrocarbon molecules (PAHs). Some transition nebulae also show a strong 6-9 micron plateau characteristic for larger PAH clusters (about 400 C-atoms). A new broad feature at about 8.8 microns is present in some sources. This feature is distinctly different from the 8.6-micron PAH feature. This 8.8-micron feature may be present in the spectra of C-rich giants as well, but is not evident in PN spectra. We suggest that large amorphous carbon grains are responsible for the 8.8-micron feature. The transition objects show large spectral variations from source to source. This contrasts with C-rich PNs, which all show very similar IR spectra dominated by PAHs. These spectral variations between transition objects of similar effective temperatures cannot be due to excitation variations but imply compositional variations of the dust. Moreover, this result suggests that circumstellar dust evolves during the transition phase from red giant to PN, perhaps as a result of grain-grain collisions and shattering in the fast winds.

Buss, R. H., Jr.↗

Altitude performance of AN-F-58 fuels in J35-C-3 single combustor

Three fuel blends conforming to AN-F-58 specifications were tested in order to determine the influence of boiling temperatures and aromatic content on altitude performance in single combustor of 4000-pound-thrust turbojet engine. At simulated engine conditions from an altitude of 30,000 to an altitude of 60,000 feet and 85-percent rated engine speed, the three AN-F-58 fuels showed little difference in performance.

COMBUSTION - EFFECT OF ENGINE OPERATING CONDITIONS↗

Altitude performance of AN-F-58 fuels in J33-A-21 single combustor

Three fuels conforming to AN-F-58 specification were investigated in order to determine the influence of boiling temperatures and aromatic content on altitude performance in single combustor of a 4600-pound-thrust turbojet engine. Combustion efficiencies of the three AN-F-58 fuels were approximately equal at each simulated engine condition for altitudes from 5,000 to 50,000 feet, 90-percent normal rated engine speed, and flight Mach numbers of 0.0 and 0.6.

FUELS - PHYSICAL PROPERTIES↗