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Organic fabric is reacted first with vapors of a phosphorus oxychloride, phosphorus oxybromide solution and then with bromine vapor, after neutralization it is flameproof in pure oxygen atmosphere. Soaking the fabric with mixture of ammonium polyphosphates increases flame resistance, but the polyphosphates are leached out during laundering.
A lidar system based on ultraviolet (UV) laser induced fluorescence (LIF) was developed for the remote detection of atmospherically dispersed biological particles and chemical vapors. This UV fluorescence lidar has many potential applications for monitoring environmental pollution, industrial waste emission, agricultural insect control, illicit chemical processing, and military defense operations. The general goal of this work is to investigate the research issues associated with the long range detection and identification of chemicals, e.g. aromatic solvents and chemical precursors, and biological materials, e.g. bacillus thuringiensis (BT) and bacillus globiggi (BG). In the detection of biological particulates, we are particularly interested in extending the detection range of an existing solar-blind 248-nm lidar system. We are investigating the use of longer excitation laser wavelengths (i.e. lambda greater than 280-nm to have more favorable atmospheric light transmission characteristics) for improving detection range to better than 10 km. In the detection of chemical plumes, our main research objectives are to determine how accurately and sensitively a chemical plume can be located at range, and how well spectrally the chemical species can be measured to allow their identification.
Chemical mechanisms of the atmospheric pressure, high-temperature (875-1500 K) gas-phase oxidation of benzene, toluene, ethylbenzene, and propylbenzene are described and discussed. Oxidation trends evident from turbulent flow reactor experiments serve as the basis for the mechanisms of the oxidation of benzene and alkylated aromatics. The potential effects of very high temperatures and pressures on the chemistry of oxidation of aromatics are described. The oxidation of benzene and phenyl radical has been found to proceed in a stepwise C6-C5-C4 sequence. Species profiles obtained from flow-reactor experiments suggest that the oxidation of benzene and phenyl radical follows the generalized route via phenoxy, cyclopentadienyl and butadienyl radical. The oxidation of the C4 species branches into multiple pathways that yield copious amounts of ethylene and acetylene. Certain major trends are evident: the alkylated aromatics on initial attack either form styrene, benzyl radical or benzene. The styrene reacts further to produce a benzyl radical or benzene. The oxidation of an alkylated aromatic hydrocarbon appears eventually to reduce to the oxidation of either phenyl radical or benzene.
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Pyrrone (polyimidazopyrrolone) polymers are a new class of thermally stable, radiation and chemical resistant aromatic-heterocyclic polymers featuring a greater chemical and mechanical durability than cellulose acetate.
The preparation of a polymer for the Pioneer-Venus Large Probe Gas Chromatograph and another polymer for gas-chromatographic analysis of the Jovian atmosphere is described. Technical-grade divinylbenzene is used as a reliable and economical source of monomer for the preparation of polymer beads. The discussion covers monomeric preparation, polymerization apparatus, first-stage polymer beads, second-stage polymer beads, amino-polymer, columns and gas-chromatographic testing instrumentation used. The polymer for the Pioneer-Venus gas chromatograph is also suitable for ammonia but not for amine analysis. However, the polymer for the analysis of the Jovian atmosphere is a chemically derivatized aromatic polymer that is suitable for amine analysis. The two-stage polymerization produces a highly efficient polymer packing clearly superior to others prepared by adjusted dilution of the aqueous-organic suspension system.
Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 per centimeter (approximately 18 to 500 micrometers) have been used to infer the vertical variations of Titan's ice abundances, as well as those of the aerosol from the surface to an altitude of 300 km [1]. The aerosol has a broad emission feature centered approximately at 140 per centimeter (71 micrometers). As seen in Figure 1, this feature cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs [2]. The far-IR is uniquely qualified for investigating low-energy vibrational motions within the lattice structures of COITIDlex aerosol. The feature observed by CIRS is broad, and does not likely arise from individual molecules, but rather is representative of the skeletal movements of macromolecules. Since Cassini's arrival at Titan, benzene (C6H6) has been detected in the atmosphere at ppm levels as well as ions that may be polycyclic aromatic hydrocarbons (PAHs) [3]. We speculate that the feature may be a blended composite that can be identified with low-energy vibrations of two-dimensional lattice structures of large molecules, such as PAHs or nitrogenated aromatics. Such structures do not dominate the composition of analog materials generated from CH4 and N2 irradiation. We are performing studies forming aerosol analog via UV irradiation of aromatic precursors - specifically C6H6 - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. The optical and chemical properties of the aromatic analog will be compared to those formed from CH4/N2 mixtures, with a focus on the as-yet unidentified far-IR absorbance feature. Preliminary results indicate that the photochemically-formed aromatic aerosol has distinct chemical composition, and may incorporate nitrogen either into the ring structure or adjoined chemical groups. These compositional differences are demonstrated in the aerosol mass spectra shown in Figure 2. The aromatic aerosol also demonstrates strong chemical reactivity when exposed to laboratory air, indicating substantial stored chemical potential. Oxidatoin and solubility studies wil be presented and implicatoins for prebiotic chemistry o nTitan will be discussed.
Polyimides of new class made from chemical reactions of aromatic dianhydrides with novel aromatic diamines in which carbonyl and ether groups connect aromatic rings. New polyimides melt-processable, strong, resistant to impacts, and resistant to solvents and other chemicals. Useful as adhesives, coatings, films, membranes, and composite matrices.
A high-temperature stable, optically transparent, low dielectric aromatic polyimide is prepared by chemically combining equimolar quantities of an aromatic dianhydride reactant and an aromatic diamine reactant, which are selected so that one reactant contains at least one Si(CH3)2 group in its molecular structure, and the other reactant contains at least one -CF3 group in its molecular structure. The reactants are chemically combined in a solvent medium to form a solution of a high molecular weight polyamic acid, which is then converted to the corresponding polyimide.
A high-temperature stable, optically transparent, low dielectric aromatic polyimide is prepared by chemically combining equimolar quantities of an aromatic dianhydride reactant and an aromatic diamine reactant, which are selected so that one reactant contains at least one Si(CH.sub.3).sub.2 group in its molecular structure, and the other reactant contains at least one --CH.sub.3 group in its molecular structure. The reactants are chemically combined in a solvent medium to form a solution of a high molecular weight polyamic acid, which is then converted to the corresponding polyimide.
The photoluminescence (fluorescence) of a film of the laboratory-synthesized quenched carbonaceous composite (filmy QCC) is shown to have a single broad emission feature with a peak wavelength that varies from 670 to 725 nm, and coincides with that of the extended red emission observed in reflection nebulae. The rapid decay of the filmy QCC red fluorescence in air and of the stable blue fluorescence of the filmy QCC dissolved in liquid Freon suggests that the red fluorescence originates from the interaction of active chemical species and aromatic components in the filmy QCC. A material similar in nature to that of the filmy QCC may be a major component of interstellar dust.
Series of addition-type thermoplastics (ATT's) exhibit useful properties. Because of their addition curing and linear structure, ATT polymers have toughness, like thermoplastics, and easily processed, like thermosets. Work undertaken to develop chemical reaction forming stable aromatic rings in backbone of ATT polymer, combining high-temperature performance and thermo-oxidative stability with toughness and easy processibility, and minimizing or eliminating necessity for tradeoffs among properties often observed in conventional polymer syntheses.
Chromatographic analysis of the Cumberland mudstone in Gale crater by the Sample Analysis at Mars (SAM) instrument revealed the detection of two to three isomers of dichlorobenzene. Their individual concentrations were estimated to be in the 0.5–17 ppbw range relative to the sample mass. We also report the first detection of trichloromethylpropane and the confirmation of the detection of chlorobenzene previously reported. Supporting laboratory experiments excluded the SAM internal background as the source of those compounds, thus confirming the organic carbon and chlorine of the newly detected chlorohydrocarbons are indigenous to the mudstone sample. Laboratory experiments also demonstrated that the chlorohydrocarbons were mainly produced from chemical reactions occurring in the SAM ovens between organic molecules and oxychlorines contained in the sample. The results we obtained show that meteoritic organics and tested chemical species (a polycyclic aromatic hydrocarbon, an amino acid, and a carboxylic acid) were plausible organic precursors of the chlorinated aromatic molecules detected with SAM, thus suggesting that they could be among the organic molecules present in the mudstone. Results from this study coupled with previously reported detections of chlorinated aromatics (<300 ppbw) indigenous to the same mudstone highlight that organics can be preserved from the harsh surface conditions even at shallow depth. The detection of new chlorohydrocarbons with SAM confirms that organic molecules should have been available in an environment favorable to life forms, strengthening the habitability aspect of Gale crater. Key Words: Mars—Chlorinated organic molecules—In situ measurements—Sample Analysis at Mars— Mudstone—Gale crater. Astrobiology 20, 292–306.
The fuel chemical property influence on a gas turbine combustor was studied using 25 test fuels. Fuel physical properties were de-emphasized by using fuel injectors which produce highly-atomized, and hence rapidly vaporizing sprays. A substantial fuel spray characterization effort was conducted to allow selection of nozzles which assured that such sprays were achieved for all fuels. The fuels were specified to cover the following wide ranges of chemical properties: hydrogen, 9.1 to 15 (wt) pct; total aromatics, 0 to 100 (vol) pct; and naphthalene, 0 to 30 (vol) pct. standard fuels (e.g., Jet A, JP4), speciality products (e.g., decalin, xylene tower bottoms) and special fuel blends were included. The latter group included six, 4-component blends prepared to achieve parametric variations in fuel hydrogen, total aromatics and naphthalene contents. The principle influences of fuel chemical properties on the combustor behavior were reflected by the radiation, liner temperature, and exhaust smoke number (or equivalently, soot number density) data. Test results indicated that naphthalene content strongly influenced the radiative heat load while parametric variations in total aromatics did not.
Flame resistant fibrous materials for space shuttle application were developed through chemical modification of commercially available aromatic polyamide fibrous products. The new surface treatment was achieved in the laboratory by ultraviolet activation of the fabric in the presence of fluoroolefin monomers and a diluent gas. The monomers grafted under these conditions provide the improved properties of the fabric in flame resistance, chemical inertness, and nonwettability without the sacrifice of color or physical properties. The laboratory reaction vessel was scaled-up to a batch continuous process, which treats ten yards of the commercial width textiles. The treated commercial width Nomex (HT-10-41) from the scaled-up reactor is self-extinguishing in an oxygen-enriched environment, water-repellent, soft, silky, and improved in chemical resistance. Unlike most textile processes, the grafting unit operates under dry conditions and no chemical by-products have to be washed out of the finished product.
A study of the questions associated with the use of alternate fuels demands knowledge of the chemical mechanism of pyrolysis and oxidation of aromatic compounds. Both pyrolysis and oxidation are important, because fuel-rich conditions may mean that pyrolysis is competitive with oxidation. Soot formation is certainly a pyrolysis problem. The complexity of system characteristics makes a detailed study of thermodynamical and kinetic conditions difficult. The matter can be simplified somewhat by generalizing the chemistry by classes of molecules. The criteria for such a generalization of the chemistry are discussed along with an evaluation of the rate constants and their temperature and pressure dependences. Attention is given to the pyrolysis of hydrocarbons, the oxidation of hydrocarbons, the oxidation reactions of alkanes, aspects of codification and extrapolation, group additivity, structural consideration, kinetics, and the pyrolysis of aromatic compounds.
Tremendous strides have been made in the understanding of interstellar material over the past twenty years thanks to significant, parallel developments in two closely related areas: observational IR astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely unknown and the notion of abundant, gas phase, polycyclic aromatic hydrocarbons (PAHs) anywhere in the interstellar medium (ISM) considered impossible. Today the dust composition of the diffuse and dense ISM is reasonably well constrained and the spectroscopic case for interstellar PAHs, impossibly large molecules by early interstellar chemistry standards, is very strong. PAH spectral features are now being used as new probes of the ISM. PAH ionization states reflect the ionization balance of the medium while PAH size and structure reflect the energetic and chemical history of the medium. Aromatic carbon-rich materials ranging in size from PAHs and PAH nanoclusters, to sub-micron and micron-sized dust grains represent an important component of the ISM. These species: (1) dominate the heating and cooling of interstellar clouds via energetic photoelectron ejection and infrared (IR) emission; (2) moderate the ionization balance in photodissociation regions and molecular clouds; (3) moderate the composition of the gas phase and play an important role in determining the chemistry of the ISM; (4) contribute to the interstellar extinction in the near IR, visible, and UV spectral regions; and (5) convert UV, visible, and near-IR radiation to mid- and far-IR radiation in the ISM and, as such, are responsible for the well known, widespread family of mid-IR emission features with major components near 3.3, 6.2, 7.7, 8.6, and 11.3 microns.