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Solid state polymerization and crystallography of polyimide precursors

Although the production of crystallinity in a polymeric system has historically led to commerically useful properties, the polyimides, prized for their high temperature characteristics, as customarily synthesized by melt or solution casting, are amorphous. It is shown that polymide containing residual crystallinity can be synthesized by isothermal annealing of crystals of the salt of the diisopropyl ester of pyromellitic acid and phenylene diamine. The reaction is topochemical in that the geometry of the polymer product is dependent upon that of the crystalline precursor. Infrared spectroscopy reveals the presence of imide absorption in the polymer, while powder diffractometry suggests residual crystallinity. Single crystal X-ray analysis of the monomer yields a structure of chains of alternating acid and base suggesting that the monomer is amenable to polymerization with a minimum of geometrical disruption.

Wakelyn, N. T.↗

An interstellar precursor mission

A mission out of the planetary system, with launch about the year 2000, could provide valuable scientific data as well as test some of the technology for a later mission to another star. Primary scientific objectives for the precursor mission concern characteristics of the heliopause, the interstellar medium, stellar distances (by parallax measurements), low energy cosmic rays, interplanetary gas distribution, and mass of the solar system. Secondary objectives include investigation of Pluto. Candidate science instruments are suggested. Individual spacecraft systems for the mission were considered, technology requirements and problem areas noted, and a number of recommendations made for technology study and advanced development. The most critical technology needs include attainment of 50-yr spacecraft lifetime and development of a long-life NEP system.

Jaffe, L. D.↗

Theoretical models of interstellar shocks. I - Radiative transfer and UV precursors

Theoretical models of interstellar radiative shocks are constructed, with special attention to the transfer of ionizing radiation. These models are 'self-consistent' in the sense that the emergent ionizing radiation (the UV precursor) is coupled with the ionization state of H, He, and the metals in the preshock gas. For shock velocities of at least 110 km/s the shocks generate sufficient UV radiation for complete preionization of H and He, the latter to He(+). At lower velocities the preionization can be much smaller, with important consequences for the cooling function, the shock structure, and the emission. For models with shock velocities of 40 to 130 km/s the intensities of the strongest emission lines in the UV, optical, and infrared are tabulated, as well as postshock column densities of metal ions potentially observable by UV absorption spectroscopy. Possible applications to supernova remnants and high-velocity interstellar gas are assessed.

Shull, J. M.↗

Possible existence and role of excited ozone precursors in the stratosphere

Laboratory kinetic experiments, quantum theoretical studies and certain recently discovered infrared emissions from the stratosphere together imply the possible existence of a metastable, energetic, and reactive form of ozone in the upper atmosphere. This species can potentially affect the upper atmospheric photochemistry and heat balance. For these reasons there is a need for further quantum theoretical and laboratory chemical kinetic studies addressing some of the relevant properties of the internally excited ozone precursors.

Prasad, S. S.↗

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.

Van De Meent, D.↗

Precursor active galaxies and the cosmic X-ray background

It is argued that the cosmic X-ray background (CXB) is not dominated by sources that are usual active galaxies or quasars. A comparable number of objects, young galaxies at z approximately 4 containing massive black holes surrounded by hot optically thin accretion disks, constitute the precursor active galaxies (PAG) postulated here for producing the thermal type spectrum required for the CXB. An evolutionary track for such PAG objects is described which would lead to the active galaxies observed as individual nonthermal sources. Unresolved emission from active galaxies at z 1 could then readily account for most of the nonthermal background observed in the gamma ray band.

Boldt, E. A.↗

An interstellar precursor mission

A mission out of the planetary system, launched about the year 2000, could provide valuable scientific data as well as test some of the technology for a later mission to another star. Primary scientific objectives for the precursor mission concern characteristics of the heliopause, the interstellar medium, stellar distances (by parallax measurements), low-energy cosmic rays, interplanetary gas distribution, and the mass of the solar system. Secondary objectives include investigation of Pluto. The mission should extend to 400-1000 AU from the sun. A heliocentric hyperbolic escape velocity of 50-100 km/sec or more is needed to attain this distance within a reasonable mission duration (20-50 years). The trajectory should be toward the incoming interstellar gas. For a year 2000 launch, a Pluto encounter and orbiter can be included. A second mission targeted parallel to the solar axis would also be worthwhile. The mission duration is 20 years, with an extended mission to a total of 50 years. A system using one or two stages of nuclear electric propulsion (NEP) was selected as a possible baseline. The most promising alternatives are ultralight solar sails or laser sailing, with the lasers in earth orbit, for example. The NEP baseline design allows the option of carrying a Pluto orbiter as a daughter spacecraft.

Jaffe, L. D.↗

Precursor active galaxies and the cosmic X-ray background

Consideration is given to Carr's theory (1980) that most cosmic X-ray background is produced by thermal X-ray emission associated with black hole accretion disks for compact objects. It is posited that the onset of significant X-rays occurs during galaxy formation when accretion disks are formed by the interaction of young galaxies and massive black holes of pregalactic origin. The study suggests that most cosmic X-ray background could be produced from distant sources with a low ratio of optical to X-ray luminosity. Precursor active galaxy objects involving a massive black hole surrounded by a hot optically thin accretion disk radiating near the Eddington luminosity limit and with an effective temperature of about 2 x 10 to the 9th K would fulfill the condition and produce the correct background spectrum and intensity. This model also associates cosmic X-ray background and nonthermal gamma-ray background to active galaxies, thus implying that massive black holes are associated with their internal dynamics.

Boldt, E.↗

Oxidation and formation of deposit precursors in hydrocarbon fuels

A practical fuel, home heating oil no. 2 (Fuel C), and the pure hydrocarbon, n-dodecane, were subjected to mild oxidation at 130 C and the resulting oxygenated reaction products, deposit precursors, were analyzed using field ionization mass spectrometry. Results for fuel C indicated that, as oxidation was initially extended, certain oxygenated reaction products of increasing molecular weights in the form of monomers, dimers and some trimers were produced. Further oxidation time increase resulted in further increase in monomers but a marked decrease in dimers and trimers. This suggests that these larger molecular weight products have proceeded to form deposit and separated from the fuel mixture. Results for a dodecane indicated that yields for dimers and trimers were very low. Dimers were produced as a result of interaction between oxygenated products with each other rather than with another fuel molecule. This occurred even though fuel molecule concentration was 50 times, or more greater than that for these oxygenated reaction products.

Buttrill, S. E., Jr.↗

Precursor active galaxies, active galaxies and the X-ray and gamma-ray background

A description is presented of a model in which the X-ray and gamma-ray background can result from the superposition of radiation from active galaxies in different stages of their evolutionary history. This scheme is based on the generalization of a black-hole model developed for gamma-ray production in active galaxies by Leiter (1980). Both thermal and nonthermal accretion disk processes around massive rotating Kerr black holes are considered. Attention is given to cosmological conditions leading to precursor active galaxies (PAG), PAG as origin of the cosmic X-ray background, and the evolution of PAG into Seyfert galaxies as origin of the gamma-ray background. It is found that after spin-up of the central black hole an active galactic nucleus can generate nonthermal radiation very efficiently up to a few MeV.

Leiter, D.↗

Precursor gases of aerosols in the Mount St. Helens eruption plumes at stratospheric altitudes

Nineteen stratospheric samples from the eruption plumes of Mount St. Helens were collected in five flight experiments. The plume samples were collected at various altitudes from 13.1 to 20.7 km by using the Ames cryogenic sampling system on board the NASA U-2 aircraft. The enriched, cryogenically collected samples were analyzed by chromatography. The concentrations of aerosols precursor gases (OCS, SO2, and CS2), CH3Cl, N2O, CF2Cl2, and CFCl3 were measured by gas chromatography. Large enhancement of the mixing ratio of SO2 and moderate enhancement of CS2 and OCS were found in the plume samples compared with similar measurement under pre-volcanic conditions. A fast decay rate of the SO2 mixing ratio in the plume was observed. Measurement of Cl(-), SO2(2-), and NO3(-) by ion chromatography was also carried out on water solutions prepared from the plume samples. The results obtained with this technique imply large mixing ratios of HCl, (NO + NO2 + HNO3), and SO2, in which these constituents are the respective sources of the anions. Measurement of the Rn222 concentration in the plume was made. Other stratospheric constituents in the plume samples, such as H2O, CO2, CH4, and CO, were also observed.

Inn, E. C. Y.↗

Beryllium-10 in Australasian tektites - Evidence for a sedimentary precursor

Each of seven Australasian tektites contains about 100 micron atoms of beryllium-10 (half-life, 1.53 million years) per gram. Cosmic-ray bombardment of the australites cannot have produced the measured amounts of beryllium-10 either at the earth's surface or in space. The beryllium-10 contents of these australites are consistent with a sedimentary precursor that adsorbed from precipitation beryllium-10 produced in the atmosphere. The sediments must have spent several thousand years at the earth's surface within a few million years of the tektite-producing event.

Pal, D. K.↗

On the abiotic formation of amino acids. I - HCN as a precursor of amino acids detected in extracts of lunar samples. II - Formation of HCN and amino acids from simulated mixtures of gases released from lunar samples

Two studies on the abiotic formation of amino acids are presented. The first study demonstrates the role of hydrogen cyanide as a precursor of amino acids detected in extracts of lunar samples. The formation of several amino acids, including glycine, alanine, aspartic acid, and glutamic acid, under conditions similar to those used for the analysis of lunar samples is demonstrated. The second study investigates the formation of hydrogen cyanide as well as amino acids from lunar-sample gas mixtures under electrical discharge conditions. These results extend the possibility of synthesis of amino acids to planetary bodies with primordial atmospheres less reducing than a mixture of methane, ammonia, hydrogen and water.

Yuasa, S.↗

Silicon carbide-silicon nitride fibers: Preparation and characterization of polycarbosilazane precursors

This study examines the effect of modifications of the chemical structure of the monomers on the properties of the polymeric precursor and and ceramic fibers. A group of silaneamines, R'-Si (NH-R) sub 3, taken from the series where R' is methyl or phenyl and R is n-propyl, n-butyl, phenyl or allyl, are converted to polycarbosilazanes by heating in excess of 500 C. Resins obtained from this polymerization are characterized by NMR and IR spectroscopy and GPC. Each resin is tested for fiber-forming properties. Resin samples and fibers are hydrolytically cured. Thermogravimetric analyses are conducted on the cured resins to compare the relative thermal stability and examine the pyrolysis process. Cured fibers are tested for tensil strength.

Crouse, D. J.↗

Flare precursors and onset

A report on the progress of a search for precursors that have direct physical connections to the start of subsequent solar flares is presented. The discussion includes recent results at radio, visible, ultraviolet, and X-ray wavelengths, which are relevant to the preimpulsive (onset) phase. Relationships between various aspects of a theoretical scenario are also established, based on magnetic reconnection with transport-coefficient phase changes, in order to explain flare onset. The pertinent time scales for preimpulsive temporal developments are discussed.

Van Hoven, G.↗

Silsesquioxanes as precursors to ceramic composites

Silsesquioxanes having the general structure RSiO sub 1.5, where R = methyl, propyl, or phenyl, melt flow at 70 to 100 C. Above 100 C, free -OH groups condense. At 225 C further crosslinking occurs, and the materials form thermosets. Pyrolysis, with accompanying loss of volatiles, takes place at nominally 525 C. At higher temperatures, the R group serves as an internal carbon soruce for carbo-thermal reduction to SiC accompanied by the evolution of CO. By blending silsesquioxanes with varying R groups, both the melt rheology and composition of the fired ceramic can be controlled. Fibers can be spun from the melt which are stable in argon in 1400 C. The silsesquioxanes also were used as matrix precursors for Nicalon and alpha-SiC platelet reinforced composites.

Hurwitz, Frances I.↗

Petrology and precursors of lithic clasts from feldspathic fragmental breccia 67975

Textures and mineral chemistry (by INAA) of five lithic clasts, including both light green and light gray clasts, from feldspathic fragmental breccia 67975 were studied. The presence of five rock types was confirmed: feldspathic microporphyritic melt breccia, metamorphosed mafic-rich melt breccia with zoned and mantled clasts, 'typical' reequilibrated lunar feldspathic granulites with granoblastic texture and homogeneous mineral chemistry, hornfels, and a recrystallized mafic-rich granulite with relict igneous texture and the composition of a ferroan anorthositic norite. The mineralogy and textural data corroborate the grouping of the light green clasts proposed by Lindstrom (1984). However, the light gray clasts do not appear to be coherent in petrologic (or chemical) characteristics; one is a plagioclase-rich, possibly monomict rock with ferroan anorthositic precursor(s), and the other represents a mixture of feldspathic granulite and ferroan anorthositic norite lithologies.

Mcgee, James J.↗