The photolysis of N2O at 1470 A. Ionospheric research
Photolysis of nitrogen oxide, nitrogen oxide/ nitrogen mixtures, and nitrogen olefin mixtures
Dodge, M. C.↗
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Materials investigation and tests for the development of space compatible electrical connectors
A molding study of compounds based on copolymers of highly fluorinated olefins and of flame retardant silicone is reported. Both single cavity and four cavity molds having size 22 and 24 holes with three webs in each hole were used. Also covered are dielectric strength, arc resistance, Bashore rebound, and maintenance aging tests on the various materials that have been successfully molded.
Pomeroy, C.↗
Some current problems in oxidation kinetics
Experimental data in low temperature and high temperature oxidations are examined from the point of view of reported quantitative inconsistencies. Activation energies for tBuO2 metathesis reactions with alkanes appear to be 7 kcal/mole higher than for comparable reactions of HO2. Related isomerization reactions are examined in the light of these differences without reaching any simple conclusions. The Russell mechanism for a 6-membered, cyclic, transition state for termination of primary and secondary alkyl peroxy radicals is shown to be either inconsistent with thermochemical data, or else unique to solution reactions. Addition reactions of O3 with olefins and acetylenes are shown thermochemically to have the possibility of following concerted and biradical pathways, respectively. Recent data showing strong inhibition by PbO coated surfaces of both oxidation and pyrolysis of i-C4H10 are examined in terms of mechanism.
Benson, S. W.↗
Study of the organic matter in the DSDP /JOIDES/ cores, legs 10-15
The composition of the organic matter collected on legs 10 to 15 of the DSDP (Deep Sea Drilling Project) is described. Distributions of various alkanes, carboxylic acids, steroids and terpenoids, isoprenoid ketones and olefins, and aromatic polycyclic compounds are given. Samples analyzed had terrigenous clay components, with variable organic carbon contents and thus diverse solvent soluble matter. The distribution patterns for the various compound series monitored were of marine derivation, with the terrigenous components superimposed. Diagenesis of steroids appeared to proceed via both stanones and stanols to their respective steranes. Degradative processes were observed to be operative: oxidative products, mainly ketones derived from steroids and phytol, were identified, probably due to microbial alteration prior to or during sedimentation. Loss of alkane and fatty acid C preferences and presence of polycyclic aromatics evinced maturation. Results indicate that the accumulation, degradation, diagenesis and maturation of organic matter occurs in various steps in the deep sea environment.
Simoneit, B. R. T.↗
Novel aminobenzyl and imidobenzyl benzenes
Compounds are useful as intermediates for several classes of polymers. Amines can function as cross-linking agents for epoxide and urethane polymers, as well as intermediates for synthesis of thermally-stable addition-type polyimides. Imide derivatives can be obtained by reacting amines with certain monoanhydrides containing olefinic unsaturation.
Bell, V. L.↗
Catalysts for low-energy aldehyde processes
Photochemical reaction of dicobalt octacarbonyl with polymeric support systems results in formation of polymer bonded metal catalyst. Catalyst is used in hydroformylation (addition of carbon dioxide and hydrogen) of olefins to yield aldehydes.
Gupta, A.↗
Flame and acid resistant polymide fibers
Economical process improves flame resistance and resistance to acids of polyamide fibers, without modifying colors of mechanical properties. Process improves general safety of garments and other items made from polyamide fibers and makes them suitable for applications requiring exposure to oxygen-rich atmosphere or corrosive acids. Halo-olefins are added to surface of fibers by photoadditon in sealed chamber. Process could be used with films and other forms of polyamide.
Stringham, R. S.↗
Chemical kinetics of homogeneous atmospheric oxidation of sulfur dioxide
A systematic evaluation of known homogeneous SO2 reactions which might be important in air pollution chemistry is carried out. A mechanism is developed to represent the chemistry of NOx/hydrocarbon/SO2 systems, and the mechanism is used to analyze available experimental data appropriate for quantitative analysis of SO2 oxidation kinetics. Detailed comparisons of observed and predicted concentration behavior are presented. In all cases, observed SO2 oxidation rates cannot be explained solely on the basis of those SO2 reactions for which rate constants have been measured. The role of ozone-olefin reactions in SO2 oxidation is elucidated.
Sander, S. P.↗
Nuclear alkylated pyridine aldehyde polymers and conductive compositions thereof
A thermally stable, relatively conductive polymer was disclosed. The polymer was synthesized by condensing in the presence of catalyst a 2, 4, or 6 nuclear alklylated 2, 3, or 4 pyridine aldehyde or quaternary derivatives thereof to form a polymer. The pyridine groups were liked by olefinic groups between 2-4, 2-6, 2-3, 3-4, 3-6 or 4-6 positions. Conductive compositions were prepared by dissolving the quaternary polymer and an organic charge transfer complexing agent such as TCNQ in a mutual solvent such as methanol.
Rembaum, A.↗
High performance, high density hydrocarbon fuels
The fuels were selected from 77 original candidates on the basis of estimated merit index and cost effectiveness. The ten candidates consisted of 3 pure compounds, 4 chemical plant streams and 3 refinery streams. Critical physical and chemical properties of the candidate fuels were measured including heat of combustion, density, and viscosity as a function of temperature, freezing points, vapor pressure, boiling point, thermal stability. The best all around candidate was found to be a chemical plant olefin stream rich in dicyclopentadiene. This material has a high merit index and is available at low cost. Possible problem areas were identified as low temperature flow properties and thermal stability. An economic analysis was carried out to determine the production costs of top candidates. The chemical plant and refinery streams were all less than 44 cent/kg while the pure compounds were greater than 44 cent/kg. A literature survey was conducted on the state of the art of advanced hydrocarbon fuel technology as applied to high energy propellents. Several areas for additional research were identified.
Frankenfeld, J. W.↗
Rates of the reactions of 1, 1, 1-trichloroethane /methyl chloroform/ and 1, 1, 2-trichloroethane with OH
Highly purified samples of the two chlorocarbons, trichloroethane and methyl chloroform, were reacted with OH over the temperature range of 278 to 460 K in a discharge-flow system with resonance flourescence detection of OH. Attention is given to the data obtained at various temperature levels and to the graph of Arrhenius' diagram. It is determined that the methyl chloroform reaction was slower and its temperature dependence somewhat steeper than the earlier measurements had indicated, probably due to the presence of faster reacting olefinic impurities in prior studies. Implications for stratospheric ozone reductions by C10-sub-x catalysis and for tropospheric OH-budget are briefly discussed.
Jeong, K.-M.↗
Photosensitized oxidation of unsaturated polymers
A review of the photosensitized oxidation of singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds is presented. The cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene) are studied, and their microstructural changes which occur on reaction with (IO2) in solution were investigated by infrared, (H-1) and (C-13) NMR spectroscopy. The polymers yielded allylic hydroperoxides with shifted double bonds according to the 'ene' mechanism of simple olefins. It was shown that single oxygenation of unsaturated polymers is similar to their low molecular weight analogs, and that the differences are due to secondary processes affecting the (IO2)-reacted polymers.
Golub, M. A.↗
Spectroscopic study of the effect on an EHD contact of trichloroethane addition to a traction fluid
Addition of trichloroethane to a traction fluid was studied in a ball/diamond plate EHD apparatus by infrared emission spectroscopy of the radiation transmitted through the plate. Small concentrations of an organic chloride at first increased infrared radiance, then decreased it. Large concentrations caused a rapid decrease. During running, the infrared spectrum showed an increase of aromatics and olefins. A polymeric deposit formed on the plate. X-ray examination of the ball surface showed the presence of chlorine. Reuse of the same ball with fresh fluid resulted in similar chain of events, indicating that adsorbed chloride could promote fluid deterioration.
Lauer, J. L.↗
Improved Fire-Resistant Resins for Laminates
Fire-resistant resins for fabricating laminates with inorganic fibers, especially graphite fibers, are formed from bisimides containing main-chain phosphorus and olefinic end groups. Bisimides are thermally polymerized to form resins and laminates virtually imcombustible in pure oxygen at 300 degrees C. New resins are suitable for many applications requiring good adhesion and excellent resistance to heat, fire, solvents and chemicals.
Fohlen, G. M.↗
Composition and method for making polyimide resin-reinforced fabric
A composition for making polyimide resin reinforced fibers or fabric is discussed. The composition includes a polyfunctional ester, a polyfunctional amine, and an end capping agent. The composition is impregnated into fibers or fabric and heated to form prepreg material. The tack retention characteristics of this prepreg material are improved by incorporating into the composition a liquid olefinic material compatible with the other ingredients of the composition. The prepreg material is heated at a higher temperature to effect formation of the polyimide resin and the monomeric additive is incorporated in the polyimide polymer structure.
Serafini, T. T.↗
Determination of physical and chemical states of lubricants in concentrated contacts, part 2
Infrared emission spectroscopy through a window in an operating bearing continued to provide most of the information gathered on the state of lubricants subjected to elastohydrodynamic (EHD) conditions. Other measurements were traction, scanning electron microscopy and elemental surface analysis X-rays. A very significant finding was the decomposition of a naphthenic oil lubricant in the presence of small concentrations of an organic chloride. Olefins and aromatics were formed in ever increasing amounts prior to total lubricant failure. An aromatic fluid also failed in the presence of chloride. A correlation was found between changes of the alignment of lubricant molecules evidence by infrared polarization and changes of traction under varying EHD stresses.
Lauer, J. L.↗
The photochemistry of anthropogenic nonmethane hydrocarbons in the troposphere
A lumped, nonmethane hydrocarbon (NMHC) chemical mechanism is presently applied to a one-dimensional photochemical model of the troposphere. The profiles of OH, HO2, NO(x), and HNO3, showed only slight changes when NMHC chemistry was added. The integrated column of peroxyacetylnitrate (PAN), when NMHC chemistry was included, comprised 17 percent of the odd nitrogen budget. Advection is noted as an important possible mechanism for the removal of PAN at midlatitudes. The inclusion of such intermediate lifetime species as aldehydes and olefins has both provided additional sources of short-lived NMHC radicals, such as the peroxyacetyl radical that is the radical precursor of PAN, and offered a more detailed description of the concentrations of short-lived species and the overall NMHC chemistry.
Brewer, D. A.↗
Research on aviation fuel instability
Current aircraft turbine fuels do not present a significant problem with fuel thermal stability. However, turbine fuels with broadened properties or nonpetroleum derived fuels may have reduced thermal stability because of their higher content of olefins, heteroatoms, and trace metals. Moreover, advanced turbine engines will increase the thermal stress on fuels because of their higher pressure ratios and combustion temperature. In recognition of the importance of this problem, NASA Lewis is currently engaged in a broadly based research effort to better understand the underlying causes of fuel thermal degradation. The progress and status of our various activities in this area are discussed. Topics covered include: nature of fuel instability and its temperature dependence, methods of measuring the instability, chemical mechanisms involved in deposit formation, and instrumental methods for characterizing fuel deposits. Finally, some preliminary thoughts on design approaches for minimizing the effects of lowered thermal stability are briefly discussed.
Baker, C. E.↗