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At least 559 records · Page 31

Preparation of perfluorinated 1,2,4-oxadiazoles

Fluorinated alkyl or alkylether 1,2,4 oxadiazole compounds are prepared by cyclizing the corresponding alkyl or alkylether imidoyl amidoximes in vacuo or in an inert atmosphere at a temperature within the range of 40 C to 100 C. for a period of 8 to 144 hours in the presence of an acid compound which can accept ammonia to form a salt. The imidoyl amidoximes usable in this process are either polymeric or nonpolymeric. The products, when polymeric, have excellent heat, chemical and solvent resistance.

Kratzer, R. H.↗

Halogens in the atmosphere

Atmospheric halogen measurement data are presented for: (1) inorganic and organic gaseous compounds of chlorine, fluorine, bromine and iodine; and (2) chloride, fluoride, bromide and iodine in particulate form and in precipitation. The roles that these data and other, unavailable data play in the determination of the global cycles of the halogens are discussed. It is found that the speciation of the halogen gases in the troposphere is uncertain, with the only inorganic species detected by species-specific methods being HC1 and SF6. It is shown that heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes, need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, quantitative comparisons are made between measured and predicted concentrations.

Cicerone, R. J.↗

Synthesis of perfluorinated polyethers

A series of highly fluorinated acetylenes was prepared and their cyclization reactions were studied. A series of perfluoropolytriazines with -CF2I pendent groups were prepared. These materials can be cured thermally or photochemically to an elastomeric gum. Perfluoropolytriazines with -CN pendent groups were prepared. These materials can be crosslinked by reaction with terephthalonitrile oxide.

Depasquale, R. J.↗

An investigation of adhesive/adherend and fiber/matrix interactions. Part B: SEM/ESCA analysis of fracture surfaces

Adhesion was studied with emphasis on the characterization of surface oxide layers, the analysis of fracture surfaces, and the interaction of matrices and fibers. A number of surface features of the fractured lap shear samples were noted in the SEM photomicrographs including the beta phase alloy of the Ti 6-4 adherend, the imprint of the adherend on the adhesive failure surface, increased void density for high temperature samples, and the alumina filler particles. Interfacial failure of some of the fractured lap shear samples is invariably characterized by the appearance of an ESCA oxygen photopeak at 530.3 eV assigned to the surface oxide layer of Ti 6-4 adherend. The effect of grit blasting on carbon fiber composites is evident in the SEM analysis. A high surface fluorine concentration on the composite surface is reduced some ten fold by grit blasting.

Beck, B.↗

Research on planetary samples

Sputtering yields of solid SO2 by high energy ions were measured in order to study the mechanism for sputtering dielectrics with ions in the electronic stopping power region. The incident ions were helium and fluorine with energies ranging from 1.5 MeV to 25 MeV. Yields as high as 7000 SO2 molecules/incident F ion were measured; the 1.5 MeV He4 beam had a sputtering yield of 50. The data are compared to yield measurements made on UF4 and H2O targets. There is a striking similarity in the yield as a function of the Energy for all three targets. The data compare favorably with theoretical curves based on a model for the sputtering which considers the electronic excitations induced the target by the incident beam. Measurements and calculations of the sort are also useful in understanding processes which occur on the surface of Jupiter's satellite Io, which is covered with SO2 frost and bombarded by energetic ions trapped in the Jovian magnetosphere.

Tombrello, T. A.↗

A review of liquid lubricant thermal/oxidative degradation

The fundamental processes occurring during the thermal and oxidative degradation of hydrocarbons are reviewed. Particular emphasis is given to various classes of liquid lubricants such as mineral oils, esters, polyphenyl ethers, C-ethers, and fluorinated polyethers. Experimental techniques for determining thermal and oxidative stabilities of lubricants are discussed. The role of inhibitors and catalysis is also covered.

Jones, W. R., Jr.↗

Sputtering of SO2 by high energy ions

Sputtering yields of solid SO2 by high energy ions were measured in order to study the mechanism for sputtering dielectrics with ions in the electronic stopping power region. The incident ions were helium and fluorine with energies ranging from 1.5 MeV to 25 MeV. Yields as high as 7000 SO2 molecules/incident F ion were measured; the 1.5 MeV He-4 beam had a sputtering yield of 50. The data are compared to yield measurements made on UF4 and H2O targets. There is a striking similarity in the yield as a function of the incident F energy for all three targets. The data compare favorably with theoretical yield curves based on a new model for the sputtering which considers the electronic excitations induced in the target by the incident beam. Measurements and calculations of this sort are also useful in understanding processes which occur on the surface of Jupiter's satellite Io, which is covered with SO2 frost and bombarded by energetic ions trapped in the Jovian magnetosphere.

Lepoire, D. J.↗

Preventing Fires in Cryogenic Oxidizer Lines

Friction and compression induced ignition prevented by heat-dissipation layer. Thin layer of copper placed inside surfaces of pipes and other parts in contact with flowing liquid oxygen, fluorine, or other oxidizers. Copper layer of only 0.001 to 0.005 inch (0.0254 to 0.127 mm) ensures heat away from hotspots thereby discouraging ignition. Copper layer increases oxygen ignition threshold of pipe by 5 to 20 times.

Wagner, W. R.↗

Structure-activity correlations for organophosphorus ester anticholinesterases. Part 2: CNDO/2 calculations applied to ester hydrolysis rates

Quantitative structure-activity relationships are presented for the hydrolysis of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. CNDO/2 calculations provide values for molecular parameters that correlate with alkaline hydrolysis rates. For each subset of esters with the same leaving group, X, the CNDO-derived net atomic charge at the central phosphorus atom correlates well with the alkaline hydrolysis rate constants. For the whole set of esters with different leaving groups, equations are derived that relate charge, orbital energy and bond order to the hydrolysis rate constants.

Johnson, H.↗

Thermal and Oxidative Stabilities of Liquid Lubricants

The fundamental processes which occur during the thermal and oxidation degradation of hydrocarbons is reviewed. Various classes of liquid lubricants such as mineral oils, esters, polyphenyl ethers, C-ethers, and fluorinated polyethers are emphasized. Techniques to determine thermal and oxidative stabilities of lubricants are discussed. The role of inhibitors and catalysis is examined.

Jones, W. R., Jr.↗

Evaluation of two polyimides and of an improved liner retention design for self-lubricating bushings

Two different polyimide polymers were studied and the effectiveness of a design feature to improve retention of the self lubricating composite liners under high load was evaluated. The basic bearing design consisted of a molded layer of chopped graphite-fiber-reinforced-polyimide (GFRP) composite bonded to the bore of a steel bushing. The friction, wear, and load carrying ability of the bushings were determined in oscillating tests at 25, 260 and 315 C at radial unit loads up to 260 MPa. Friction coefficients were typically 0.15 to 0.25. Bushings with liners containing a new partially fluorinated polymer were functional, but had a lower load capacity and higher wear rate than those containing a more conventional, high temperature polyimide. The liner retention design feature reduced the tendency of the liners to crack and work out of the contact zone under high oscillating loads.

Sliney, H. E.↗

Improved high temperature resistant matrix resins

The objective was to develop organic matrix resins suitable for service at temperatures up to 644 K (700 F) and at air pressures up to 0.4 MPa (60 psia) for time durations of a minimum of 100 hours. Matrix resins capable of withstanding these extreme oxidative environmental conditions would lead to increased use of polymer matrix composites in aircraft engines and provide significant weight and cost savings. Six linear condensation, aromatic/heterocyclic polymers containing fluorinated and/or diphenyl linkages were synthesized. The thermo-oxidative stability of the resins was determined at 644 K and compressed air pressures up to 0.4 MPa. Two formulations, both containing perfluoroisopropylidene linkages in the polymer backbone structure, exhibited potential for 644 K service to meet the program objectives. Two other formulations could not be fabricated into compression molded zero defect specimens.

Chang, G. E.↗

Photovoltaic module encapsulation design and materials section, volume 2

Tests for chemical structure, material properties, water absorption, aging and curing agent of Ethylene Vinyl Acetate (EVA) and UV absorption studies are carried out. A computer model was developed for thermal optical modeling, to investigate dependence between module operating temperature and solar insolation, and heat dissapation behavior. Structural analyses were performed in order to determine the stress distribution under wind and heat conditions. Curves are shown for thermal loading conditions. An electrical isolation was carried out to investigate electrical stress aging of non-metallic encapsulation materials and limiting material flaws, and to develop a computer model of electrical fields and stresses in encapsulation materials. In addition, a mathematical model was developed and tests were conducted to predict hygroscopic and thermal expansion and contraction on a plastic coated wooden substrate. Thermal cycle and humidity freezing cycle tests, partial discharge tests, and hail impact tests were also carried out. Finally, the effects of soiling on the surface of photovoltaic modules were investigated. Two antisoiling coatings, a fluorinated silane and perflourodecanoic acid were considered.

Cuddihy, E. F.↗

Fire- and heat-resistant laminating resins based on maleimido-substituted aromatic cyclotriphosphazenes

A novel class of flame- and heat-resistant polymers has been synthesized by the thermal polymerization of maleimido-substituted aromatic cyclotriphosphazenes. The polymer obtained from tris-(aminophenoxy)tris(maleimidophenoxy)cyclotriphosphazene has good thermal stability and is noteworthy for its high char yield, viz., 82 percent at 800 C in nitrogen and 81 percent at 700 C in air. Graphite-fabric laminates prepared with this polymer did not burn in pure oxygen, even at 300 C, and were tested for mechanical properties. Hexakis(4-maleimidophenoxy)cyclotriphosphazene and some fluorine-containing monomers have also been synthesized. The structures of these cyclic phosphazene precursors and polymers were characterized by FT IR spectrophotometry, H-1 NMR, F-19 NMR, and P-31 solid-state magic angle spinning NMR spectroscopy, and mass spectrometry. The curing behavior of the polymer precursors and the thermal stabilities of the polymers were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA).

Kumar, D.↗

Latitudinal distributions and temporal changes of stratospheric HCl and HF

Hydrogen chloride and hydrogen fluoride are important sinks in the stratosphere for free halogens. The major sources of chlorine and fluorine in the stratosphere are anthropogenic; therefore, a measurement of HCl and HF gives information about the magnitude of anthropogenic effects on stratospheric chemistry and may give some information about the stratospheric hydroxyl concentration as well. The total column amount of HCl and HF above 12 km has been determined by measuring infrared absorption spectra with a high-resolution Fourier transform spectrometer flown on a jet aircraft. The HCl column varies from 0.7 x 10 to the 15th molecules/ sq cm near the equator to 2.7 x 10 to the 15th molecules/sq cm at 70 N; the HF column is about a factor of 5 lower. The HCl:HF ratio is almost independent of latitude, and neither constituent shows substantial seasonal or diurnal variation. At mid-latitudes, the data from 1978 to 1982 show an annual increase of 5 percent per year for HCl and 12 percent per year for HF.

Mankin, W. G.↗

Elemental composition of arctic particulate matter

Measurements were made of the elemental composition of particulate matter collected in flights in the Arctic in spring 1983 as part of the Arctic Gas and Aerosol Sampling Program (AGASP). Ten samples of size-selected particles were analyzed by four nondestructive techniques at Davis. Concentrations were determined for H, C, N, and O by Forward Alpha Scattering Techniques (FAST) and for elements heavier than fluorine by Particle Induced X-ray Emission (PIXE). Total mass was measured gravimetrically, and optical absorption was measured using the Laser Integrating Plate Method (LIPM). Results of the analyses show dramatic differences in concentrations and elemental ratios from the Alaskan Arctic to the Norwegian Arctic, with indications of wood smoke and sulfuric acid in the arctic atmosphere.

Cahill, T. A.↗

A measurement of the vibrational band strength for the v3 band of the HO2 radical

Laboratory measurements of the v(3) band strength of HO2 using a tunable diode laser to measure the absorption strength of a vibration-rotation line in the P branch near 1080/cm are reported. The HO2 is generated in a discharge-flow system by reaction of fluorine atoms with excess H2O2: F + H2O2 - HO2 + HF. The HO2 concentration is determined from measurements of F-atom concentrations using both chemical titration with Cl2 and tunable diode laser absorption by the F-atom spin-orbit transition near 404/cm. The experimental data are consistent with a value of k(3) = (1.6 + or - 0.3) x 10 to the 12th cu cm/s and a ratio k(4)/k(1) = 1.0 + or - 0.4. The line strength for the 6(15) - 7(16)F(1) transition is 2.9 x 10 to the -21 sq cm/molecule/cm, which corresponds to a v(3) band strength of 35 + or - 9/sq cm/(STP atm). This value is a factor of 1.6 to 6 lower than previous ab initio calculations.

Zahniser, M. S.↗

Experimental determination of geomagnetically trapped energetic heavy ion fluxes

The observed spatial, directional and spectral characteristics of geomagnetically trapped heavy ions are reviewed. It is found that ions heavier than protons are significantly abundant in the earth's radiation belts, not only at low (ring-current) energies, but also at multi-MeV energies. Observations both at the geomagnetic equator and at low altitudes on the corresponding L-shell show the important roles played by the heavy ions. The heavy ion-to-proton flux ratio can exceed unity when compared at equal total ion energy. This is particularly the case at several MeV energies and in the outer radiation zone. In contrast, comparisons at equal energy per nucleon generally favor protons. The trapped fluxes of helium ions, of carbon, nitrogen and oxygen (CNO) ions, and of ions heavier than fluorine all exhibit high degrees of pitch angle anisotropy. Many of the observed radiation belt particle distribution characteristics are in agreement with first-order (quiet time) theoretical predictions, although some of the finer details await further research.

Spjeldvik, W. N.↗