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At least 19 records

Determination of aromatics and olefins in wide-boiling petroleum fractions

A chromatographic method is described herein for the analysis of aromatics and olefins in wide boiling petroleum fractions. The fuel is split into four fractions: nonaromatic, intermediate, pure aromatic, and wash. The analysis, which need be run only on the intermediate cut to determine aromatics in the fuel, is based on specific dispersion. With analysis times of less than 8 hours, accuracies of 1 percent were attained.

FUELS - TURBINE ENGINES, RAM JETS, AND PULSE JETS↗

Photochemical preparation of olefin addition catalysts

Novel polymer supported catalysts are prepared by photo-irradiation of low valent transition metal compounds such as Co.sub.2 (CO).sub.8, Rh.sub.4 (CO).sub.12 or Ru.sub.3 (CO).sub.12 in the presence of solid polymers containing amine ligands such as polyvinyl pyridine. Hydroformylation of olefins to aldehydes at ambient conditions has been demonstrated.

Gray, Harry B.↗

Evaluation of Cyclo Olefin Polymer as Sabot Material for High-Density Projectiles

Assuring the integrity of spacecraft and its occupants are a priority in the field of space exploration. Micrometeoroids and orbital debris are one of the primary threats that affect spacecraft materials due to the high kinetic energies involved with hypervelocity impacts. Improvement of projectile launching capabilities prompts the investigation of adequate materials for the manufacturing of sabots able to carry high-density projectiles without catastrophic failure. Polycarbonate has been the chosen material by the Hypervelocity Team at White Sands Test Facility for sabots on the 0.50 caliber launcher; however, there is a material constraint when the projectile becomes significantly dense and the inertial stresses surpass the yield strength of the sabot material. This research proposes a new polymer material for manufacturing sabots, known as cyclo olefin polymer (COP) with the purpose of successfully shooting the intended high-density projectiles. In this investigation, both polycarbonate and COP were analyzed using tensile and impact testing to observe the differences in their mechanical properties. The experimental details along with the detailed characterization of the materials are presented.

Tarango, Estebanne↗

Far-Infrared Properties of Cyclic Olefin Copolymer

Cyclic olefin copolymer (COC) is an amorphous thermoplastic with desirable dielectric and mechanical characteristics for optical applications. In particular, its low refractive index, overall mechanical strength, and absence of strong absorption features make it a promising substrate material for far-infrared applications, which include frequency-selective surfaces, scattering filters, and windows. The dielectric properties of selected COC formulations are surveyed from ≈10−700 per.cm (1000−14µm), and representative usage as a thin film membrane structure in optical filters is presented.

Wollack, Edward J.↗

Activation energies for addition of O/3P/ to simple olefins.

Description of relative rate measurements for the addition of O(3P) to C2H4, C2F4, C3H6, and C4H8-1 in liquid argon at 87.5 K. The data strongly indicate that the activation energies for the addition of O(3P) to the double bonds of propylene and butene-1 are identical, probably to within 0.1 kcal/mole. It is very doubtful that differences in pre-exponential factors or other factors such as solvent effects, could invalidate this conclusion. A similar argument holds for the C2H4 and C2F4 reactions. Furthermore, the experiments suggest that the activation energy for addition of O(3P) to the double bond of butene-1 is about 0.1 kcal/mole.

Demore, W. B.↗

Relative Rates for Plasma Homo- and Copolymerizations of Olefins in a Homologous Series of Fluorinated Ethylenes

The relative rates of plasma (co)polymerizations of ethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene and tetrafluoroethylene (VF(sub x); x = 0-4, respectively) were determined in an rf, capacitively coupled, tubular reactor with external electrodes using identical plasma parameters. The averages of deposition rates obtained by both microgravimetry and ellipsometry were plotted versus the F/C ratios of the monomers or monomer blends. The deposition rates for VF(sub x)(x = 1-3) and 20 monomer blends were all located above a straight line joining the rates for VF(sub 0) and VF(sub 4), following a concave-downward plot of deposition rate versus F/C ratio similar to that reported previously for VF(sub 0)/VF(sub 4) blends. The deposition rates for VF(sub m)/VF(sub n) blends (m = 3 or 4; n = 0-2) were all greater than expected for non-interacting monomers; those for VF(sub 0)/VF(sub 2) and VF(sub 1)/VF(sub 2) blends were all lower than expected; while those for VF(sub 0)/VF(sub 1) and VF(sub 3)/VF(sub 4) blends fen on a straightline plot versus F/C ratio, indicative of apparent non-interaction between monomers. The mechanisms for plasma (co)polymerizations of VF(sub x) monomers responsible for the wide range of relative deposition rates remain to be elucidated.

Golub, Morton A.↗

Relative rates for plasma homo- and copolymerizations of olefins in a homologous series of fluorinated ethylenes

It is well known that the rate of plasma polymerization, or deposition rate, of a given monomer depends on various plasma process parameters, e.g., monomer flow rate, pressure, power, frequency (DC, rf or microwave), location of the substrate in the reactor, reactor geometry or configuration, and temperature. In contrast, little work has been done to relate deposition rates to monomer structures for a homologous series of monomers where the rates are obtained under identical plasma process parameters. For the particular series of fluorinated ethylenes (C2HxF4-x; x = 0-4), deposition rates were reported for ethylene (ET), vinyl fluoride, vinylidene fluoride and tetrafluoroethylene (TFE), but for plasma polymerizations carried out under different discharge conditions, e.g., pressure, current density, and electrode temperature. Apparently, relative deposition rates were reported for only two members of that series (ET, x = 4, and TFE, x = 0) for which the plasma polymerizations were conducted under identical conditions. We now present relative deposition rates for both homopolymerizations and copolymerizations of the entire series of fluorinated ethylenes (x = 0-4). Our interest in such rates stems from prior work on the plasma copolymerization of ET and TFE in which it was found that the deposition rates for the plasma copolymers, when plotted versus mol % TFE in the ET/TFE feed stock, followed a concave-downward curve situated above the straight line joining the deposition rates for the plasma homopolymers. This type of plot (observed also for an argon-ET/TFE plasma copolymerization) indicated a positive interaction between ET and TFE such that each monomer apparently "sensitized" the plasma copolymerization of the other. Since the shape of that plot is not altered if mol % TFE is replaced by F/C, the fluorine-to-carbon ratio, this paper aims (1) to show how the relative deposition rates for plasma copolymers drawn from all pairs of monomers in the C2HxF4-x series, as well as the deposition rates for the individual plasma homopolymers, vary with F/C ratios of the monomers or monomer blends, and (2) to see if those rates give rise to a common plot.

NASA Center ARC↗

Group-type hydrocarbon standards for high-performance liquid chromatographic analysis of middistillate fuels

A new high-performance liquid chromatographic (HPLC) method for group-type analysis of middistillate fuels is described. It uses a refractive index detector and standards that are prepared by reacting a portion of the fuel sample with sulfuric acid. A complete analysis of a middistillate fuel for saturates and aromatics (including the preparation of the standard) requires about 15 min if standards for several fuels are prepared simultaneously. From model fuel studies, the method was found to be accurate to within 0.4 vol% saturates or aromatics, and provides a precision of + or - 0.4 vol%. Olefin determinations require an additional 15 min of analysis time. However, this determination is needed only for those fuels displaying a significant olefin response at 200 nm (obtained routinely during the saturated/aromatics analysis procedure). The olefin determination uses the responses of the olefins and the corresponding saturates, as well as the average value of their refractive index sensitivity ratios (1.1). Studied indicated that, although the relative error in the olefins result could reach 10 percent by using this average sensitivity ratio, it was 5 percent for the fuels used in this study. Olefin concentrations as low as 0.1 vol% have been determined using this method.

Otterson, D. A.↗

Infrared spectroscopy for the determination of hydrocarbon types in jet fuels

The concentration of hydrocarbon types in conventional jet fuels and synfuels can be measured using a computerized infrared spectrophotometer. The computerized spectrophotometer is calibrated using a fuel of known aromatic and olefinic content. Once calibration is completed, other fuels can be rapidly analyzed using an analytical program built into the computer. The concentration of saturates can be calculated as 100 percent minus the sum of the aromatic and olefinic concentrations. The analysis of a number of jet fuels produced an average standard deviation of 1.76 percent for aromatic types and one of 3.99 percent for olefinic types. Other substances such as oils and organic mixtures can be analyzed for their hydrocarbon content.

Buchar, C. S.↗

High performance liquid chromatographic hydrocarbon group-type analyses of mid-distillates employing fuel-derived fractions as standards

Two high performance liquid chromatographic (HPLC) methods have been developed for the determination of saturates, olefins and aromatics in petroleum and shale derived mid-distillate fuels. In one method the fuel to be analyzed is reacted with sulfuric acid, to remove a substantial portion of the aromatics, which provides a reacted fuel fraction for use in group type quantitation. The second involves the removal of a substantial portion of the saturates fraction from the HPLC system to permit the determination of olefin concentrations as low as 0.3 volume percent, and to improve the accuracy and precision of olefins determinations. Each method was evaluated using model compound mixtures and real fuel samples.

Seng, G. T.↗

Photosensitized oxidation of unsaturated polymers

The photosensitized oxidation or singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds was reviewed. Emphasis was on cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene), and on 1,4-poly(2,3-dimethyl-1,3-butadiene). The microstructural changes which occur in these polymers on reaction with O2-1 in solution were investigated by infrared H-1 and C-13 NMR spectroscopy. The polymers were shown to yield allylic hydroperoxides with shifted double bonds according to the ene mechanism established for simple olefins. The photosensitized oxidation of the above unsaturated polymer exhibited zero order kinetics, the relative rates paralleling the reactivities of the corresponding simple olefins towards O2-1.

Golub, M. A.↗