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Polymerization technique using equimolar amounts of trifluoronitrosomethane and tetrafluoroethylene to increase yield of copolymer is described. Yields were increased by ninety percent and final product displayed better physical properties. Test equipment and chemical reactions for process are described.
A report describes experiments performed as part of a continuing investigation of the feasibility of laser ablation of materials as a means of propulsion for small spacecraft. In each experiment, a specimen of ablative material was mounted on a torsion pendulum and irradiated with a laser pulse having an energy of 5 J. The amplitude of the resulting rotation of the torsion pendulum was taken to be an indication of the momentum transferred from the laser beam. Of the ablative materials tested, aluminum foils yielded the smallest rotation amplitudes of the order of 10 degrees. Black coating materials yielded rotation amplitudes of the order of 90 degrees. Samples of silver coated with a fluorinated ethylene propylene (FEP) copolymer yielded the largest rotation amplitudes 6 to 8 full revolutions. The report presents a theory involving heating of a confined plasma followed by escape of the plasma to explain the superior momentum transfer performance of the FEP specimens. It briefly discusses some concepts for optimizing designs of spacecraft engines to maximize the thrust obtainable by exploiting the physical mechanisms of the theory. Also discussed is the use of laser-ablation engines with other types of spacecraft engines.
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.
Photolysis of cyanoacetylene with 185- or 206-nm light yields 1,3,5-tricyanobenzene while 254-nm radiation yields a mixture of tetracyanocyclooctatetraenes, 1,2,4- and 1,3,5-tricyanobenzene. A polymer of cyanoacetylene is the major photoproduct. 1,3,5-Tricarbomethoxybenzene was the only photoproduct identified from the irradiation of methyl propiolate at 254 nm. Mono-, di-, and tricyanobenzenes are formed by irradiation of mixtures of acetylene and cyanoacetylene at 185, 206, and 254 nm along with trace amounts of cyclooctatetraenes. No photoadducts were detected on photolysis of mixtures of cyanoacetylene and CO or HCN. The tetracyanocyclooctatetraene structures were established by UV, MS, and NMR analyses. The 1H NMR of the product mixture exhibited a singlet at delta 7.028 consistent with either 1 or 2 and two singlets at delta 6.85 and 6.91 assigned to 3. Photolysis of mixtures of dicyanoacetylene and acetylene with either 185- or 206-nm light yielded 1,2-dicyanobenzene and (E,Z)-1-buten-3-yne-1,4-dicarbonitrile. These products were also obtained using 254-nm light along with a mixture of tetracyanocyclooctatetraenes. The same three singlets were observed in this product mixture as were observed in the tetracyanocyclooctatetraenes obtained from cyanoacetylene. From this observation it was concluded that the delta 7.02 signal is due to 2 and not 1. The photolysis of cyanoacetylene and dicyanoacetylene in the presence of ethylene with 185-nm light yields 1-cyanocylobutene and 1,2-dicyanocyclobutene, respectively. 2-Cyanobutadiene and 2,3-dicyanobutadiene are the photoproducts with 254-nm light. Reaction pathways are proposed to explain these findings.
Experimental measurements have been obtained for the chemical yields of hydrogen cyanide, acetylene, ethylene, ethane, and propane from simulated lightning discharges, in order to ascertain whether lightning in the troposphere of Titan may be contributing to the hydrocarbon inventory. A comparison of these results with those obtained on the basis of thermodynamic equilibrium considerations shows substantial discrepancies and implies that thermodynamic equilibrium theories are inadequate. The production of ethylene by lightning and its subsequent stratospheric diffusion nevertheless appears to be one reasonable mechanism.
Titan has an atmosphere which is subject to dramatic chemical evolution due mainly to the dramatic effect of the UV flux from the Sun. The energetic solar photons and other particles are converting the methane-nitrogen atmosphere into the unsaturated carbon compounds observed by the Voyager probes. These same solar photons are also converting some of these unsaturated reaction products into the aerosols observed in the atmosphere which obscure the view of the surface of Titan. In particular, the photochemical reactions of cyanoacetylene, dicyanoacetylene, acetylene and ethylene may result in the formation of the higher hydrocarbons and polymers which result in the aerosols observed in Titan's atmosphere. Polymers are the principal reaction products formed by irradiation of cyanoacetylene and dicyanoacetylene. Irradiation of cyanoacetylene with 185 nm of light also yields 1,3,5-tricyanobenzene while irradiation at 254 nm yields 1,2,4-tricyanobenzene and tetracyano cyclooctatetraenes. Photolyses of mixtures of cyanoacetylene and acetylene yields mono- and di- cyanobenzenes. The 1-Cyanocyclobutene is formed from the photochemical addition of cyanoacetylene with ethylene. The photolysis of dicyanoacetylene with acetylene yields 2,3-dicyano-1,3-butadiene and 1,2-dicyanobenzene. Tetracyano cyclooctatetraene products were also observed in the photolysis of mixtures of dicyanoacetylene and acetylene with 254 nm light. The 1,2-Dicyano cyclobutene is obtained from the photolysis dicyanoacetylene and ethylene. Reaction mechanisms will be proposed to explain the observed photoproducts.
The extent of hydrogen atom exchange in the reaction, CH3(+) + CH4 yields C2H5(+) + H2, is determined by examining the product distribution for the reactions CH3(+) + CD4 and CD3(+) + CH4 as a function of relative kinetic energy from thermal energies to 10 eV. It is found that the reaction of CH4(+) with the parent neutral proceeds both via proton transfer and hydrogen abstraction accompanied by approximately 10% hydrogen atom exchange during the reaction.
The Polymers Experiment was exposed to the low Earth orbit (LEO) space environment for 2.14 and 2.0 years as part of the Materials International Space Station Experiment 8 (MISSE 8) and the Optical Reflector Materials Experiment-III (ORMatE-III), respectively. The experiment contained 42 samples, which were flown in either ram, wake, or zenith orientations. The primary objective was to determine the effect of solar exposure on the atomic oxygen erosion yield (Ey) of fluoropolymers. This paper provides an overview of the experiment with details on the polymers flown, the characterization techniques used, the atomic oxygen fluence for each exposure orientation, and the LEO Ey results. The Ey values for the fluoropolymers range from 1.45 x 10(exp -25) cm(exp 3)/atom for white Tedlar Registered Trademark (polyvinyl fluoride with white titanium dioxide pigment) flown in the ram orientation to 6.32 x 10(exp -24) cm(exp 3)/atom for aluminized-Teflon Registered Trademark fluorinated ethylene propylene (Al-FEP) flown in the zenith orientation. Erosion yield data for FEP flown in ram, wake and zenith orientations are compared, and the Ey was found to be highly dependent on orientation, hence environmental exposure. Teflon FEP had an order of magnitude higher Ey when flown in the zenith direction (6.32 x10(exp -24) cm(exp3)/atom) as compared to the ram direction (2.37 x 10(exp -25) cm(exp 3)/atom). The Ey of FEP was found to increase with a direct correlation to the solar exposure/AO fluence ratio showing the effect of solar radiation and/or heating due to solar exposure on FEP erosion. In addition, back-surface carbon painted FEP (C-FEP) flown in the zenith orientation had a significantly higher Ey than clear FEP or Al-FEP further indicating that heating has a significant impact on the erosion of FEP, particularly in the zenith orientation.
The Long Duration Exposure Facility (LDEF) spacecraft represents the first controlled unidirectional exposure of high-fluence atomic oxygen on fluorinated ethylene propylene (FEP Teflon) and silicones. The atomic oxygen erosion yield for FEP Teflon was found to be significantly in excess of previous low fluence orbital data and is an order of magnitude below that of polyimide Kapton. LDEF FEP Teflon erosion yield data as a function of angle of attack is presented. Atomic oxygen interaction with silicon polymers results in crazing of the silicones as well as deposition of dark contaminant oxidation products on adjoining surfaces. Documentation of results and possible mechanistic explanations are presented.
The Long Duration Exposure Facility (LDEF) spacecraft has enabled the measurement of the effects of fixed orientation exposure of high fluence atomic oxygen on fluorinated ethylene propylene (FEP Teflon) and silicones. The atomic oxygen erosion yield for the FEP Teflon was found to be 3.64 x 10(exp -25) cm(exp 3)/atom. This erosion yield is significantly higher than that measured from previous low fluence orbital data. The FEP Teflon erosion yield was found to have the same dependence on oxygen arrival angle as Kapton and Mylar. Atomic oxygen interaction with silicon polymers results in the crazing of silicon. Released silicone contaminants were found to darken upon further atomic oxygen exposure.
The atmosphere of Titan is known to contain aerosols, as evidenced by the Voyager observations of at least three haze layers. Such aerosols can have significant effects on the reflection spectrum of Titan and on the chemistry and thermal structure of its atmosphere. To investigate some of these effects laboratory simulations of the chemistry of Titan's atmosphere have been done. The results of these studies show that photolysis of acetylene, ethylene, and hydrogen cyanide, known constituents of Titan's atmosphere, yields sub-micron sized spheres, with mean diameters ranging from 0.4 to 0.8 micron, depending on the pressures of the reactant gases. Most of the spheres are contained in near-linear aggregates. The formation of the aggregates is consistent with models of Titan's reflection spectrum and polarization, which are best fit with non-spherical particles. At room temperature, the particles are very sticky, but their properties at low temperatures on Titan are presently not known.
The formation of the ethylene oxide molecular ion and its subsequent ion-molecule reactions leading to the products C2H5O(+) and C3H5O(+) have been studied using time-resolved photoionization mass spectroscopy, ion cyclotron resonance spectroscopy, and photoelectron spectroscopy. An examination of the effects of internal energy on reactivity shows that the ratio of C3H5O(+) to C2H5O(+) increases by an order of magnitude with a single quantum of vibrational energy. The formation of (C2H4O/+/)-asterisk in a collision-induced isomerization is found which yields a ring-opened structure by C-C bond cleavage. The relaxed ring-opened C2H4O(+) ion reacts with neutral ethylene oxide by CH2(+) transfer to yield an intermediate product ion C3H6O(+) which gives C3H5O(+) by loss of H.
Ethylene production by 10 or 20 m2 stands of wheat, soybean, lettuce, potato, and tomato was monitored throughout growth and development in an atmospherically closed plant chamber. Chamber ethylene levels varied among species and rose during periods of canopy expansion and rapid growth for all species. Following this, ethylene levels either declined during seed fill and maturation for wheat and soybean, or remained relatively constant for potato and tomato (during flowering and early fruit development). Lettuce plants were harvested during rapid growth and peak ethylene production. Chamber ethylene levels increased rapidly during tomato ripening, reaching concentrations about 10 times that measured during vegetative growth. The highest ethylene production rates during vegetative growth ranged from 1.6 to 2.5 nmol m-2 d-1 during rapid growth of lettuce and wheat stands, or about 0.3 to 0.5 nmol g-1 fresh weight per hour. Estimates of stand ethylene production during tomato ripening showed that rates reached 43 nmol m-2 d-1 in one study and 93 nmol m-2 d-1 in a second study with higher lighting, or about 50x that of the rate during vegetative growth of tomato. In a related test with potato, the photoperiod was extended from 12 to 24 hours (continuous light) at 58 days after planting (to increase tuber yield), but this change in the environment caused a sharp increase in ethylene production from the basal rate of 0.4 to 6.2 nmol m-2 d-1. Following this, the photoperiod was changed back to 12 h at 61 days and ethylene levels decreased. The results suggest three separate categories of ethylene production were observed with whole stands of plants: 1) production during rapid vegetative growth, 2) production during climacteric fruit ripening, and 3) production from environmental stress.
Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3 yields C3H5 + CH3. This reaction occurs even at moderate pressures of approx.200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(exp -3) - 10(exp 5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3 +/- 0.1.
Photodissociation channels and the final product yields from the 193 nm photolysis of propene-h6 (CH2=CHCH3) and propene-d6 (CD2=CDCD3) have been investigated, employing gas chromatography, mass spectroscopy, and flame ionization (GC/MS/FID) detection methods. The yields of methane as well as butadiene relative to ethane show considerable variations when propene-h6 or propene-d6 are photolyzed. This suggests significant variances in the relative importance of primary photolytic processes and/or secondary radical reactions, occurring subsequent to the photolysis. Theoretical calculations suggest the potential occurrence of an intramolecular dissociation through a mechanism involving vinylidene formation, accompanied by an ethylenic H-migration through the pi-orbitals. This process affects the final yields of methane-h4 versus methane-d4 with respect to other products. The product yields from previous studies of the 193 nm photolysis of methyl vinyl ketone-h6 and -d6 (CH2=CHCOCH3, CD2=CDCOCD3), alternative precursors for generating methyl and vinyl radicals, are compared with the current results for propene.
H Atoms have been created by the photolysis of H2S. These then initiated reactions in mixtures involving acetylene-ammonia-water and ethylene-ammonia-water. In the case of the acetylene system, the products consisted of two amino acids, ethylene and a group of primarily cyclic thio-compounds, but no free sulfur. In the case of the ethylene systems, seven amino acids, including an aromatic one, ethane, free sulfur, and a group of solely linear thio-compounds were produced. Total quantum yields for the production of amino acids were about 3 x 10 to the -5th and about 2 x 10 to the -4th with ethylene and acetylene respectively as carbon substrates. Consideration is given of the mechanism for the formation of some of the products and implications regarding planetary atmosphere chemistry, particularly that of Jupiter, are explored.
Addition-elimination reactions of S atom in its P-3 ground state with acetylene (C2H2) and ethylene (C2H4) were characterized with both molecular orbital and density functional theory calculations employing correlation consistent basis sets in order to assess the likelihood either reaction might play a general role in astrochemistry or a specific role in the formation of S2 (X (sup 3 SIGMA (sub g) (sup -)) via a mechanism proposed by Saxena and Misra (Mon. Not. R. Astron. Soc. 1995, 272, 89). The acetylene and ethylene reactions proceed through C2H2S ((sup 3)A")) and C2H4S ((sup 3)A")) intermediates, respectively, to yield HCCS ((sup 2)II)) and C2H3S ((sup 2)A')). Substantial barriers were found in the exit channels for every combination of method and basis set considered in this work, which effectively precludes hydrogen elimination pathways for both S + C2H2 and S + C2H4 in the ultracold interstellar medium where only very modest barriers can be surmounted and processes without barriers tend to predominate. However, if one or both intermediates is formed and stabilized efficiently under cometary or dense interstellar cloud conditions, they could serve as temporary reservoirs for S atom and participate in reactions such as S + C2H2S (right arrow) S2 = C2H2 or S + C2H4S (right arrow) S2 + C2H4. For formation and stabilization to be efficient, the reaction must possess a barrier height small enough to be surmountable at low temperatures yet large enough to prevent redissociation to reactants. Barrier heights computed with B3LYP and large basis sets are very low, but more rigorous QCISD(T) and RCCSD(T) results indicate that the barrier heights are closer to 3-4 kcal/mol. The calculations therefore indicate that S + C2H2 or S + C2H4 could contribute to the formation of S2 in comets and may serve as a means to gauge coma temperature. The energetics of the ethylene reaction are more favorable.
A large-eddy simulation / Reynolds-averaged Navier-Stokes (LES/RANS) methodology is used to simulate premixed ethylene-air combustion in a model scramjet designed for dual mode operation and equipped with a cavity for flameholding. A 22-species reduced mechanism for ethylene-air combustion is employed, and the calculations are performed on a mesh containing 93 million cells. Fuel plumes injected at the isolator entrance are processed by the isolator shock train, yielding a premixed fuel-air mixture at an equivalence ratio of 0.42 at the cavity entrance plane. A premixed flame is anchored within the cavity and propagates toward the opposite wall. Near complete combustion of ethylene is obtained. The combustor is highly dynamic, exhibiting a large-scale oscillation in global heat release and mass flow rate with a period of about 2.8 ms. Maximum heat release occurs when the flame front reaches its most downstream extent, as the flame surface area is larger. Minimum heat release is associated with flame propagation toward the cavity and occurs through a reduction in core flow velocity that is correlated with an upstream movement of the shock train. Reasonable agreement between simulation results and available wall pressure, particle image velocimetry, and OH-PLIF data is obtained, but it is not yet clear whether the system-level oscillations seen in the calculations are actually present in the experiment.