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At least 73 records · Page 4

Adhesive and composite evaluation of acetylene-terminated phenylquinoxaline resins

A series of acetylene-terminated phenylquinoxaline (ATPQ) oligomers of various molecular weights were prepared and subsequently chain extended by the thermally induced reaction of the ethynyl groups. The processability and thermal properties of these oligomers and their cured resins were compared with that of a relatively high molecular weight linear polyphenylquinoxaline (PPQ) with the same chemical backbone. The ATPQ oligomers exhibited significantly better processability than the linear PPQ but the PPQ displayed substantially better thermooxidative stability. Adhesive (Ti/Ti) and composite (graphite filament reinforcement) work was performed to evaluate the potential of these materials for structural applications. The PPQ exhibited better retention of adhesive and laminate properties than the ATPQ resins at 260 C after aging for 500 hr at 260 C in circulating air.

Hergenrother, P. M.↗

HCN formation on Jupiter - The coupled photochemistry of ammonia and Acetylene

HCN formation in the upper troposphere and lower stratosphere of Jupiter is presently modeled in terms of UV pyrolysis of the C2H5N isomer aziridine, which is a product of the NH2 and C2H3 radicals that originate from ammonia photolysis and the addition of H atoms to acetylene, respectively. The sensitivity of the HCN column density to the individual rate constants and the eddy diffusion coefficient profile is considered, along with the possibility that additional HCN-yielding pathways may exist. Both ammonia and phosphine are strongly depleted by photolysis.

Kaye, J. A.↗

Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

Bosco, S. R.↗

An improved processible acetylene-terminated polyimide for composites

The newest member of a family of thermosetting acetylene-substituted polyimide oligomers is HR600P. This oligomer is the isoimide version of the oligomer known as HR600P and Thermid 600. Although both types of material yield the same heat resistant end products after cure, HR600P has much superior processing characteristics. This attributed to its lower melting temperature (160 + or - 10 C, 320 + or - 20 F) in contrast to 202 C (396 F) for Thermid MC-600, its longer gel time at its processing temperature (16 to 30 minutes bvs 3 minutes), and its excellent solubility in low boiling solvents such as tetrahydrofuran, glymes, or 4:1 methyl ethyl ketone/toluene mixtures. These advantages provide more acceptable coating and impregnation procedures, allow for more complete removal at lower temperatures, provide a longer pot life or working time, and allow composite structure fabrication in conventional autoclaves used for epoxy composite curing. The excellent processing characteristics of HR600P allow its use in large area laminated structures, structural composites, and molding compositions.

Landis, A. L.↗

Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

Frenklach, M.↗

Interpenetrating polymer networks from acetylene terminated materials

As part of a program to develop high temperature/high performance structural resins for aerospace applications, the chemistry and properties of a novel class of interpenetrating polymer networks (IPNs) were investigated. These IPNs consist of a simple diacetylenic compound (aspartimide) blended with an acetylene terminated arylene ether oligomer. Various compositional blends were prepared and thermally cured to evaluate the effect of crosslink density on resin properties. The cured IPNs exhibited glass transition temperatures ranging from 197 to 254 C depending upon the composition and cure temperature. The solvent resistance, fracture toughness and coefficient of thermal expansion of the cured blends were related to the crosslink density. Isothermal aging of neat resin moldings, adhesive and composite specimens showed a postcure effect which resulted in improved elevated temperature properties. The chemistry, physical and mechanical properties of these materials will be discussed.

Connell, J. W.↗

Infrared spectroscopy and Mie scattering of acetylene aerosols formed in a low temperature diffusion cell

A method is described for forming and spectroscopically characterizing cryogenic aerosols formed in a low temperature gas cell. By adjusting the cell pressure, gas composition and flow rate, the size distribution of aerosol particles can be varied over a wide range. The combination of pressure and flow rate determine the residence time of the aerosols in the cell and hence the time available for the particles to grow. FTIR spectroscopy, over the range from 600/cm to 6000/cm, is used to characterize the aerosols. The particle size distribution can be varied so that, at one extreme, the spectra show only absorption features associated with the infrared active vibrational bands and, at the other, they display both absorption and Mie scattering. In the latter case, Mie scattering theory is used to obtain semiquantitative aerosol size distributions, which can be understood in terms of the interplay between nucleation and condensation. In the case of acetylene aerosols, the infrared spectra suggest that the particles exist in the high temperature cubic phase of the solid.

Dunder, T.↗

Theoretical study of the C-H bond dissociation energy of acetylene

The authors present a theoretical study of the convergence of the C-H bond dissociation energy (D sub o) of acetylene with respect to both the one- and n-particle spaces. Their best estimate for D sub o of 130.1 plus or minus 1.0 kcal/mole is slightly below previous theoretical estimates, but substantially above the value determined using Stark anticrossing spectroscopy that is asserted to be an upper bound.

Taylor, Peter R.↗

Decoupling in the line mixing of acetylene infrared Q branches

A difference-frequency laser spectrometer was used to record the Q-branch profiles of the nu1 + nu5, nu3 + nu4, and nu2 + 2nu4 + nu5 Pi(u)-Sigma(g) combination bands in the 2.5 micron C-H stretch-bend region of acetylene. The experiment was carried out at pressures in the range of 1 to 500 Torr. It is shown that line mixing causes substantial deviation of collisionally overlapped Q-branch profiles from the independently additive superposition of Lorentzian line shapes. It is also found that the degree of line mixing is greatly reduced from that assuming all the broadening arises from rotationally inelastic collisions coupling Q-branch lines only to one another.

Pine, A. S.↗

The energy separation between the classical and nonclassical isomers of protonated acetylene - An extensive study in one- and n-particle space saturation

The energy separation between the classical and nonclassical forms of protonated acetylene has been reinvestigated in light of the recent experimentally deduced lower bound to this value of 6.0 kcal/mol. The objective of the present study is to use state-of-the-art ab initio quantum mechanical methods to establish this energy difference to within chemical accuracy (i.e., about 1 kcal/mol). The one-particle basis sets include up to g-type functions and the electron correlation methods include single and double excitation coupled-cluster (CCSD), the CCSD(T) extension, multireference configuration interaction, and the averaged coupled-pair functional methods. A correction for zero-point vibrational energies has also been included, yielding a best estimate for the energy difference between the classical and nonclassical forms of 3.7 + or - 1.3 kcal/mol.

Lindh, Roland↗

Acetylene-chromene terminated resins as high temperature thermosets

A novel phase transfer catalyzed process for the preparation of propargyl ethers has been developed. The propargyl ethers serve as precursors to a new class of thermosetting resins called acetylene-chromene terminated (ACT) resins. Heat treatment of a solution of propargyl ethers with various catalysts, followed by removal of solvent leads to the ACT resins via partial conversion of the propargyl ether groups to chromenes. This process reduces the energy content of the resin systems and reduces the amount of shrinkage found during cure. Due to the presence of the solvent the process is safe and gives rise to low viscosity products suitable for resin transfer molding and filament winding type applications. Due to the high glass transition temperature, high modulus, and low moisture uptake the cured resins display better than 232 C/wet performance. The thermal stability of the ACT resins in air at 204 C is superior to that of conventional bismaleimide resins. The resins also display excellent electrical properties.

Godschalx, J. P.↗

Protonated acetylene - An important circumstellar and interstellar ion

In a circumstellar envelope, a substantial amount of acetylene is transported in a wind to the outer envelope, where it can be photoionized by interstellar radiation and then converted into C2H3(+) by a low-temperature reaction with H2. New chemical modeling calculations indicate that sufficient C2H3(+) may be produced in the outer envelope of IRC + 10216 to be observable. Similar considerations suggest that C2H3(+) should also be detectable in interstellar clouds, provided its rotational spectrum has been measured accurately in the laboratory.

Glassgold, A. E.↗

Oligomers Terminated By Maleimide And Acetylene

Oligomeric molecules terminated with maleimide and acetylene groups synthesized and thermally treated to form cross-linked polymers exhibiting high or undetectable glass-transition temperatures and high thermo-oxidative stabilities. Compounds used to make thermally stable, glassy polymers.

St. Clair, Terry L.↗

Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.

Non-NASA Center↗

Detection of acetylene in the infrared spectrum of comet Hyakutake

Comets are rich in volatile materials, of which roughly 80% (by number) are water molecules. Considerable progress is being made in identifying the other volatile species, the abundances of which should enable us to determine whether comets formed primarily from ice-covered interstellar grains, or from material that was chemically processed in the early solar nebula. Here we report the detection of acetylene (C2H2) in the infrared spectrum of comet C/1996 B2 (Hyakutake). The estimated abundance is 0.3-0.9%, relative to water, which is comparable to the predicted solid-phase abundance in cold interstellar clouds. This suggests that the volatiles in comet Hyakotake may have come from ice-covered interstellar grains, rather than material processed in the accretion disk out of which the Solar System formed.

Acetylene/analysis↗

Heat of Combustion of the Product Formed by the Reaction of Acetylene and Diborane (LFPL-CZ-3)

The heat of combustion of the product formed by the reaction acetylene and diborane was found to be 20,100 +/- 100 Btu per pound for the reaction of liquid fuel to gaseous carbon dioxide, gaseous water, and solid boric oxide. The measurements were made in a Parr oxygen-bomb calorimeter, and chemical analyses both of the sample and of the combustion products indicated combustion in the bomb calorimeter to have been 97 percent complete. The estimated net heat of combustion for complete combustion would therefore be 20,700 +/- 100 Btu per pound.

Allen, Harrison, Jr.↗