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At least 163 records · Page 9

The composition of comets

Questions concerning the origin of comets are considered. It is pointed out that the molecular composition of a dense interstellar cloud appears to have exactly the composition needed to produce the observed features of the visible cometary spectrum, which consists mainly of emission bands of unstable free radicals. A working model of cometary structure is discussed together with the classical observations which have led to it. The discussed model was originally described by Whipple (1951). It is emphasized that the model can serve only as a rough guide in efforts to interpret the evolution of cometary behavior. A survey is provided of new techniques which have only recently been applied to cometary observations, taking into account the spectrum of a comet, radio observations, and ultraviolet observations.

Feldman, P. D.↗

Stability of the equilibrium for atomic H in solid H2

The previously reported phenomenological rate process theory for the storage of atomic hydrogen free radicals in a tritium-impregnated crystalline molecular hydrogen solid is used to determine the dynamical stability of the constant uniform equilibrium solution. The analysis indicates that the equilibrium is unstable (thus, unattainable experimentally) for storage temperatures in a certain range (specifically between 0.134 and 0.80 K for 0.03% tritium by weight, and between 0.165 and 0.80 K for 1.20% tritium by weight), while being absolutely stable with respect to arbitrary small-amplitude perturbations for all storage temperatures below and above this range. The theory also predicts the maximum size for a stable H/H2 sample with an appreciable concentration of trapped H and a net excess rate of volumetric heating due to the tritium decay.

Rosen, G.↗

Some speculations about the origin of the high speed HCN jets in Comet Kohoutek /1973f/

The origin of the high-speed HCN jets observed in Comet Kohoutek (1973f) is considered. It is argued that the occurrence of these jets with Doppler shifts corresponding to velocities of approximately 3-5 km/s with respect to the nucleus cannot be explained in terms of either explosive outbursts of trapped sub-surface volatiles, highly exothermic chemical reactions involving free radicals, or the outward expansion of the cometary atmosphere with additional heating. Instead, acceleration of the precursor ions of HCN by energetic electrons in the ionospheric current sheets or current arcs is suggested to play an important role.

Ip, W.-H.↗

NO-NO2 measurements in a methane-fueled swirl-stabilized combustor

Exhaust plane measurements of NO and NO2 emissions from a methane-fueled swirl-stabilized combustor are reported. Samples were obtained by water-cooled probes and analyzed by chemiluminescent and UV absorption techniques. The combustor consists of two confined concentric jets having swirl. The inner jet flows premixed fuel and air, the outer jet is air. Variable outer jet swirl allows operation with jets swirling either in the same or opposite directions (co- or counter-swirl), and the combustion is stabilized by the resulting recirculation zone formed on the combustor centerline. Swirl conditions strongly affect the NOx emissions because of the influence of swirl on the combustion process. In the co-swirl conditions, the inner flow reaches high temperatures, and the correspondingly high NOx emissions are primarily NO. Under counter-swirl conditions much lower values of total NO are found, and these emissions are almost entirely NO2. In this case vigorous mixing in the inter-jet shear layer leads to severe flame quenching and lower temperatures. Formation of NO2 is associated with quenching processes in the combustor and is thought to be formed via NO oxidation by HO2 free radicals.

Oven, M. J.↗

Wear of steel by rubber

Wear of a steel blade used as a scraper to abrade rubber surfaces has been found to take place much more rapidly on a cis-polyisoprene (natural rubber) surface than on a cis-polybutadiene surface, and much more rapidly in an inert atmosphere than in air. These observations are attributed to the direct attack upon steel of free-radical species generated by mechanical rupture of elastomer molecules during abrasion.

Gent, A. N.↗

Synthesis of improved phenolic resins

Twenty seven addition cured phenolic resin compositions were prepared and tested for their ability to give char residues comparable to state-of-the-art phenolic resins. Cyanate, epoxy, allyl, acrylate, methacrylate and ethynyl derivatized phenolic oligomers were investigated. The novolac-cyanate and propargyl-novolac resins provided anaerobic char yields at 800 C of 58 percent. A 59 percent char yield was obtained from modified epoxy novolacs. A phosphonitrilic derivative was found to be effective as an additive for increasing char yields. The novolac-cyanate, epoxy-novolac and methacrylate-epoxy-novolac systems were investigated as composite matrices with Thornel 300 graphite fiber. All three resins showed good potential as composite matrices. The free radical cured methacrylate-epoxy-novolac graphite composite provided short beam shear strengths at room temperature of 93.3 MPa (13.5 ksi). The novolac-cyanate graphite composite produced a short beam shear strength of 74 MPa (10.7 ksi) and flexural strength of 1302 MPa (189 ksi) at 177 C. Air heat aging of the novolac-cyanate and epoxy novolac based composites for 12 weeks at 204 C showed good property retention.

Delano, C. B.↗

Electric propulsion technology

The advanced electric propulsion program is directed towards lowering the specific impulse and increasing the thrust per unit of ion thruster systems. In addition, electrothermal and electromagnetic propulsion technologies are being developed to attempt to fill the gap between the conventional ion thruster and chemical rocket systems. Most of these new concepts are exagenous and are represented by rail accelerators, ablative Teflon thrusters, MPD arcs, Free Radicals, etc. Endogenous systems such as metallic hydrogen offer great promise and are also being pursued.

Finke, R. C.↗

Stratospheric free chlorine measured by balloon-borne in situ resonance fluorescence

Eight balloon-borne in situ measurements of ClO in the stratosphere are analyzed and are compared with recent model calculations. While the use of in situ stratospheric studies of free radicals to test models by comparing observed and predicted concentration profiles is essential for a prognosis of changes in stratospheric ozone, resulting from future changes in stratospheric ozone, such studies provide only limited insight into the nature of stratospheric photochemistry, because natural variability and the large number of fast reactions which compete in the coupling among the key radicals frustrate a detailed comparison between a mean distribution provided by the models and an instantaneous distribution provided by a single observation.

Anderson, J. G.↗

Iodine - Its possible role in tropospheric photochemistry

A detailed study of the photochemistry of iodine and its oxides indicates that iodine species may play an important role in the tropospheric photochemical system. Methyl iodide, often observed in the marine troposphere with an average concentration of 5-10 ppt, is photolyzed and thereby produces I atoms. Chemical interactions with O3, HxOy, and NOx cause I to be converted to other inorganic compounds such as IO, HOI, IONO2, and I2. The production of these species and their subsequent recycling back to I can lead to the catalytic removal of tropospheric O3, the enhancement of the NO2/NO ratio, the destruction of HxOy free radicals, and the conversion of HO2 to OH. Ultimately, tropospheric inorganic iodine is removed by heterogeneous processes. Calculations using a numerical model to simulate tropospheric photochemistry indicate that iodine may have a strong impact upon the atmospheric O3-NOx-HxOy system. The magnitude of these effects is dependent upon the value of several uncertain rate constants and the primary source distributions of CH3I and other organic and inorganic iodine compounds.

Chameides, W. L.↗

Prediction of molecular infrared band and line intensities

The general problem of predicting infrared intensities is examined. The problem of predicting line intensities is discussed with attention focussed specifically on the problem of predicting vibrational strengths (or total band intensities). Two methods are considered: predictions based on ab initio quantum mechanical calculations, and predictions based on the transfer of atomic polar tensor parameters from small model molecules to the molecule of interest. Comparisons of predicted spectra with experimental spectra are shown for CH3OH, CH3OCH3, C2H5OH, and HOC2. It is suggested that the most important application of this work may be to the prediction of intensities for free radicals, ions, and reactive intermediates so that the infrared spectrum can be used in the quantitative analysis for these interesting species.

Person, W. B.↗

Investigation of degradation mechanisms in composite matrices

Degradation mechanisms were investigated for graphite/polysulfone and graphite/epoxy laminates exposed to ultraviolet and high-energy electron radiations in vacuum up to 960 equivalent sun hours and 10 to the ninth power rads respectively. Based on GC and combined GC/MS analysis of volatile by-products evolved during irradiation, several free radical mechanisms of composite degradation were identified. The radiation resistance of different matrices was compared in terms of G values and quantum yields for gas formation. All the composite materials evaluated show high electron radiation stability and relatively low ultraviolet stability as indicated by low G values and high quantum for gas formation. Mechanical property measurements of irradiated samples did not reveal significant changes, with the possible exception of UV exposed polysulfone laminates. Hydrogen and methane were identified as the main by-products of irradiation, along with unexpectedly high levels of CO and CO2.

Giori, C.↗

Atmospheric methyl iodide /CH3I/

It is found that atmospheric concentrations of CH3I are not greater than about 3 pptv over most of the earth's surface and drop to less than half this value above the boundary layer, suggesting that the compound is not likely to play such important roles, on a global scale, as the destruction of tropospheric O3 and free radicals and the increasing of the NO2/NO ratio and hydroxyl radical densities. It is hypothesized that a large portion of the global CH3I comes from oceanic regions of high biomass productivity, where the compound may play a key role in local atmospheric chemistry. Attention is given to CH3I measurement uncertainties with regard to global distribution, sources, and sinks.

Rasmussen, R. A.↗

Conversion of para and ortho hydrogen in the Jovian planets

A mechanism is proposed which partially equilibrates the para and ortho rotational levels of molecular hydrogen in the atmospheres of Jupiter, Saturn, and Uranus. Catalytic reactions between the free-radical surface sites of aerosol particles and hydrogen modecules yield significant equilibration near 1 bar pressure, if the efficiency of conversion per collision is between 10 to the -8th and 10 to the -10th and the effective eddy mixing coefficient is 10,000 sq cm/sec. At lower pressures the ortho-para ratio retains the value at the top of the cloud layer, except for a very small effect from conversion in the thermosphere. The influence of conversion on the specific heat and adiabatic lapse rate is also investigated. The effect is found to be generally small, though is can rise to 10% inside the aerosol layer.

Massie, S. T.↗

Characterization of advanced electric propulsion systems

Characteristic parameters of several advanced electric propulsion systems are evaluated and compared. The propulsion systems studied are mass driver, rail gun, argon MPD thruster, hydrogen free radical thruster and mercury electron bombardment ion engine. Overall, ion engines have somewhat better characteristics as compared to the other electric propulsion systems.

Ray, P. K.↗

Shock tube measurements of growth constants in the branched chain formaldehyde-carbon monoxide-oxygen system

Exponential free radical growth constants were measured for formaldehyde carbon monoxide-oxygen systems by monitoring the growth of oxygen atom concentration as manifested by CO flame band emission. Data were obtained over the temperature range of 1200 to 2000 K. The data were analyzed using a formaldehyde oxidation mechanism involving 12 elementary reaction steps. The computed growth constants are roughly in accord with experimental values, but are much more temperature dependent. The data was also analyzed assuming formaldehyde is rapidly decomposed to carbon monoxide and hydrogen. Growth constants computed for the resulting carbon monoxide hydrogen oxygen mixtures have a temperature dependence similar to experiments; however, for most mixtures, the computed growth constants were larger than experimental values.

Brabbs, T. A.↗

Is cell aging caused by respiration-dependent injury to the mitochondrial genome

Though intrinsic mitochondrial aging has been considered before as a possible cause of cellular senescence, the mechanisms of such mitochondrial aging have remained obscure. In this article, the hypothesis of free-radical-induced inhibition of mitochondrial replenishment in fixed postmitotic cells is expanded. It is maintained that the respiration-dependent production of superoxide and hydroxyl radicals may not be fully counteracted, leading to a continuous production of lipoperoxides and malonaldehyde in actively respiring mitochondria. These compounds, in turn, can easily react with the mitochondrial DNA which is in close spatial relationship with the inner mitochondrial membrane, producing an injury that the mitochondria may be unable to counteract because of their apparent lack of adequate repair mechanisms. Mitochondrial division may thus be inhibited leading to age-related reduction of mitochondrial numbers, a deficit in energy production with a concomitant decrease in protein synthesis, deterioration of physiological performance, and, therefore, of organismic performance.

Fleming, J. E.↗

Experimental and theoretical study of combustion jet ignition

A combustion jet ignition system was developed to generate turbulent jets of combustion products containing free radicals and to discharge them as ignition sources into a combustible medium. In order to understand the ignition and the inflammation processes caused by combustion jets, the studies of the fluid mechanical properties of turbulent jets with and without combustion were conducted theoretically and experimentally. Experiments using a specially designed igniter, with a prechamber to build up and control the stagnation pressure upstream of the orifice, were conducted to investigate the formation processes of turbulent jets of combustion products. The penetration speed of combustion jets has been found to be constant initially and then decreases monotonically as turbulent jets of combustion products travel closer to the wall. This initial penetration speed to combustion jets is proportional to the initial stagnation pressure upstream of the orifice for the same stoichiometric mixture. Computer simulations by Chorin's Random Vortex Method implemented with the flame propagation algorithm for the theoretical model of turbulent jets with and without combustion were performed to study the turbulent jet flow field. In the formation processes of the turbulent jets, the large-scale eddy structure of turbulence, the so-called coherent structure, dominates the entrainment and mixing processes. The large-scale eddy structure of turbulent jets in this study is constructed by a series of vortex pairs, which are organized in the form of a staggered array of vortex clouds generating local recirculation flow patterns.

Chen, D. Y.↗

Module degradation catalyzed by metal-encapsulation reactions

Four major properties are considered to be relevant in determining service life of a photovoltaic module: (1) Mechanical: creep resistance, modulus, tensile strength; (2) Optical: integrated transmission at 0.4 to 1.1 m wavelength; (3) Chemical: inertness with respect to metals and other components, retention of stabilizers, etc. and (4) Electrical; maintaining effective isolation of conductive components. These properties were measured after exposing polymer specimens to three types of accelerated stress: thermal, ultraviolet radiation and metal catalysts. These conditions give rise to a large number of complex interrelated free-radical reactions that result in the deterioration of polymeric materials.

Gallagher, B. D.↗