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At least 577 records · Page 32

A measurement of the vibrational band strength for the upsilon sub 3 band of the HO2 radical

The HO2 radicals generated in a discharge-flow system were observed with tunable diode laser absorption in the P-branch of the nu(3) vibrationall band at 1080/cm. The observed line positions agree with those calculated from the molecular constants for the nu(3) bland obtained from a previous study using laser magnetic resonance spectroscopy. The band strength was determined by observing line center absoptions when HO2 is produced in the reaction F + H2O2 yields HO2 + HF (k1) with a measured concentration of atomic fluorine and excess hydrogen peroxide. F-atom concentrations are measured by diode laser absorption of the spin-orbit transition at 404/cm. The analysis accounts for HO2 losses due to the reactions of HO2 + HO2 yields H2O2 + O2 (k3) and F + HO2 yields HF + O2 (k4). The line strength for the 6(15) 7(16) F(1) transition is 2.9 x 10 to the 21st power sq cm/molecule/cm which corresponds to a nu(3) band strength of 34 +/- 9 sq/cm(STP atm). This value is a factor of 6 lower than previous ab initio calculations. These results will be useful in assessing the feasibility of atmospheric measurements of HO2 using infrared absorption techniques.

Zahniser, M. S.↗

Atomic hydrogen maser measurements with wall surfaces of carbon tetrafluoride

The principal objectives of the Smithsonian Astrophysical Observatory cold maser research programs are given. This work is aimed principally at understanding more about the interaction of hydrogen atoms with wall coatings of fluorinated ethylene propylene (Dupont Teflon FEP-120 co-polymer) and of carbon tetrafluoride (CE4). The principal measured quantity in these experiments is the wall shift of the maser's output frequency. The wall shift per atomic collision was calculated from the measured wall frequency shift. This assumes that the wall surface area is smooth on a molecular scale.

Vessot, R. F. C.↗

Search for heavy antinuclei in the cosmic radiation

The existence of significant amounts of antimatter in the Universe is demonstrated through cosmic radiation. The data from the Danish-French Cosmic Ray Spectrometer on the HEAO-3 satellite offers an opportunity to search for heavy antinuclei, since all the relevant parameters (charge, velocity, arrival direction, and satellite position at the time of arrival) are measured for each recorded nucleus. Using the 22676 positive only events in the data seletion corresponding to L 1.5 as a measure of our exposure factor to heavy antinuclei and noting that no corresponding antinuclei were found, an upper limit (95% confidence) is given to the ratio of antinuclei to nuclei as 1.4 x .0001 for particles with Z 9. The upper limit resulting from this work is compared with previous results of searches for heavy antimatter in the cosmic radiation. It is seen that, if one regards only antiparticles heavier than fluorine, then the present result represents a reduced upper limit over previous data. When taken together, all the available experiment data now push the upper limit for the ratio of antiparticles to particles well below .0001.

Lund, N.↗

The far-infrared laser magnetic resonance spectrum of the SiH radical and determination of ground state parameters

The far-infrared laser magnetic resonance spectrum of the SiH radical in the v = O level of its X2Pi state has been recorded. The signals are rather weak. The molecules were generated in the reaction between fluorine atoms and SiH4. Rotational transitions have been detected in both 2Pi1/2 and 2Pi3/2 spin components but no fine structure transitions between the spin components were observed. Proton hyperfine splittings were resolved on some lines. The measurements have been analyzed, subjected to a least-squares fit using an effective Hamiltonian, and the appropriate molecular parameters determined. The weakness of the spectrum and the failure of attempts to power saturate favorable lines are both consistent with a small value for the electric dipole moment for SiH.

Brown, J. M.↗

Propulsion evaluation for orbit-on-demand vehicles

Future earth-to-orbit vehicles may be required to reach orbit within hours or even minutes of a decision. A study has been conducted to consider vehicles with such a capability. In Phase I of the study, 11 vehicles were designed to deploy 5000 lb to a polar orbit. Changes in the designs were examined parametrically for increased on-orbit maneuvers, increased payload, and other mission variations. Based on the results, two concepts were selected for Phase II design work: a vertical-takeoff, two-stage system and a horizontal-takeoff, two-stage system with an airbreathing subsonic first stage. The results of several propulsion evaluations are presented, including liftoff thrust-to-weight effects, dual-fuel propulsion for a horizontal-takeoff concept, and the effect of using fluorine.

Martin, J. A.↗

Secondary electron emission from a charged dielectric

Charges on the surface of fluorinated-ethylene-propylene affect its secondary electron emission coefficient. Measurements with impact energies exceeding that energy which causes peak emission have been made in regions where the local electric field produced by the surface charge is normal to the surface and in regions where it is oblique. The surface of the 6-mm wide specimen was charged to either 6 or 10 kV. Because the impinging primary beam was deflected by the charged specimen, numerical modeling was used to predict the beam's impact energy E, impact angle theta, and the impact point. The formula predicts the coefficient in the region of normal field up to 60 deg although E(0) depends upon the electric field and also on the history of the specimen. Near the edges where the field is oblique, the measured coefficient departs significantly from what the formula predicts.

Budd, P. A.↗

SEM/XPS analysis of fractured adhesively bonded graphite fibre-reinforced polyimide composites

The surfaces of the graphite fiber-reinforced polyimide composites presently pretreated prior to bonding with polyimide adhesive contained variable amounts of a fluoropolymer, as determined by X-ray photoelectron spectroscopy. Lap shear strengths were determined for unaged samples and for those aged over 500- and 1000-hour periods at 177 and 232 C. Unaged sample lap strengths, which were the highest obtained, exhibited no variation with surface pretreatment, but a significant decrease is noted with increasing aging temperature. These thermally aged samples, however, had increased surface fluorine concentration, while a minimal concentration was found in unaged samples. SEM demonstrated a progressive shift from cohesive to adhesive failure for elevated temperature-aged composites.

Devilbiss, T. A.↗

High-temperature Adhesive Development and Evaluation

High-temperature adhesive systems are evaluated for short and long-term stability at temperatures ranging from 232C to 427C. The resins selected for characterization include: NASA Langley developed polyphenylquinoxaline (PPQ), and commercially available polyimides (PI). The primary method of bond testing is single lap shear. The PPQ candidates are evaluated on 6A1-4V titanium adherends with chromic acid anodize and phosphate fluoride etch surface preparations. The remaining adhesives are evaluated on 15-5 PH stainless steel with a sulfuric acid anodize surface preparation. Preliminary data indicate that the PPQ adhesives tested have stability to 3000 hours at 450F with chromic acid anodize surface preparation. Additional studies are continuing to attempt to improve the PPQ's high-performance by formulating adhesive films with a boron filler and utilizing the phosphate fluoride surface preparation on titanium. Evaluation of the polyimide candidates on stainless-steel adherends indicates that the FM-35 (American Cyanamid), PMR-15 (U.S. Polymeric/Ferro), TRW partially fluorinated polyimide and NR 150B2S6X (DuPont) adhesives show sufficient promise to justify additional testing.

Hendricks, C. L.↗

Prediction of heat release effects on a mixing layer

A fully second-order closure model for turbulent reacting flows is suggested based on Favre statistics. For diffusion flames the local thermodynamic state is related to single conserved scalar. The properties of pressure fluctuations are analyzed for turbulent flows with fluctuating density. Closure models for pressure correlations are discussed and modeled transport equations for Reynolds stresses, turbulent kinetic energy dissipation, density-velocity correlations, scalar moments and dissipation are presented and solved, together with the mean equations for momentum and mixture fraction. Solutions of these equations are compared with the experimental data for high heat release free mixing layers of fluorine and hydrogen in a nitrogen diluent.

Farshchi, M.↗

The preparation of new perfluoroether fluids exhibiting excellent thermal-oxidative stabilities

A series of low molecular weight perfluoroalkylethers (PFAE) were synthesized by direct fluorination. Viscosity-temperature properties and oxidation stabilities were determined. Viscosity-temperature correlations indicated that increases in branching and increases in the size of the branching substituent caused a deterioration in viscometric properties (i.e., an increase in ASTM slope). In addition, increasing the ratio of carbon to oxygen in these compounds also increased the ASTM slope. Preliminary oxidation stability tests indicated that highly branched PFAE fluids. (i.e., those containing quaternary carbons) may be less stable than either those containing a single trifluoromethyl pendant group or those containing no branching at all.

Jones, W. R., Jr.↗

Characterization of the tribological coating composition 77 wt % CaF2 - 23 wt % Li F fused to IN-750 alloy

A coating composed of 77 wt % CaF2 - 23 wt % LiF fused on IN-750 nickel-based alloy was studied using SEM, XRD, EDX, and optical microscopic methods. The surfaces examined were the as-fused coating with no subsequent treatment, the coating after ultrasonic cleaning in water, and the uncoated polished and etched metal. It was found that the coating reacts during fusion with Ti and Nb rich inclusions in the alloy. Numerous small rectangular crystallites of Ca(Ti,Nb) oxide are formed beneath an overlay of fused fluoride composition. These crystallines are stubby and appear to be embedded in the metal substrate surface. It is known from previous studies that this coating-alloy system has good tribological properties in extreme conditions, such as liquid fluorine. It has been concluded from the present study that the short firmly embedded crystalline protuberances contribute to the coating adherence and thereby to enhanced coating wear life.

Deadmore, D. L.↗

Infrared and far-infrared laser magnetic resonance spectroscopy of the GeH radical - Determination of ground state parameters

The GeH radical has been detected in its ground 2 Pi state in the gas phase reaction of fluorine atoms with GeH4 by laser magnetic resonance techniques. Rotational transitions within both 2 Pi 1/2 and 2 Pi 3/2 manifolds have been observed at far-infrared wavelengths and rotational transitions between the two fine structure components have been detected at infrared wavelengths (10 microns). Signals have been observed for all five naturally occurring isotopes of germanium. Nuclear hyperfine structure for H-1 and Ge-73 has also been observed. The data for the dominant isotope (/Ge-74/H) have been fitted to within experimental error by an effective Hamiltonian to give a set of molecular parameters for the X 2 Pi state which is very nearly complete. In addition, the dipole moment of GeH in its ground state has been estimated from the relative intensities of electric and magnetic dipole transitions in the 10 micron spectrum to be 1.24(+ or - 0.10) D.

Brown, J. M.↗

Prediction of heat release effects on a mixing layer

A fully second-order closure model for turbulent reacting flows is suggested based on Favre statistics. For diffusion flames the local thermodynamic state is related to a single conserved scalar. The properties of pressure fluctuations are analyzed for turbulent flows with fluctuating density. Closure models for pressure correlations are discussed and modelled transport equations for Reynolds stresses, turbulent kinetic energy dissipation, density-velocity correlations, scalar moments and dissipation are presented and solved, together with the mean equations for momentum and mixture fraction. Solutions of these equations are compared with the experimental data for high heat release free mixing layers of fluorine and hydrogen in a nitrogen diluent.

Farshchi, M.↗

Distribution of nitrogen and defects in SiO(x)N(y)/Si structures formed by the thermal nitridation of SiO2/Si

Previously reported nitrogen distributions in SiO2 films on Si which have been thermally nitrided at 1000 C have been explained by a kinetic model of the nitridation process which rests upon the effects of interfacial strain. A critical test of this kinetic model is the validity of the predictions regarding nitrogen distributions obtained at other nitridation temperatures. In this work, nitrogen distributions determined via X-ray photoelectron spectroscopy are reported for samples nitrided at 800 and 1150 C, and are shown to be consistent with the kinetic model. In addition, the intensity of a fluorine marker is found to correlate with the nitrogen distribution, and is postulated to be related to kinetically generated defects in the dielectric film, consistent with the strain-dependent energy of formation of defects proposed recently to explain electrical data.

Vasquez, R. P.↗

Analyses of spacecraft polymeric materials

Partial analytical characterizations are made by four different techniques of three polymeric materials used in conjunction with the Space Telescope for samples flown on mission STS-8. The polymers were Tedlar, Kapton H, and Kapton F. The surfaces of the three polymers were attacked and oxidized by atomic oxygen, and fluorine is lost from the surface of Kapton F, largely due to displacement by atomic oxygen.

Worley, S. D.↗

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set 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. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

Johnson, H.↗

An X-ray photoelectron spectroscopy study of the thermal nitridation of SiO2/Si

The dependence of the nitrogen distribution in thermally nitrided SiO2 films on the nitridation time and temperature has been studied by means of X-ray photoelectron spectroscopy (XPS). The photoelectron peak intensities were measured by fitting Voigt profiles to the XPS spectra and were used to calculate the film composition as a function of film depth, applying an analytical method described in detail. The times of appearance of the maxima in interfacial nitrogen concentration are shown for 800, 1000, and 1150 C, and the data are related to a kinetic model of Vasquez and Madhukar (1985), which considers the effect of interfacial strain on the nitridation kinetics. In addition, the intensity of a fluorine marker (from the HF used in the etching step) was found to correlate with the nitrogen concentration. It is postulated that the F bonds preferentially to defects. This hypothesis and the measured F intensities are consistent with the proposed strain-dependent energy of defect formation.

Vasquez, R. P.↗

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.

Johnson, H.↗