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At least 91 records · Page 5

Heterogeneous reactions of N2O5 with H2O and HCl on ice surfaces - Implications for Antarctic ozone depletion

This paper reports on the measurements of reaction probabilities for heterogeneous reaction of N2O5 with H2O and HCl on ice surfaces at 195 K, using a fast-flow reactor coupled with a quadrupole mass spectrometer. The reaction probability for N2O5 on pure-water ice was found to be 0.028 + or - 0.011, with nitric acid in the solid phase as the sole product. In the presence of HCl in ice, the probability of N2O5 reaction was enhanced (to 0.037); the reaction produced, besides solid-phase nitric acid, ClNO2 and ClONO which were released into the gas phase within a few milliseconds. The latter two compounds can be readily photolyzed in the austral spring to form active chlorine which would remove stratospheric ozone. It is suggested that, since the polar stratospheric clouds are believed to contain HCl-ice mixture on the surface, the reactions of N2O5 on H2O/HCl particles is a major factor in the Antarctic springtime ozone depletion.

Leu, Ming-Taun↗

Space Station Freedom coupling tasks: An evaluation of their telerobotic and EVA compatibility

Of the couplings included in this study, several design components were found to be of interest. With respect to the operation of the couplings, the various concepts resulted in differing reactions from the four subjects who participated in this study. The purpose of this study was not to conceive the final coupling design. Rather, it was intended as a step along an interactive process. The newly modified coupling will be included in a series of further controlled, as well as subjective, evaluations. This part of the ongoing work in the Remote Operator Interaction Laboratory (ROIL) designed to enhance the overall interface by improving design at both the teleoperator and telerobot ends of the system.

Sampaio, Carlos E.↗

Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

Meador, Mary Ann B.↗

Chemical Kinetics of the TPS and Base Bleeding During Flight Test

The present research deals with thermal degradation of polyurethane foam (PUF) during flight test. Model of thermal decomposition was developed that accounts for polyurethane kinetics parameters extracted from thermogravimetric analyses and radial heat losses to the surrounding environment. The model predicts mass loss of foam, the temperature and kinetic of release of the exhaust gases and char as function of heat and radiation loads. When PUF is heated, urethane bond break into polyol and isocyanate. In the first stage, isocyanate pyrolyses and oxidizes. As a result, the thermo-char and oil droplets (yellow smoke) are released. In the second decomposition stage, pyrolysis and oxidization of liquid polyol occur. Next, the kinetics of chemical compound release and the information about the reactions occurring in the base area are coupled to the CFD simulations of the base flow in a single first stage motor vertically stacked vehicle configuration. The CFD simulations are performed to estimate the contribution of the hot out-gassing, chemical reactions, and char oxidation to the temperature rise of the base flow. The results of simulations are compared with the flight test data.

Osipov, Viatcheslav↗

RCS jet-flow field interaction effects on the aerodynamics of the space shuttle orbiter

A study was conducted to determine the external effects caused by operation of the reaction control system during entry of the space shuttle orbiter. The effects of jet plume-external flow interactions were emphasized. Force data were obtained for the basic airframe characteristics plus induced effects when the reaction control system is operating. Resulting control amplification and/or coupling were derived and their effects on the aerodynamic stability and control of the orbiter and the reaction control system thrust were determined.

Rausch, J. R.↗

Competition between charge exchange and chemical reaction - The D2/+/ + H system

Study of the special features of molecular charge exchange and its competition with chemical reaction in the case of the D2(+) + H system. The trajectory surface hopping (TSH) model proposed by Tully and Preston (1971) is used to study this competition for a number of reactions involving the above system. The diatomics-in-molecules zero-overlap approximation is used to calculate the three adiabatic surfaces - one triplet and two singlet - which are needed to describe this system. One of the significant results of this study is that the chemical reaction and charge exchange are strongly coupled. It is also found that the number of trajectories passing into the chemical regions of the three surfaces depends very strongly on the surface crossings.-

Preston, R. K.↗

Passive components for high temperature operation

The development of resistors, capacitors, and interconnect metalizations utilizing a low pressure chemical vapor deposition (LPCVD) process is described. The LPCVD process allows the passive components to be fabricated at temperatures higher than their highest operating temperatures. The deposition of thin films by LPCVD is accomplished by reacting one or more gases on the surface of a heated substrate. The substrates to be coated are placed on a graphite susceptor and then loaded into the center of a quartz reaction tube. The RF power is applied to the coil on the outside of the reaction tube which in turn is coupled into the graphite susceptor causing it to heat. Pressures of several torr or less are typical, with carrier flow rates of 0.1 to 2.0 liters/min. Nitrogen, hydrogen, and helium are typical carrier gases. These are controlled with mass flow controllers and the pressure is continuously monitored with a capacitive manometer. Materials selection and device testing are also discussed.

Raymond, L. S.↗

The detailed chemistry and thermodynamics of sodium in oxygen-rich flames

Measurement of sodium and OH concentrations in ten oxygen-rich H2/O2/N2 flames by respective saturated and low-power laser induced fluorescence techniques have permitted a detailed examination of the pronounced flame chemistry of sodium in such oxygen rich media. Previous interpretations have been shown to be largely incomplete or in error. The flame downstream profiles indicate that the amount of free sodium tracks the decay of H-atom and as the flame radicals decay sodium becomes increasingly bound in a molecular form. A detailed kinetic model indicates that the sodium is distributed between NaOH and NaO2 species. Concentrations of NaO are very small and NaH negligible. The actual distribution is controlled by the state of equilibrium of the flames' basic free radicals. Na, NaO2 and NaOH are all coupled to one another by fast reactions which can rapidly interconvert one to another as flame conditions vary. Above about 2000K, NaOH becomes dominant whereas NaO2 plays an increasingly important contribution at lower temperatures.

Hynes, A. J.↗

Ceramic fabrication process before firing-surface treatment of ceramic powder

The surface treatment of powders is discussed. Stability of ceramic powders and surfaces and the improvement of moldability are addressed. Characteristics of surface treatment technology are given, including formation of inorganic surface-treated layers, liquid phase reactions, gas treatment, surface treatment by coupling agents, and the formation of results of surface treatment.

Tsunoda, T.↗

Protecting Li/TiS2 Cells Against Overcharge

New electrolyte additive, N,N,N',N'- tetramethyl-1,4-phenylenediamine (TMPD), helps protect lithium/titanium disulfide rechargeable cells against overcharge. TMPD is redox couple: during overcharge, it undergoes electrochemical reactions at both electrodes and takes up excess input charge. Without TMPD, overcharge results in oxidative degradation of nonaqueous electrolyte, leading to loss of rechargeability and safety problems. Li/TiS2 cells currently being considered for spacecraft and military applications.

Narayanan, S. R.↗

Calcium requirement of phytochrome-mediated fern-spore germination: no direct phytochrome-calcium interaction in the phytochrome-initiated transduction chain

Phytochrome-mediated germination of fern spores of Dryopteris paleacea Sw. was initiated by a saturating red-light (R) irradiation after 20 h of imbibition. For its realization external Ca2+ was required, with a threshold at a submicromolar concentration, and an optimum was reached around 10(-4) M. At concentrations > or = 10(-1) M only a reduced response was obtained, based probably on an unspecific osmotic or ionic effect. The germination response was inhibited by La3+, an antagonist of Ca2+. From these results it is concluded that Ca2+ influx from the medium into the spores may be an important event in phytochrome-mediated germination. In the absence of Ca2+ the R-stimulated system remained capable of responding to Ca2+, added as late as 40 h after R. Moreover, Ca2+ was effective even if added after the active form of phytochrome, Pfr, had been abolished by far-red (FR) 24 h after R. Thus, the primary effect of Pfr, that initiates the transduction chain, does not require calcium. "Coupling" of Pfr to subsequent dark reactions has been investigated by R-FR irradiations with various dark intervals. The resulting "escape kinetics" were characterized by a lag phase (6 h) and half-maximal escape from FR reversibility (19 h). These kinetics were not significantly changed by the presence or absence of calcium. Thus, direct interaction of Pfr and calcium is not a step in the transduction chain initiated by the active form of phytochrome.

Non-NASA Center↗

Field Effects of Buoyancy on a Premixed Turbulent Flame Studied by Particle Image Velocimetry

Typical laboratory flames for the scientific investigation of flame/turbulence interactions are prone to buoyancy effects. Buoyancy acts on these open flame systems and provides upstream feedbacks that control the global flame properties as well as local turbulence/flame interactions. Consequently the flame structures, stabilization limits, and turbulent reaction rates are directly or indirectly coupled with buoyancy. The objective of this study is to characterize the differences between premixed turbulent flames pointing upwards (1g), pointing downwards (-1g), and in microgravity (mg). The configuration is an inverted conical flame stabilized by a small cone-shaped bluff body that we call CLEAN Flames (Cone-Stabilized Lean Flames). We use two laser diagnostics to capture the velocity and scalar fields. Particle image velocimetry (PIV) measures the mean and root mean square velocities and planar imaging by the flame fronts method outlines the flame wrinkle topology. The results were obtained under typical conditions of small domestic heating systems such as water heaters, ovens, and furnaces. Significant differences between the 1g and -1g flames point to the need for including buoyancy contributions in theoretical and numerical calculations. In Earth gravity, there is a complex coupling of buoyancy with the turbulent flow and heat release in the flame. An investigation of buoyancy-free flames in microgravity will provide the key to discern gravity contributions. Data obtained in microgravity flames will provide the benchmark for interpreting and analyzing 1g and -1g flame results.

Cheng, Robert K.↗

Quenching of Excited Na due to He Collisions

The quenching and elastic scattering of excited Sodium by collisions with Helium have been investigated for energies between 10(exp -13) eV and 10 eV. With the ab initio adiabatic potentials and nonadiabatic radial and rotational couplings obtained from multireference single- and double-excitation configuration interaction approach, we carried out scattering calculations by the quantum-mechanical molecular-orbital close-coupling method. Cross sections for quenching reactions and elastic collisions are presented. Quenching and elastic collisional rate coefficients as a function of temperature between 1 micro-K and 10,000 K are also obtained. The results are relevant to modeling non-LTE effects on Na D absorption lines in extrasolar planets and brown dwarfs.

Lin, C. Y.↗

Role of Transport and Kinetics in Growth of Renal Stones

Renal stone disease is not only a concern on earth but could conceivably pose as a serious risk to the astronauts health and safety in Space. In this paper, a combined transport-kinetics model for growth of calcium oxalate crystals is presented. The model is used to parametrically investigate the growth of renal calculi in urine with a focus on the coupled effects of transport and surface reaction on the ionic concentrations at the surface of the crystal and their impact on the resulting growth rates. It is shown that under nominal conditions of low solution supersaturation and low Damkohler number that typically exist on Earth, the surface concentrations of calcium and oxalate approach their bulk solution values in the urine and the growth rate is most likely limited by the surface reaction kinetics. But for higher solution supersaturations and larger Damkohler numbers that may be prevalent in the microgravity environment of Space, the calcium and oxalate surface concentrations tend to shift more towards their equilibrium or saturation values and thus the growth process may be limited by the transport through the medium. Furthermore, parametric numerical studies suggest that changes to the renal biochemistry of astronauts due in space may promote development of renal calculi during long duration space expeditions.

Kassemi, Mohammad↗

Are models of catalytic removal of O3 by HO(x) accurate? Constraints from in situ measurements of the OH to HO2 ratio

Measurements of the ratio OH/HO2, NO, O3, ClO, and BrO were obtained at altitudes from 15-20 km and latitudes from 15-60 deg N. A method is presented for interpreting the rates of chemical transformations that (1) are responsible for over half the ozone removal rate in the lower stratosphere via reactions of HO2; and (2) control the abundance of HO2 through coupling to nitrogen and halogen radicals. The results show our understanding of the chemical reactions controlling the partitioning of OH and HO2 is complete and accurate and that the potential effects of 'missing chemistry' are strickly constrained in the region of the atmosphere encompassed by the observations. The analysis demonstrates that the sensitivity of the ratio OH/HO2 to changes in NO is described to within 12% by current models. This reduces by more than a factor of 2 the effect of uncertainty in the coupling of hydrogen and nitrogen radicals on the analysis of the potential effects of perturbations to odd notrogen in the lower statosphere.

Cohen, R. C.↗

Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

Leu, Ming-Taun↗