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NASA NTRS1993

The photophysics of monomeric bacteriochlorophylls c and d and their derivatives: properties of the triplet state and singlet oxygen photogeneration and quenching

Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen.

NASA Discipline Number 52-30↗

NASA NTRS2000

Structure of Laminar Permanently Blue, Opposed-Jet Ethylene-Fueled Diffusion Flames

The structure and state relationships of laminar soot-free (permanently blue) ethylene-fueled diffusion flames at various strain rates were studied both experimentally and computationally using an opposed-jet configuration. Measurements of gas velocities, temperatures, and compositions were carried out along the stagnation stream line. Corresponding predictions of flame structure were obtained, based on numerical simulations using several contemporary reaction mechanisms for methane oxidation. Flame conditions studied included ethylene-fueled opposed-jet diffusion flames having stoichiometric mixture fractions of 0.7 with measurements involving strain rates of 60-240/s and predictions involving strain rates of 0-1140/s at normal temperature and pressure. It was found that measured major gas species concentrations and temperature distributions were in reasonably good agreement with predictions using mechanisms due to GRI-Mech and Peters and that effects of preferential diffusion significantly influence flame structure even when reactant mass diffusivities are similar. Oxygen leakage to fuel-rich conditions and carbon monoxide leakage to fuel-lean conditions both increased as strain rates increased. Furthermore, increased strain rates caused increased fuel concentrations near the flame sheet, decreased peak gas temperatures, and decreased concentrations of carbon dioxide and water vapor throughout the flames. State relationships for major gas species and gas temperatures were found to exist over a broad range of strain rates, providing potential for significant computational simplifications for modeling purposes in some instances.

Lin, K.-C.↗

NASA NTRS2000

Structure of Laminar Permanently Blue, Opposed-Jet Ethylene-Fueled Diffusion Flames

Lin, K.-C.↗

NASA NTRS1972

Mechanisms of oxidation in the Co-Cr system.

Oxidation has been studied both as a function of temperature in the range from 900 to 1300 C and of the partial pressure of oxygen in the range from 0.05 to 760 torr. In addition, microstructures of oxide scales have been studied and characterized in more detail utilizing metallographic and X-ray techniques combined with electron microprobe analysis. The parabolic rate constants in 1100 C and at 100 and 10 torr oxygen are presented in a graph as a function of chromium content. Three main different mechanisms of oxidation in the Co-Cr system have been identified. In two of these, the rate determining process controlling the oxidation is the solid state diffusion of cobalt through the oxide CoO. The rate controlling process governing the oxidation for the third mechanism is chromium diffusion in dichromium trioxide.

Kofstad, P. K.↗

NASA NTRS1986

Prediction and rational correlation of thermophoretically reduced particle mass transfer to hot surfaces across laminar or turbulent forced-convection gas boundary layers

A formulation previously developed to predict and correlate the thermophoretically-augmented submicron particle mass transfer rate to cold surfaces is found to account for the thermophoretically reduced particle mass transfer rate to overheated surfaces such that thermophoresis brings about a 10-decade reduction below the convective mass transfer rate expected by pure Brownian diffusion and convection alone. Thermophoretic blowing is shown to produce effects on particle concentration boundary-layer (BL) structure and wall mass transfer rates similar to those produced by real blowing through a porous wall. The applicability of the correlations to developing BL-situations is demonstrated by a numerical example relevant to wet-steam technology.

Gokoglu, Suleyman A.↗

NASA NTRS1981

Energetic oxygen and sulfur in the Jovian magnetosphere

Measurements made in the Jovian magnetosphere by the cosmic ray subsystem on Voyager 1 and 2 are reported. Energy spectra of oxygen ions in the energy range 1-20 MeV/nuc between 5 and 20 Jovian radii are presented, and phase space densities are calculated. A steep positive radial gradient in the phase space density of the energetic oxygen ions is observed, indicating an inward diffusive flow. The upper limit on the rate at which oxygen ions with greater than 400 MeV/nuc-G diffuse across 10 Jovian radii is calculated to be 5 x 10 to the 21st ions per second, indicating that about 10 to the -7th of the ions from Io are accelerated to over 400 MeV/nuc-G and diffuse to 10 Jovian radii. Observations also suggest that oxygen and sulfur ions in the Io plasma torus diffuse radially outward, are nonadiabatically accelerated in a region outside 17 Jovian radii, and diffuse inward and outward from the accelerated region.

Gehrels, N.↗

NASA NTRS1986

A theory for turbulent curved wall jets

A simple theoretical model is proposed to describe the flow of a turbulent wall jet along a curved surface into a quiescent atmosphere. An integral method is used to solve the momentum equation and identifies three contributions to the spreading rate of the wall jet: (1) turbulent diffusion in the wall jet; (2) wall curvature; and (3) rate of change of wall curvature. Closed from approximate solutions are found for the case of a plane wall, a circular cylinder, and a logarithmic spiral surface. Comparison with experimental data for these three cases is made showing good agreement.

Roberts, Leonard↗

NASA NTRS1987

Remote measurement of in-plane diffusivity components in plates

A method of determining thermal diffusivity in thin plates is presented. The method, using infrared images of evolving thermal patterns previously injected with a laser, is noncontacting, one-sided, and remote. It does not require independent estimates of either the emissivity of the sample or the sample thickness. With a line-segment pattern for thermal input, it yields the inplane components of the diffusivity tensor in anisotropic materials and also the rate of heat loss to the environment of the plate. Two methods of data analysis are presented, one corresponding to a heating line of general cross section and the other considering a Gaussian cross section, thereby saving considerable computer time. Both methods produce a statistical evaluation of measurement quality as well as estimates of diffusivity and loss rate. Results are shown for plates of metals and graphite-epoxy composite materials. Principal components and orientation for the diffusivity tensor are obtained in the anisotropic graphite-epoxy sample.

Welch, Christopher S.↗

NASA NTRS1994

The radio emission from the ultraluminous far-infrared galaxy NGC 6240

We present new radio observations of the 'prototypical' ultraluminous far-infrared galaxy NGC 6240, obtained using the Very Large Array (VLA) at lambda = 20 cm in B-configuration and at lambda = 3.6 cm in A-configuration. These data, along with those from four previous VLA observations, are used to perform a comprehensive study of the radio emission from NGC 6240. Approximately 70% (approximately 3 x 10(exp 23) W/Hz) of the total radio power at 20 cm originates from the nuclear region (approximately less than 1.5 kpc), of which half is emitted by two unresolved (R approximately less than 36 pc) cores and half by a diffuse component. The radio spectrum of the nuclear emission is relatively flat (alpha approximately equals 0.6; S(sub nu) proportional to nu(exp -alpha). The supernova rate required to power the diffuse component is consistent with that predicted by the stellar evolution models of Rieke et al. (1985). If the radio emission from the two compact cores is powered by supernova remnants, then either the remnants overlap and form hot bubbles in the cores, or they are very young (approximately less than 100 yr.) Nearly all of the remaining 30% of the total radio power comes from an 'armlike' region extending westward from the nuclear region. The western arm emission has a steep spectrum (alpha approximately equals 1.0), suggestive of aging effects from synchrotron or inverse-Compton losses, and is not correlated with starlight; we suggest that it is synchrotron emission from a shell of material driven by a galactic superwind. Inverse Compton scattering of far-infrared photons in the radio sources is expected to produce an X-ray flux of approximately 2 - 6 x 10(exp -14) ergs/s/sq cm in the 2 - 10 keV band. No significant radio emission is detected from or near the possible ultramassive 'dark core'.

Colbert, Edward J. M.↗

NASA NTRS1998

Diffusion Characteristics of Upwind Schemes on Unstructured Triangulations

The diffusive characteristics of two upwind schemes, multi-dimensional fluctuation splitting and dimensionally-split finite volume, are compared for scalar advection-diffusion problems. Algorithms for the two schemes are developed for node-based data representation on median-dual meshes associated with unstructured triangulations in two spatial dimensions. Four model equations are considered: linear advection, non-linear advection, diffusion, and advection-diffusion. Modular coding is employed to isolate the effects of the two approaches for upwind flux evaluation, allowing for head-to-head accuracy and efficiency comparisons. Both the stability of compressive limiters and the amount of artificial diffusion generated by the schemes is found to be grid-orientation dependent, with the fluctuation splitting scheme producing less artificial diffusion than the dimensionally-split finite volume scheme. Convergence rates are compared for the combined advection-diffusion problem, with a speedup of 2-3 seen for fluctuation splitting versus finite volume when solved on the same mesh. However, accurate solutions to problems with small diffusion coefficients can be achieved on coarser meshes using fluctuation splitting rather than finite volume, so that when comparing convergence rates to reach a given accuracy, fluctuation splitting shows a 20-25 speedup over finite volume.

Wood, William A.↗

NASA NTRS2000

Rhenium-Oxygen Interactions at High Temperatures

The reaction of pure rhenium metal with dilute oxygen/argon mixtures was studied from 600 to 1400 C. Temperature, oxygen pressure, and flow rates were systematically varied to determine the rate-controlling steps. At lower temperatures the oxygen/rhenium chemical reaction is rate limiting; at higher temperatures gas-phase diffusion of oxygen through the static boundary layer is rate limiting. At all temperatures post-reaction microstructures indicate preferential attack along certain crystallographic planes and defects.

Jacobson, Nathan S.↗

NASA NTRS1991

Parameterization of planetary wave breaking in the middle atmosphere

A parameterization of planetary wave breaking in the middle atmosphere has been developed and tested in a numerical model which includes governing equations for a single wave and the zonal-mean state. The parameterization is based on the assumption that wave breaking represents a steady-state equilibrium between the flux of wave activity and its dissipation by nonlinear processes, and that the latter can be represented as linear damping of the primary wave. With this and the additional assumption that the effect of breaking is to prevent further amplitude growth, the required dissipation rate is readily obtained from the steady-state equation for wave activity; diffusivity coefficients then follow from the dissipation rate. The assumptions made in the derivation are equivalent to those commonly used in parameterizations for gravity wave breaking, but the formulation in terms of wave activity helps highlight the central role of the wave group velocity in determining the dissipation rate. Comparison of model results with nonlinear calculations of wave breaking and with diagnostic determinations of stratospheric diffusion coefficients reveals remarkably good agreement, and suggests that the parameterization could be useful for simulating inexpensively, but realistically, the effects of planetary wave transport.

Garcia, Rolando R.↗

NASA NTRS1977

Kinetics data for diffusion of outgas species from RTV 560

A detailed analytical and experimental study was made of the outgassing behavior of RTV 560 silicone rubber. The four outgas species which predominate in the temperature range of 285 K to 425 K were separately identified. The initial concentration of these species in the parent material and their bulk volatilities were determined. The diffusion coefficients and activation energy for diffusion of the two major species were deduced from outgassing rate data. It is shown that by using these data in a diffusion theory model, the outgassing rates of these major species can be predicted for arbitrary geometry and any temperature within the range studied.

Liu, C. K.↗

NASA NTRS1992

Structure of turbulent non-premixed flames modeled with two-step chemistry

Direct numerical simulations of turbulent diffusion flames modeled with finite-rate, two-step chemistry, A + B yields I, A + I yields P, were carried out. A detailed analysis of the turbulent flame structure reveals the complex nature of the penetration of various reactive species across two reaction zones in mixture fraction space. Due to this two zone structure, these flames were found to be robust, resisting extinction over the parameter ranges investigated. As in single-step computations, mixture fraction dissipation rate and the mixture fraction were found to be statistically correlated. Simulations involving unequal molecular diffusivities suggest that the small scale mixing process and, hence, the turbulent flame structure is sensitive to the Schmidt number.

Chen, J. H.↗

NASA NTRS1993

Positrons from supernovae

Positrons are produced in the ejecta of supernovae by the decay of nucleosynthetic Co-56, Ti-44, and Al-26. We calculate the probability that these positrons can survive without annihilating in the supernova ejecta, and we show that enough of these positrons should escape into the interstellar medium to account for the observed diffuse Galactic annihilation radiation. The surviving positrons are carried by the expanding ejecta into the interstellar medium where their annihilation lifetime of 10 exp 5 - 10 exp 6 yr is much longer than the average supernovae occurrence time of about 100 yr. Thus, annihilating positrons from thousands of supernovae throughout the Galaxy produce a steady diffuse flux of annihilation radiation. We further show that combining the calculated positron survival fractions and nucleosynthetic yields for current supernova models with the estimated supernova rates and the observed flux of diffuse Galactic annihilation radiation suggests that the present Galactic rate of Fe-56 nucleosynthesis is about 0.8 +/- 0.6 solar mass per 100 yr.

Chan, Kai-Wing↗

NASA NTRS2020

Asteroid Cooling Rates Indicated by K-Feldspar Exsolution Textures in H4 Ordinary Chondrites

Undisturbed thermal metamorphism in ordinary chondrite (OC) asteroids, produced through the radioactive decay of 26Al, is expected to result in an onion-shell-like structure. In such a structure, the inner layers of the asteroid experience more extensive thermal metamorphism, as represented by higher petrologic type, than the exterior layers. Furthermore, cooling rates are expected to be slower for OCs of high petrologic type than those of low petrologic type. However, cooling rates determined using metallographic methods and pyroxene diffusion are inconsistent with onion-shell-style cooling and have resulted in new models. These models argue for the disruption of the asteroid after peak metamorphism followed by reaccretion into a rubble pile. Improved constraints on cooling rates would provide a better understanding of the timing and scale of disruptive events. Feldspar microtextures are another tool that can be used to determine asteroid cooling rates. In OC chondrules, plagioclase is present as either a primary phase, or a secondary phase forming from the crystallization of mesostasis glass through petrologic type 4, followed by chemical and textural equilibration. Potas-sium feldspar is observed in petrologic types 3.6-6, as either patches or lamellae exsolved from albite in a perthite texture, often near pores or fractures. Exsolution occurs most commonly, and most extensively, in petrologic type 4. Because the feldspar exsolution wavelength is related to the rate at which grains cooled from the solvus temperature, determined from the mineral’s bulk composition, the chondrite cooling rate can be measured from regions of exsolution. We have previously reported the perthite exsolution cooling rate of Avanhandava, an H4 chondrite, to be 1 °C per 1-4 months over a temperature interval of 765-670 °C. A peristerite exsolution texture was also present in the Na-rich lamellae for which we estimated a cooling rate of 1 °C in 103-104 years from 570-540 °C. Overall, the cooling rates determined from Avanhandava are consistent with pyroxene diffusion (fast cooling at high temperatures) and metallographic rates (slow cooling at low temperatures), hence with the rubble pile model of disruption and reaccretion. Here, we characterize feldspar microtextures in four additional H4 chondrites to test the consistency of feldspar cooling rates across a range of samples. We show that all H4s are similar and support rubble pile models.

Lewis, J. A.↗

NASA NTRS1983

On the possibly low H2 formation rate in dense clouds

It has been found for the Rho Ophiuchi cloud, and suggested for diffuse cloud cores in general, that H2 has a lower formation rate than normally expected in diffuse clouds. It is proposed that this may be due to a reduction in grain surface area per unit volume, if the grains in these regions are enlarged due to coagulation. For the Rho Oph cloud, there is independent evidence that grain coagulation has occurred, so this hypothesis regarding H2 formation has a more substantial basis than for other clouds, where the evidence for suppressed H2 formation is less certain, and for which there is little information on grain sizes.

Snow, T. P.↗

NASA NTRS1988

Experimental and theoretical analysis of the rate of solvent equilibration in the hanging drop method of protein crystal growth

The principles of the hanging-drop method of crystal growth are discussed, and the rate of water evaporation in a water droplet (containing protein, buffer, and a precipitating agent) suspended above a well containing a double concentration of precipitating agent is investigated theoretically. It is shown that, on earth, the rate of evaporation may be determined from diffusion theory and the colligative properties of solutions. The parameters affecting the rate of evaporation include the temperature, the vapor pressure of water, the ionization constant of the salt, the volume of the drop, the contact angle between the droplet and the coverslip, the number of moles of salt in the droplet, the number of moles of water and salt in the well, the molar volumes of water and salt, the distance from the droplet to the well, and the coefficient of diffusion of water vapor through air. To test the theoretical equations, hanging-drop experiments were conducted using various reagent concentrations in 25-microliter droplets and measuring the evaporation times at 4 C and 25 C. The results showed good agreement with the theory.

Fowlis, William W.↗