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At least 343 records · Page 19

The Effects of Gravity on Combustion and Structure Formation During Synthesis of Advanced Materials

Combustion in a variety of heterogeneous systems, leading to the synthesis of advanced materials, is characterized by high temperatures (2000-3500 K) and heating rates (up to 10(exp 6) K/s) at and ahead of the reaction front. These high temperatures generate liquids and gases which are subject to gravity-driven flow. The removal of such gravitational effects is likely to provide increased control of the reaction front, with a consequent improvement in control of the microstructure of the synthesized products. Thus, microgravity experiments can lead to major advances in the understanding of fundamental aspects of combustion and structure formation under the extreme conditions of the combustion synthesis wave. In addition, the specific features of microgravity environment allow one to produce unique materials, which cannot be obtained under terrestrial conditions. The general goals of the current research are: 1) to improve the understanding of fundamental phenomena taking place during combustion of heterogeneous systems, 2) to use low-gravity experiments for insight into the physics and chemistry of materials synthesis processes, and 3) based on the obtained knowledge, to optimize processing conditions for synthesis of advanced materials with desired microstructures and properties. This research follows logically from the results of investigations we have conducted in the framework of our previous grant on gravity influence on combustion synthesis (CS) of gasless systems. Prior work, by others and by us, has clearly demonstrated that gravity plays an important role during combustion synthesis of materials. The immediate tasks for the future are to quantitatively identify the nature of observed effects, and to create accurate local kinetic models of the processes, which can lead to a control of the microstructure and properties of the synthesized materials. In summary, this is the value of the proposed research. Based on our prior work, we focus on the fundamental aspects of combustion and structure formation under the unique condition of microgravity.

Varma, A.↗

SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

SiC and Si3N4 materials were tested under various turbine engine combustion environments, chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high speed aircraft. Representative CVD, sintered, and composite materials were evaluated in both furnace and high pressure burner rig exposure. While protective SiO2 scales form in all cases, evidence is presented to support paralinear growth kinetics, i.e. parabolic growth moderated simultaneously by linear volatilization. The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were used to map SiO2 volatility (and SiC recession) over a range of temperature, pressure, and velocity. The functional dependency of material recession (volatility) that emerged followed the form: exp(-QIRT) * P(exp x) * v(exp y). These empirical relations were compared to rates predicted from the thermodynamics of volatile SiO and SiO(sub x)H(sub Y) reaction products and a kinetic model of diffusion through a moving, boundary layer. For typical combustion conditions, recession of 0.2 to 2 micron/h is predicted at 1200- 1400C, far in excess of acceptable long term limits.

Smialek, James L.↗

Inner Magnetospheric Superthermal Electron Transport: Photoelectron and Plasma Sheet Electron Sources

Two time-dependent kinetic models of superthermal electron transport are combined to conduct global calculations of the nonthermal electron distribution function throughout the inner magnetosphere. It is shown that the energy range of validity for this combined model extends down to the superthermal-thermal intersection at a few eV, allowing for the calculation of the en- tire distribution function and thus an accurate heating rate to the thermal plasma. Because of the linearity of the formulas, the source terms are separated to calculate the distributions from the various populations, namely photoelectrons (PEs) and plasma sheet electrons (PSEs). These distributions are discussed in detail, examining the processes responsible for their formation in the various regions of the inner magnetosphere. It is shown that convection, corotation, and Coulomb collisions are the dominant processes in the formation of the PE distribution function and that PSEs are dominated by the interplay between the drift terms. Of note is that the PEs propagate around the nightside in a narrow channel at the edge of the plasmasphere as Coulomb collisions reduce the fluxes inside of this and convection compresses the flux tubes inward. These distributions are then recombined to show the development of the total superthermal electron distribution function in the inner magnetosphere and their influence on the thermal plasma. PEs usually dominate the dayside heating, with integral energy fluxes to the ionosphere reaching 10(exp 10) eV/sq cm/s in the plasmasphere, while heating from the PSEs typically does not exceed 10(exp 8) eV/sq cm/s. On the nightside, the inner plasmasphere is usually unheated by superthermal electrons. A feature of these combined spectra is that the distribution often has upward slopes with energy, particularly at the crossover from PE to PSE dominance, indicating that instabilities are possible.

Khazanov, G. V.↗

Inner Magnetospheric Superthermal Electron Transport: Photoelectron and Plasma Sheet Electron Sources

Two time-dependent kinetic models of superthermal electron transport are combined to conduct global calculations of the nonthermal electron distribution function throughout the inner magnetosphere. It is shown that the energy range of validity for this combined model extends down to the superthermal-thermal intersection at a few eV, allowing for the calculation of the entire distribution function and thus an accurate heating rate to the thermal plasma. Because of the linearity of the formulas, the source terms are separated to calculate the distributions from the various populations, namely photoelectrons (PEs) and plasma sheet electrons (PSEs). These distributions are discussed in detail, examining the processes responsible for their formation in the various regions of the inner magnetosphere. It is shown that convection, corotation, and Coulomb collisions are the dominant processes in the formation of the PE distribution function, and that PSEs are dominated by the interplay between the drift terms. Of note is that the PEs propagate around the nightside in a narrow channel at the edge of the plasmasphere as Coulomb collisions reduce the fluxes inside of this and convection compresses the flux tubes inward. These distributions are then recombined to show the development of the total superthermal electron distribution function in the inner magnetosphere and their influence on the thermal plasma. PEs usually dominate the dayside heating, with integral energy fluxes to the ionosphere reaching 10(exp 10) eV/sq cm/s in the plasmasphere, while heating from the PSEs typically does not exceed 10(exp 8)eV/sq cm/s. On the nightside, the inner plasmasphere is usually unheated by superthermal electrons. A feature of these combined spectra is that the distribution often has upward slopes with energy, particularly at the crossover from PE to PSE dominance, indicating that instabilities are possible.

Khazanov, G. V.↗

Ensemble Diffraction Measurements of Spray Combustion in a Novel Vitiated Coflow Turbulent Jet Flame Burner

An experimental investigation is presented of a novel vitiated coflow spray flame burner. The vitiated coflow emulates the recirculation region of most combustors, such as gas turbines or furnaces; additionally, since the vitiated gases are coflowing, the burner allows exploration of the chemistry of recirculation without the corresponding fluid mechanics of recirculation. As such, this burner allows for chemical kinetic model development without obscurations caused by fluid mechanics. The burner consists of a central fuel jet (droplet or gaseous) surrounded by the oxygen rich combustion products of a lean premixed flame that is stabilized on a perforated, brass plate. The design presented allows for the reacting coflow to span a large range of temperatures and oxygen concentrations. Several experiments measuring the relationships between mixture stoichiometry and flame temperature are used to map out the operating ranges of the coflow burner. These include temperatures as low 300 C to stoichiometric and oxygen concentrations from 18 percent to zero. This is achieved by stabilizing hydrogen-air premixed flames on a perforated plate. Furthermore, all of the CO2 generated is from the jet combustion. Thus, a probe sample of NO(sub X) and CO2 yields uniquely an emission index, as is commonly done in gas turbine engine exhaust research. The ability to adjust the oxygen content of the coflow allows us to steadily increase the coflow temperature surrounding the jet. At some temperature, the jet ignites far downstream from the injector tube. Further increases in the coflow temperature results in autoignition occurring closer to the nozzle. Examples are given of methane jetting into a coflow that is lean, stoichiometric, and even rich. Furthermore, an air jet with a rich coflow produced a normal looking flame that is actually 'inverted' (air on the inside, surrounded by fuel). In the special case of spray injection, we demonstrate the efficacy of this novel burner with a methanol spray in a vitiated coflow. As a proof of concept, an ensemble light diffraction (ELD) optical instrument was used to conduct preliminary measurements of droplet size distribution and liquid volume fraction.

Cabra, R.↗

Transport of Photoelectrons in the Nightside Magnetosphere

Kinetic modeling results are analyzed to examine the transport of photoelectrons through the nightside inner magnetosphere. A natural filter exists on the nightside for these particles, with Coulomb collisions eroding the distribution at low energies and low L shells, and magnetospheric convection compressing the flux tubes as they corotate towards dawn. This leads to an electron population with very distinctive features. It is shown that, for low activity levels, a band of photoelectrons forms between L=4 and 6 that extends throughout the nightside local times and into the morning sector. Modeled energy and pitch angle distributions are presented to show the development and features of this electron band, as well as their influences on the thermal plasma. Such a population should be observable in satellite spectrometer measurements.

Khazanov, G. V.↗

Transport of Photoelectrons in the Nightside Magnetosphere

Kinetic modeling results are analyzed to examine the transport of photoelectrons through the nightside inner magnetosphere. Two sources are considered, those on the dayside from direct solar illumination, and those at all local times from light scattered by the upper atmosphere and geocorona. For the dayside photoelectrons, a natural filter exists oil the nightside for these particles, with Coulomb collisions eroding the distribution at low energies and low L shells, and magnetospheric convection compressing the flux tubes as they corotate towards dawn. It is shown that, for low activity levels, a band of photoelectrons forms between L=4 and 6 that extends throughout the nightside local times and into the morning sector. For the scattered light photoelectrons, the trapped zone throughout the nightside is filled for energies less than 30 eV. Convective compression on the nightside and expansion on the dayside yields an accelerated population up to 50 eV at high L shells around dawn. Modeled energy and pitch angle distributions are presented to show the development and features of these populations. Such distinctive features should be observable in satellite spectrometer measurements.

Khazanov, G. V.↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

Transition from Gaseous Compounds to Aerosols in Titan's Atmosphere

We investigate the chemical transition of simple molecules like C2H2 and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help understand and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, that will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics (PAHs), polymers of HCN and other nitriles, and polynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C2H2, HCN, HC3N and other nitriles, C6H6) from the gas phase to the haze. We use a 1-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursors macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4 x 10(exp -14) g/ sq cm s and a C/N approx. = 4. These results are compared with experimental data, and to microphysical models requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, that will be a great challenge for our understanding of those chemical processes.

Lebonnois, Sebastien↗

Mineralogic and Petrologic Studies of Meteorites

This report lists publications related to work done under NASA grant. Topics as indicated by title include: condensation in fractionated nebular systems, nebular processes in different constituents of the CH chondrite NWA 470, growth mechanism and additional constraints on FeNi metal condensation in the solar nebula, the ZONMET thermodynamic and kinetic model of metal condensation, the first occurrence of CaAl2O4 in a CAI (calcium aluminum inclusion) from the new CH chondrite NWA 470.

Wood, John↗

Structural Basis for Flip-Flop Action of Thiamin-Dependent Enzymes Revealed by Crystal Structure of Human Pyruvate Dehydrogenase

The biologically active derivative of vitamin B1; thiamin pyrophosphate; is used as cofactor by many enzymes that perform a wide range of catalytic functions in the pathways of energy production. In alpha2beta2-heterotetrameric human pyruvate dehydrogenase, the first catalytic component enzyme of human pyruvate dehydrogenase complex, this cofactor is used to cleave the C(sup alpha)-C(=0) bond of pyruvate followed by reductive acetyl transfer to lipoyl-dihydrolipoamide acetyltransferase, the second catalytic component of the complex. The dynamic nonequivalence of two, otherwise chemically equivalent, catalytic sites have puzzled researchers from earlier functional studies of this enzyme. In order to gain insight into the mechanism of action of this enzyme, we determined the crystal structure of the holoform of human pyruvate dehydrogenase at 1.958, resolution. We propose a kinetic model for the flip-flop action of this enzyme through the concerted approx. 2A, shuttle-like motion of the heterodimers. The similarity of thiamin pyrophosphate binding in human pyruvate dehydrogenase and other functionally related enzymes suggests this newly defined mechanism of shuttle-like motion of domains to be common for the family of thiamin pyrophosphate-dependent enzymes.

Ciszak, Ewa↗

Transport of Photoelectrons in the Nightside Magnetosphere

Kinetic modeling results are analyzed to examine the transport of photoelectrons through the nightside inner magnetosphere. Two sources are considered, those on the dayside from direct solar illumination and those across the nightside from light scattered by the upper atmosphere and geocorona. A natural filter exists on the nightside for the dayside photoelectrons. Coulomb collisions erode the distribution at low energies and low L shells, and magnetospheric convection compresses the electrons as they drift toward dawn. It is shown that for low-activity levels a band of photoelectrons forms between L = 4 and 6 that extends throughout the nightside local times and into the morning sector. For the scattered light photoelectrons the trapped zone throughout the nightside is populated with electrons of E less than 30 eV. At high L shells near dawn, convective compression on the nightside yields an accelerated population with electrons at energies up to twice the ionospheric energy maximum (that is, roughly 1200 eV for dayside photoelectrons and 60 eV for scattered light electrons). Modeled energy and pitch angle distributions are presented to show the features of these populations.

Khazanov, G. V.↗

Large Eddy Simulation Of Gravitational Effects In Transitional And Turbulent Gas-Jet Diffusion Flames

The influence of gravity on the spatial and the compositional structures of transitional and turbulent hydrocarbon diffusion flames are studies via large eddy simulation (LES) and direct numerical simulation (DNS) of round and planar jets. The subgrid-scale (SGS) closures in LES are based on the filtered mass density function (FMDF) methodology. The FMDF represents the joint probability density function (PDF) of the SGS scalars, and is obtained by solving its transport equation. The fundamental advantage of LES/FMDF is that it accounts for the effects of chemical reaction and buoyancy exactly. The methodology is employed for capturing some of the fundamental influences of gravity in equilibrium flames via realistic chemical kinetic schemes. Some preliminary investigation of the gravity effects in non-equilibrium flames is also conducted, but with idealized chemical kinetics models.

Jaberi, Farhad A.↗

Cool Flames in Propane-Oxygen Premixtures at Low and Intermediate Temperatures at Reduced-Gravity

The Cool Flame Experiment aims to address the role of diffusive transport on the structure and the stability of gas-phase, non-isothermal, hydrocarbon oxidation reactions, cool flames and auto-ignition fronts in an unstirred, static reactor. These reactions cannot be studied on Earth where natural convection due to self-heating during the course of slow reaction dominates diffusive transport and produces spatio-temporal variations in the thermal and thus species concentration profiles. On Earth, reactions with associated Rayleigh numbers (Ra) less than the critical Ra for onset of convection (Ra(sub cr) approx. 600) cannot be achieved in laboratory-scale vessels for conditions representative of nearly all low-temperature reactions. In fact, the Ra at 1g ranges from 10(exp 4) - 10(exp 5) (or larger), while at reduced-gravity, these values can be reduced two to six orders of magnitude (below Ra(sub cr)), depending on the reduced-gravity test facility. Currently, laboratory (1g) and NASA s KC-135 reduced-gravity (g) aircraft studies are being conducted in parallel with the development of a detailed chemical kinetic model that includes thermal and species diffusion. Select experiments have also been conducted at partial gravity (Martian, 0.3gearth) aboard the KC-135 aircraft. This paper discusses these preliminary results for propane-oxygen premixtures in the low to intermediate temperature range (310- 350 C) at reduced-gravity.

Pearlman, Howard↗

Prediction and Validation of Mars Pathfinder Hypersonic Aerodynamic Data Base

Postflight analysis of the Mars Pathfinder hypersonic, continuum aerodynamic data base is presented. Measured data include accelerations along the body axis and axis normal directions. Comparisons of preflight simulation and measurements show good agreement. The prediction of two static instabilities associated with movement of the sonic line from the shoulder to the nose and back was confirmed by measured normal accelerations. Reconstruction of atmospheric density during entry has an uncertainty directly proportional to the uncertainty in the predicted axial coefficient. The sensitivity of the moment coefficient to freestream density, kinetic models and center-of-gravity location are examined to provide additional consistency checks of the simulation with flight data. The atmospheric density as derived from axial coefficient and measured axial accelerations falls within the range required for sonic line shift and static stability transition as independently determined from normal accelerations.

Gnoffo, Peter A.↗

Role of microbes in the smectite-to-illite reaction

Temperature, pressure, and time have been thought to control the smectite-to-illite (S-I) reaction, an important diagenetic process used for petroleum exploration. We demonstrated that microorganisms can promote the S-I reaction by dissolving smectite through reduction of structural Fe(III) at room temperature and 1 atmosphere within 14 days. This reaction typically requires conditions of 300 degrees to 350 degrees C, 100 megapascals, and 4 to 5 months in the absence of microbial activity. These results challenge the conventional concept of the S-I reaction and of reaction kinetic models.

Minerals/chemistry/metabolism↗

Angiogenesis and osteogenesis in an orthopedically expanded suture

The purpose of this study was to examine the angiogenic and the subsequent osteogenic responses during a 96-hour time-course after sutural expansion. Fifty rats were divided into: (1) a control group that received only angiogenic induction through injection of 5 ng/gm recombinant human endothelial cell growth factor (rhECGF); (2) an experimental group that received orthopedic expansion and rhECGF; (3) a sham group that received expansion and sodium chloride (NaCl) injection; and (4) a baseline group that received no expansion or injection. All rats were injected with 3H-thymidine (1.0 microCi/gm) 1 hour before death to label the DNA of S-phase cells. Demineralized sections (4 microm thick) were stained with hematoxylin and eosin. Angiogenesis and cell migration were analyzed with a previously established cell kinetics model. Analysis of variance was used to test the hypothesis that enhancement of angiogenesis stimulates reestablishment of osteogenic capability. Blood vessel number, area, and endothelial cell-labeled index significantly increased in experimental groups, but no difference was found between control and baseline groups. Labeled-pericyte index and activated pericyte numbers in the experimental group were also higher than in the sham groups. These results show that supplemental rhECGF enhances angiogenesis in expanded sutures but not in nonexpanded sutures. Data also suggest that pericytes are the source of osteoblasts in an orthopedically expanded suture.

NASA Discipline Musculoskeletal↗

DNA Damage by Ionizing Radiation: Tandem Double Lesions by Charged Particles

Oxidative damages by ionizing radiation are the source of radiation-induced carcinogenesis, damage to the central nervous system, lowering of the immune response, as well as other radiation-induced damages to human health. Monte Carlo track simulations and kinetic modeling of radiation damages to the DNA employ available molecular and cellular data to simulate the biological effect of high and low LET radiation io the DNA. While the simulations predict single and double strand breaks and base damages, so far all complex lesions are the result of stochastic coincidence from independent processes. Tandem double lesions have not yet been taken into account. Unlike the standard double lesions that are produced by two separate attacks by charged particles or radicals, tandem double lesions are produced by one single attack. The standard double lesions dominate at the high dosage regime. On the other hand, tandem double lesions do not depend on stochastic coincidences and become important at the low dosage regime of particular interest to NASA. Tandem double lesions by hydroxyl radical attack of guanine in isolated DNA have been reported at a dosage of radiation as low as 10 Gy. The formation of two tandem base lesions was found to be linear with the applied doses, a characteristic of tandem lesions. However, tandem double lesions from attack by a charged particle have not been reported.

Huo, Winifred M.↗