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At least 271 records · Page 15

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

Silicon carbide (SiC) and Si3N4 materials were tested in various turbine engine combustion environments chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high-speed aircraft. Representative chemical vapor-deposited (CVD), sintered, and composite materials were evaluated by furnace and high-pressure burner rig exposures. Although protective SiO2 scales formed in all cases, the evidence presented supports a model based on 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 thus used to map SiO2 volatility (and SiC recession) over a range of temperatures, pressures, and velocities. The functional dependency of material recession (volatility) that emerged followed the form A[exp(-Q / RT)](P(sup x)v(sup y). These empirical relations were compared with rates predicted from the thermodynamics of volatile SiO and SiOxHy reaction products and a kinetic model of diffusion through a moving boundary layer. For typical combustion conditions, recession of 0.2 to 2 micrometers/hr is predicted at 1200 to 1400 C, far in excess of acceptable long-term limits.

Smialek, James L.↗

On Orbit Measurement of Response vs. Scan Angle for the Infrared Bands on TRMM/VIRS

The Visible and Infrared Scanner on the Tropical Rainfall Measuring Mission (TRMM/VIRS) is a whiskbroom imaging radiometer with two reflected solar bands and three emissive infrared bands. All five detectors are on a single cooled focal plane. This configuration necessitated the use of a paddlewheel scan mirror to avoid the effects of focal plane rotation that arise when using a scan mirror that is inclined to its axis of rotation. System radiometric requirements led to the need for protected silver as the mirror surface. Unfortunately, the SiO(x) coatings currently used to protect silver from oxidation introduce a change in reflectance with angle of incidence (AOI). This AOI dependence results in a modulation of system level response with scan angle. Measurement of system response vs. scan angle (RVS) was not difficult for the VIRS reflected solar bands, but attaining the required accuracy for the IR bands in the laboratory was not possible without a large vacuum chamber and a considerable amount of custom designed testing apparatus. Therefore, the decision was made to conduct the measurement on-orbit. On three separate occasions, the TRMM spacecraft was rotated about its pitch axis and, after the nadir view passed over the Earth's limb, the VIRS performed several thousand scans while viewing deep space. The resulting data has been analyzed and the RVS curves generated for the three IR bands are being used in the VIRS radiometric calibration algorithm. This, to our knowledge, the first time this measurement has been made on-orbit. Similar measurements are planned for the EOS-AM and EOS-PM MODIS sensors and are being considered for several systems under development. The VIRS on-orbit results will be compared to VIRS and MODIS system level laboratory measurements, MODIS scan mirror witness sample measurements and modeled data.

Barnes, William L.↗

Design of a Three-Layer Antireflection Coating for High Efficiency Indium Phosphide Solar Cells Using a Chemical Oxide as First Layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 microns of the illuminated surface of the cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with the p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally, a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown, thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3- layer AR coating for thermally diffused p(+)n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p(+) emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as a fairly efficient antireflective layer yielding a measured record high AM0, 25 C, open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3, MgF2 or ZnS, MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductor materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating, should work well for essentially all III-V compound-based solar cells.

Moulot, Jacques↗

Fabrication and Thermo-Optical Properties of the MLS Composite Primary Reflector

The Microwave Limb Sounder (MLS) is a limb-sounding radiometer sensing emissions in the millimeter and sub-millimeter range. MLS will contribute to an understanding of atmospheric chemistry by assessing stratospheric and tropospheric ozone depletion, climate forcings and volcanic effects. The heart of the antenna is the primary reflector, constructed from graphite/cyanate composites in a facesheet/core construction. The reflector has an aperture of one square meter, a mass of 8.7 kilos and final figure accuracy of 4.37 microns rms. The surface is also modified to ensure RF reflectivity, prevent solar concentration and provide thermal balance to the spacecraft The surface is prepared by precision beadblasting, then coated with vapor deposited aluminum (VDA) and finally a layer of silicon suboxide (SiO(x)) to control the infrared emissivity. The resulting surface has a solar absorptance of 0.43 and an absorptance/emittance ratio of 1.3. BRDF analysis shows that 93% of the incident thermal energy is reflected outside a 10 degree angle of cone. For its mass and aperture, we believe this reflector to have the highest figure accuracy yet achieved in a composite antenna construction.

Willis, Paul B.↗

Issues and Effects of Atomic Oxygen Interactions With Silicone Contamination on Spacecraft in Low Earth Orbit

The continued presence and use of silicones on spacecraft in low Earth orbit (LEO) has been found to cause the deposition of contaminant films on surfaces which are also exposed to atomic oxygen. The composition and optical properties of the resulting SiO(x)- based (where x is near 2) contaminant films may be dependent upon the relative rates of arrival of atomic oxygen, silicone contaminant and hydrocarbons. This paper presents results of in-space silicone contamination tests, ground laboratory simulation tests and analytical modeling to identify controlling processes that affect contaminant characteristics.

Banks, Bruce↗

The Postshock Chemical Lifetimes of Outflow Tracers and a Possible New Mechanism to Produce Water Ice Mantles

We have used a coupled time-dependent chemical and dynamical model to investigate the lifetime of the chemical legacy in the wake of C-type shocks. We concentrate this study on the chemistry of H2O and O2, two molecules which are predicted to have abundances that are significantly affected in shock-heated gas. Two models are presented: (1) a three-stage model of preshock, shocked, and postshock gas; and (2) a Monte Carlo cloud simulation where we explore the effects of stochastic shock activity on molecular gas over a cloud lifetime. For both models we separately examine the pure gas-phase chemistry as well as the chemistry including the interactions of molecules with grain surfaces. In agreement with previous studies, we find that shock velocities in excess of 10 km/s are required to convert all of the oxygen not locked in CO into H2O before the gas has an opportunity to cool. For pure gas phase models the lifetime of the high water abundances, or "H2O legacy," in the postshock gas is approximately (4-7) x 10(exp 5) yr, independent of the gas density. A density dependence for the lifetime of H2O is found in gas-grain models as the water molecules deplete onto grains at the depletion timescale. Through the Monte Carlo cloud simulation we demonstrate that the time-average abundance of H2O, the weighted average of the amount of time gas spends in preshock, shock, and postshock stages, is a sensitive function of the frequency of shocks. Thus we predict that the abundance of H2O, and to a lesser extent O2, can be used to trace the history of shock activity in molecular gas. We use previous large-scale surveys of molecular outflows to constrain the frequency of 10 km/s shocks in regions with varying star formation properties and discuss the observations required to test these results. We discuss the postshock lifetimes for other possible outflow tracers (e.g., SiO and CH3OH) and show that the differences between the lifetimes for various tracers can produce potentially observable chemical variations between younger and older outflows. For gas-grain models we find that the abundance of water-ice on grain surfaces can be quite large and is comparable to that observed in molecular clouds. This offers a possible alternative method to create water mantles without resorting to grain surface chemistry: gas heating and chemical modification due to a C-type shock and subsequent depletion of the gas-phase species onto grain mantles.

Bergin, Edwin A.↗

Outgassing of Flown and Unflown MIR Solar Cells

A solar panel array with more than ten years space exposure was removed from the Mir core module in November 1997, and an eight panel section was returned to Earth in January 1998. Several solar cells were removed from panel eight of the returned array and placed in a high vacuum system with a residual gas analyzer (200 amu mass spectrometer) and a cold finger. Similar unflown solar cells of the same vintage were later obtained from Energia. Several of the unflown cells were also placed in the vacuum system and outgassed residues were collected on the LN2 cold finger. Almost 3 mg of outgassed residue was collected -from a string of three unflown solar cells over a period of 94 hours under vacuum. The collected residue was weighed with a microbalance, and then the residue was analyzed by FTIR spectroscopy, and by gas chromatograph-mass spectroscopy. About 25 outgassed constituents were separated by the gas chromatograph, and a high-resolution mass spectrum was obtained of each constituent. Molecular identifications have been made for the constituents. The constituents are primarily cyclic siloxanes, and several of the constituents are isomers of the same molecule. Most of the outgassed constituents have a molecular mass of about 500 amu. Almost one mg of residue was extracted from one sq cm of coverglass/adhesive from a flown solar cell by soaking in isopropyl alcohol for 30 minutes. The gas chromatograph separated about 20 constituents. The constituents are mostly cyclic siloxanes with linear branches, hydrocarbons, and phthalates. The typical molecular mass is about 600 amu. These identifications of specific outgassing molecules have resulted in a more complete understanding of the SiO(x) contamination on the Mir solar cell coverglasses, and on the MEEP experiment trays and optical specimens during the Shuttle-Mir Phase One flight experiment program. Adjusted outgassing rates based on the data reported here, and/or measured outgassing rates and specific molecular identifications of ISS hardware samples are needed to input into model predictions of induced environment effects of the ISS.

Harvey, Gale A.↗

Quiescent Giant Molecular Cloud Cores in the Galactic Center

We have used the Long Wavelength Spectrometer (LWS) aboard the Infrared Space Observatory (ISO) to map the far-infrared continuum emission (45-175 micrometer) toward several massive Giant Molecular Cloud (GMC) cores located near the Galactic center. The observed far-infrared and submillimeter spectral energy distributions imply low temperatures (approx. 15 - 22 K) for the bulk of the dust in all the sources, consistent with external heating by the diffuse ISRF and suggest that these GMCs do not harbor high- mass star-formation sites, in spite of their large molecular mass. Observations of FIR atomic fine structure lines of C(sub II) and O(sub I) indicate an ISRF enhancement of approx. 10(exp 3) in the region. Through continuum radiative transfer modeling we show that this radiation field strength is in agreement with the observed FIR and submillimeter spectral energy distributions, assuming primarily external heating of the dust with only limited internal luminosity (approx. 2 x 10(exp 5) solar luminosity). Spectroscopic observations of millimeter-wave transitions of H2CO, CS, and C-34S carried out with the Caltech Submillimeter Observatory (CSO) and the Institut de Radio Astronomie Millimetrique (IRAM) 30-meter telescope indicate a gas temperature of approx. 80 K, significantly higher than the dust temperatures, and density of approx. 1 x 10(exp 5)/cc in GCM0.25 + 0.01, the brightest submillimeter source in the region. We suggest that shocks caused by cloud collisions in the turbulent interstellar medium in the Galactic center region are responsible for heating the molecular gas. This conclusion is supported by the presence of wide-spread emission from molecules such as SiO, SO, and CH3OH, which are considered good shock tracers. We also suggest that the GMCs studied here are representative of the "typical", pre-starforming cloud population in the Galactic center.

Lis, D. C.↗

Paralinear Oxidation of CVD SiC in Simulated Fuel-Rich Combustion

The oxidation kinetics of CVD SiC were measured by thermogravimetric analysis (TGA) in a 4H2 (central dot) 12H2O (central dot) 10CO (central dot) 7CO2 (central dot) 67N2 gas mixture flowing at 0.44 cm/s at temperatures between 1300 and 1450 C in fused quartz furnace tubes at I atm total pressure. The SiC was oxidized to form solid SiO2. At less than or = 1350 C, the SiO2 was in turn volatilized. Volatilization kinetics were consistent with the thermodynamic predictions based on SiO formation. These two simultaneous reactions resulted in overall paralinear kinetics. A curve fitting technique was used to determine the linear and parabolic rate constants from the paralinear kinetic data. Volatilization of the protective SiO2 scale resulted in accelerated consumption of SiC. Recession rates under conditions more representative of actual combustors were estimated from the furnace data.

Fox, Dennis S.↗

The Scientific Case for Sample Return from a Primitive Near-Earth Asteroid

This paper is predicated on the recent experimental findings that the smallest structural ferromagnesiosilica entities in collected chondritic aggregate interplanetary dust particles (IDPs) have a predictable metastable eutectic composition. Kinetically controlled gas to solid condensation of MgFe-SiO-O2-H2 vapors does NOT produce stoichiometric crystalline solids (i.e. minerals) such as predicted by equilibrium condensation models but instead yields amorphous solids that are chemically ordered at metastable eutectics in the binary phase diagrams. Therefore these condensed dust grains will have a considerable amount of 'internal free energy' that will make them highly responsive to changes in their environments. Their inherent high energy-content 'buys' time and energy for mineralogical modification and chemical readjustment in response to changing environmental conditions. The activation energy barrier for reactions in metastable eutectic solids will be lower than for crystalline solids. As a result the reactions can take place at much lower temperatures and on much shorter time scales. That is, they will also occur much earlier in the evolution of a parent body wherein heat-producing sources may either be immature or inefficient. The ensuing reaction chains from metastable equilibrium to full thermodynamic equilibration with the local environment will be a chaotic 'Ostwald cascade' but from a well defined starting point to a predictable end result. Here we will discuss the implications of metastable eutectic dust as we see them for dust properties in icy and ice-free parent bodies wherein circumstellar dust is still recognizable because of the primitive nature of these parent bodies. We point to potential engineering constraints on sample acquisition and storage during Earth transit. Among the scientific goals of a primitive Near Earth Asteroid (NEA) sample return mission will be verification of the nature of dust forming and modification processes during hierarchical accretion in the earliest protoplanets. We propose sampling an infrared P- or D-class NEA or an object showing cometary activity such as 2201 Oljato that could be an asteroid or evolved comet. Additional information is contained in the original extended abstract.

Rietmeijer, Frans J. M.↗

Molecular Spectroscopy by Ab Initio Methods

Due to recent advances in methods and computers, the accuracy of ab calculations has reached a point where these methods can be used to provide accurate spectroscopic constants for small molecules; this will be illustrated with several examples. We will show how ab initio calculations where used to identify the Hermann infrared system in N2 and two band systems in CO. The identification of all three of these band systems relied on very accurate calculations of quintet states. The analysis of the infrared spectra of cool stars requires knowledge of the intensity of vibrational transitions in SiO for high nu and J levels. While experiment can supply very accurate dipole moments for nu = 0 to 3, this is insufficient to construct a global dipole moment function. We show how theory, combined by the experiment, can be used to generate the line intensities up to nu = 40 and J = 250. The spectroscopy of transition metal containing systems is very difficult for both theory and experiment. We will discuss the identification of the ground state of Ti2 and the spectroscopy of AlCu as examples of how theory can contribute to the understanding of these complex systems.

Bauschlicher, Charles W., Jr.↗

The Dependence of Atomic Oxygen Undercutting of Protected Polyimide Kapton(tm) H upon Defect Size

Understanding the behavior of polymeric materials when exposed to the low-Earth-orbit (LEO) environment is important in predicting performance characteristics such as in-space durability. Atomic oxygen (AO) present in LEO is known to be the principal agent in causing undercutting erosion of SiO(x) protected polyimide Kapton(R) H film, which serves as a mechanically stable blanket material in solar arrays. The rate of undercutting is dependent on the rate of arrival, directionality and energy of the AO with respect to the film surface. The erosion rate also depends on the distribution of the size of defects existing in the protective coating. This paper presents results of experimental ground testing using low energy, isotropic AO flux together with numerical modeling to determine the dependence of undercutting erosion upon defect size.

Snyder, Aaron↗

Modeling of Transmittance Degradation Caused by Optical Surface Contamination by Atomic Oxygen Reaction with Adsorbed Silicones

A numerical procedure is presented to calculate transmittance degradation caused by contaminant films on spacecraft surfaces produced through the interaction of orbital atomic oxygen (AO) with volatile silicones and hydrocarbons from spacecraft components. In the model, contaminant accretion is dependent on the adsorption of species, depletion reactions due to gas-surface collisions, desorption, and surface reactions between AO and silicone producing SiO(x), (where x is near 2). A detailed description of the procedure used to calculate the constituents of the contaminant layer is presented, including the equations that govern the evolution of fractional coverage by specie type. As an illustrative example of film growth, calculation results using a prototype code that calculates the evolution of surface coverage by specie type is presented and discussed. An example of the transmittance degradation caused by surface interaction of AO with deposited contaminant is presented for the case of exponentially decaying contaminant flux. These examples are performed using hypothetical values for the process parameters.

Snyder, Aaron↗

Electronic spectroscopy of diatomic molecules

This article provides an overview of the principal computational approaches and their accuracy for the study of electronic spectroscopy of diatomic molecules. We include a number of examples from our work that illustrate the range of application. We show how full configuration interaction benchmark calculations were instrumental in improving the understanding of the computational requirements for obtaining accurate results for diatomic spectroscopy. With this understanding it is now possible to compute radiative lifetimes accurate to within 10% for systems involving first- and second-row atoms. We consider the determination of the infrared vibrational transition probabilities for the ground states of SiO and NO, based on a globally accurate dipole moment function. We show how we were able to assign the a(sup "5)II state of CO as the upper state in the recently observed emission bands of CO in an Ar matrix. We next discuss the assignment of the photoelectron detachment spectra of NO and the alkali oxide negative ions. We then present several examples illustrating the state-of-the-art in determining radiative lifetimes for valence-valence and valence-Rydberg transitions. We next compare the molecular spectroscopy of the valence isoelectronic B2, Al2, and AlB molecules. The final examples consider systems involving transition metal atoms, which illustrate the difficulty in describing states with different numbers of d electrons.

Partridge, Harry↗

Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

Copland, Evan↗

Micro-Detection System for Determination of the Biotic or Abiotic Origin of Amino Acids

The research involved the development of a breadboard version of a spacecraft based system for the detection of amino acid chirality (handedness) on solar system bodies. The design concept has three distinct components: a sublimation chamber for the release of amino acids from an acquired sample; a microchip based capillary electrophoresis (CE) chip for the separation of amino acids and their enantiomers; and a fluorescent based detection system. In addition, we have investigated the use of a microfluidics system for the extraction of amino acids in samples in which sublimation has proven to be problematic. This is a joint project carried out at the Scripps Institution of Oceanography (SIO), University of California at San Diego; the Jet Propulsion Laboratory (JPL), Pasadena; and the Department of Chemistry, University of California, Berkeley.

Bada, Jeffrey L.↗

The Millimeter-Wave Properties of Superconducting Microstrip Lines

We have developed a novel technique for making high quality measurements of the millimeter-wave properties of superconducting thin-film microstrip transmission lines. Our experimental technique currently covers the 75-100 GHz band. The method is based on standing wave resonances in an open ended transmission line. We obtain information on the phase velocity and loss of the microstrip. Our data for Nb/SiO/Nb lines, taken at 4.2 K and 1.6 K, can be explained by a single set of physical parameters. Our preliminary conclusion is that the loss is dominated by the SiO dielectric, with a temperature-independent loss tangent of 5.3 +/- 0.5 x 10(exp -3) for our samples.

Vayonakis, A.↗

Anomalous Heat Budgets in the Interior Pacific Ocean on Seasonal- to -Timescales and Gyre Spacescales

This study quantifies uncertainties in closing the seasonal cycle of diabatic heat storage over the Pacific Ocean from 20 degrees S to 60 degrees N through the synthesis of World Ocean Circulation Experiment (WOCE) products over 7 years from 1993-1999. We utilize WOCE reanalysis products from the following sources: diabatic heat storage (DHS) from the Scripps Institution of Oceanography (SIO); near-surface geostrophic and Ekman currents from the Earth and Space Research (ESR); and air-sea heat fluxes from Comprehensive Ocean-Atmosphere Data Set (COADS), National Centers for Environmental Prediction (NCEP), and European Center for Mid-Range Weather Forecasts (ECMWF). We interpolate these products onto a common grid, allowing the seasonal cycle of DHS to be modeled for comparison with that observed. Everywhere latent heat flux residuals dominate sensible heat flux residuals and shortwave heat flux residuals dominate longwave heat flux residuals, both comparable in magnitude to the residual horizontal heat advection. We find the root-mean-square (RMS) of the differences between observed and model residual DHS tendencies to be less than 15 W per square meters everywhere except in the Kuroshio extension. Comparable COADS and NCEP products perform better than ECMWF products in the extra-tropics, while the NCEP product performs best in the tropics. Radiative and turbulent air-sea heat flux residuals computed from ship-born measurements perform better than those computed from satellite cloud and wind measurements. Since the RMS differences derive largely from biases in measured wind speed and cloud fraction, least-squares minimization is used to correct the residual Ekman heat advection and air-sea heat flux. Minimization reduces RMS differences less than 5 W per square meters except in the Kuroshio extension, suggesting how winds, clouds, and exchange coefficients in the NCEP, ECMWF, and ESR products can be improved.

White, Warren↗