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At least 343 records · Page 19

Astronomical Problems and Laboratory Solutions

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. there is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

Oxidation Behavior of HfB2-SiC Materials in Dissociated Environments

Hafnium diboride based materials have shown promise for use in extremely high temperature applications, such as sharp leading edges on future reentry vehicles. During reentry, the oxygen and nitrogen in the atmosphere are dissociated by the shock layer ahead of the sharp leading edge such that surface reactions are determined by reactions of monatomic oxygen and nitrogen rather than O2, and N2. Simulation of the reentry environment on the ground requires the use of arc jet (plasma jet) facilities that provide monatomic species and are the closest approximation to actual flight conditions. Simple static or flowing oxidation studies under ambient pressures and atmospheres are not adequate to develop an understanding of a materials behavior in flight. Arc jet testing is required to provide the appropriate stagnation pressures, heat fluxes, enthalpies, heat loads and atmospheres encountered during flight. This work looks at the response of HfB2/SiC materials exposed to various simulated reentry environments.

Ellerby, Don↗

Comparison of automated pre-column and post-column analysis of amino acid oligomers

It has been shown that various amino acids will polymerize under plausible prebiotic conditions on mineral surfaces, such as clays and soluble salts, to form varying amounts of oligomers (n = 2-6). The investigations of these surface reactions required a quantitative method for the separation and detection of these amino acid oligomers at the picomole level in the presence of nanomole levels of the parent amino acid. In initial high-performance liquid chromatography (HPLC) studies using a classical postcolumn o-phthalaldehyde (OPA) derivatization ion-exchange HPLC procedure with fluorescence detection, problems encountered included lengthy analysis time, inadequate separation and large relative differences in sensitivity for the separated species, expressed as a variable fluorescent yield, which contributed to poor quantitation. We have compared a simple, automated, pre-column OPA derivatization and reversed-phase HPLC method with the classical post-column OPA derivatization and ion-exchange HPLC procedure. A comparison of UV and fluorescent detection of the amino acid oligomers is also presented. The conclusion reached is that the pre-column OPA derivatization, reversed-phase HPLC and UV detection produces enhanced separation, improved sensitivity and faster analysis than post-column OPA derivatization, ion-exchange HPLC and fluorescence detection.

NASA Discipline Exobiology↗

Infrared emission spectra of candidate interstellar aromatic molecules

Interstellar dust is responsible, through surface reactions, for the creation of molecular hydrogen, the main component of the interstellar clouds in which new stars form. Intermediate between small, gas-phase molecules and dust are the polycyclic aromatic hydrocarbons (PAHs). Such molecules could account for 2-30% of the carbon in the Galaxy, and may provide nucleation sites for the formation of carbonaceous dust. Although PAHs have been proposed as the sources of the unidentified infrared emission bands that are observed in the spectra of a variety of interstellar sources, the emission characteristics of such molecules are still poorly understood. Here we report laboratory emission spectra of several representative PAHs, obtained in conditions approximating those of the interstellar medium, and measured over the entire spectral region spanned by the unidentified infrared bands. We find that neutral PAHs of small and moderate size can at best make only a minor contribution to these emission bands. Cations of these molecules, as well as much larger PAHs and their cations, remain viable candidates for the sources of these bands.

Non-NASA Center↗

Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

Huang, Chen-Kuo↗

The Ice Line in Pre-Solar Protoplanetary Disks

Protoplanetary disks contain abundant quantities of water molecules in both gas and solid phases. The distribution of these two phases in an evolving protoplanetary disk will have important consequences regarding water sequestration in planetary embryos. The boundary between gaseous and solid water is the "ice line" or "snow line" A simplified model that captures the complicated two-branched structure of the ice line is developed and compared with recent investigations. The effect of an evolving Sun is also included for the first time. This latter parameter could have important consequences regarding the thermodynamic state and the surface reaction environment for the time-dependent chemical reactions occurring during the 1- to 10-million-year lifetime of the pre-solar disk.

Davis, Sanford S.↗

Submillimeter Measurements of Photolysis Products in Interstellar Ice Analogs: A New Experimental Technique

Over 150 molecular species have been confirmed in space, primarily by their rotational spectra at millimeter/submillimeter wavelengths, which yield an unambiguous identification. Many of the known interstellar organic molecules cannot be explained by gas-phase chemistry. It is now presumed that they are produced by surface reactions of the simple ices and/or grains observed and released into the gas phase by sublimation, sputtering, etc. Additionally, the chemical complexity found in meteorites and samples returned from comets far surpasses that of the remote detections for the interstellar medium (ISM), comets, and planetary atmospheres. Laboratory simulations of interstellar/cometary ices have found, from the analysis of the remnant residue of the warmed laboratory sample, that such molecules are readily formed; however, it has yet to be determined if they are formed during the warm phase or within the ice during processing. Most analysis of the ice during processing reveals molecular changes, though the exact quantities and species formed are highly uncertain with current techniques due to overwhelming features of simple ices. Remote sensing with high resolution spectroscopy is currently the only method to detect trace species in the ISM and the primary method for comets and icy bodies in the Solar System due to limitations of sample return. We have recently designed an experiment to simulate interstellar/cometary/planetary ices and detect trace species employing the same techniques used for remote observations. Preliminary results will be presented.

Milam, Stefanie N.↗

The Influence of Silicon Additions on Friction and Wear of Nickel Alloys at Temperatures to 1000 Degrees Fahrenheit

Small additions of silicon have considerable beneficial effect on performance on slider alloys. This effect has most frequently been attributed to increased hardness. The research reported was conducted to consider a hypothesis that the primary role of silicon in slider alloys is one of supporting the formation of protective surface films. Friction and wear data were obtained at temperatures from 75 to 1000 degrees Fahrenheit with a series of binary silicon-nickel alloys containing up to 10 percent silicon. Pertinent hot hardness, metallurgical and surface-film analysis data are included. Atmospheres used were air, mixtures of oxygen and argon, a mixture of hydrogen and nitrogen, and a halogenated methane gas lubricant. The results show the role of silicon as a film former to be of great importance in success of silicon-containing alloys as slider materials for extreme temperatures. The range of variables studied gave friction coefficients from 0.05 to greater than 10.00 depending on film formation tendencies. Alloys with 5 percent or more silicon having a duplex structure showed the best results. Film formation resulted from surface reactions or the smearing of the softer phase from the alloys having duplex structure.

Buckley, Donald H.↗

Analysis of Fibrous Felts for Flexible Ablators Using Synchrotron Hard X-Ray Micro-Tomography

We analyzed the material properties of low-density felts that are used as substrates for new-generation flexible and conformal carbon/phenolic ablators, and compared them with those of a rigid carbon fiber preform that is used to manufacture rigid carbon/phenolic ablators. Micro-tomography measurements were obtained using synchrotron X-rays, allowing the characterization of the materials microstructure at the scale of the fibers. Using the tomography voxels as computational grids, we computed tortuosity and room temperature conductivity. In addition we performed micro-scale simulations of the oxidation of carbon fibers using a random walk model for oxygen diffusion and a probability law to model surface reactions.

Ablation↗

1-Watt Radioisotope Power System for Small Spacecraft

A variety of mission concepts have been studied by NASA and the U. S. Department of Energy that would utilize low power Radioisotope Power Systems (RPS) for small probes, landers, rovers, and communication repeaters. These missions would contain science measuring instruments that could be distributed across planetary surfaces for operation in temporarily or permanently shadowed regions. High efficiency dynamic RPS could be mission enabling for science measurements on the moon, such as collecting real-time, event-based, or cumulative space radiation measurements including primary galactic cosmic rays (GCR), solar particle events (SPE), and secondary particles liberated during atmospheric and/or surface reactions. Small RPS would use fractional versions of the General Purpose Heat Source (GPHS) or Light Weight Radioisotope Heater Units (LWRHU), to heat the power conversion technologies. Capable of three to four times higher conversion efficiency than static technologies, dynamic RPS would provide an equal amount of power using less fuel or more power using an equal amount of fuel. Providing spacecraft with more power could decrease duty cycling of basic functions and increase the quality and abundance of science data. Low power Stirling convertors are being developed at NASA Glenn Research Center (GRC) to provide future micro spacecraft with electrical power by converting heat from one or more LWRHUs. An initial concept would convert eight Watts of heat to one Watt of electrical power output for science instruments and communication. The initial design, called Small Stirling Technology Exploration Power (smallSTEP), is 11 cm diameter X 32 cm long, weighs around 3 kg, and could be used to charge batteries or capacitors for higher power burst usage. Development of the 1-watt RPS includes maturation of a Stirling engine and linear alternator, an electronics controller, and an evacuated metal foil insulation package. Test hardware and facilities are being prepared for initial demonstration of the subassemblies in a laboratory environment.

Wilson, Scott↗

Module-Level Solutions For Degradation by Ionization Damage

After years of improving module efficiency while targeting mean degradation rates of 0.5 to 0.6 %/y for crystalline silicon technology, there is much evidence that the degradation rates are now increasing significantly. Contributing factors include:Radiation damage (UV-Light Induced Degradation): Trina solar: -4.5%/y degradation rate in Singapore, DOE National Laboratory Regional Test Centers showed degradation of -1% < r < -2%/y in crystalline silicon modules, Jinko Solar: -4% < r < -7% efficiency loss from 540 MJ/m-2 of UV-A light, ISFH: 15% relative power loss during of 1.8 GJ/m-2 UV exposure, attributed to H+. Electrical bias from positive system voltage (e.g., +1000 V, +1500 V) can drive ions and metallization through the encapsulation, NREL: Ion transport can affect the cell passivation, resulting in power loss of 5% to 40% in p-PERC+ (bifacial), NREL: Damage at cell rear with up to 17% power at cell fronts in n-PERT modules. Delamination can also occur due to cell surface reactions driven by light and bias.

module efficiency↗

Generalized Brønsted‐Evans‐Polanyi Relationships for Reactions on Metal Surfaces from Machine Learning

Abstract Brønsted‐Evans‐Polanyi (BEP) relationships, i. e., a linear scaling between reaction and activation energies, lie at the core of computational design of heterogeneous catalysts. However, BEPs are not general and often require reparameterization for each class of reactions. Here we construct generalized BEPs (gBEPs), which can predict activation energies for a diverse dataset of reactions of C, O, N and H containing molecules on metal surfaces. In a first step we develop a set of descriptors based on scaling relationships that can capture the change in chemical identity of reactants during the reaction. Subsequently, we use the reaction energy, these descriptors and a single descriptor for the surface structure to parameterize machine learning based regression approaches for the prediction of activation energies. The best approach we developed shows a Mean Absolute Error (MAE) of 0.11 eV for the training set (80 % of the data set) and 0.23 eV for the test set (20 % of the data set). The methodology presented here allows to calculate activation energies within fractions of seconds on a typical personal computer and due to its generality, accuracy and simplicity in application it might prove to be useful in transition metal catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The possible role of solid surface area in condensation reactions during chemical evolution - Reevaluation

Using surface concentration and reaction rate as the main criteria for the feasibility of condensation reactions, four types of prebiotic environments were analyzed: (1) an ocean-sediment system, (2) a dehydrated lagoon bed produced by evaporation, (3) the surface of a frozen sediment, and (4) a fluctuating system where hydration (rainstorms, tidal variations, flooding) and dehydration (evaporation) take place in a cyclic manner. With the possible exception of nucleotides, low adsorption of organomonomers on sediment surfaces of a prebiotic ocean (pH 8) is expected, and significant condensation is considered unlikely. In dehydrated and frozen systems, high surface concentrations are probable and condensation is more likely. In fluctuating environments, condensation rates will be enhanced and the size distribution of the oligomers formed during dehydration may be influenced by a 'redistribution mechanism' in which adsorbed oligomers and monomers are desorbed and redistributed on the solid surface during the next hydration-dehydration cycle.

Lahav, N.↗

Mathematical Framework Underlying the In Situ Electrochemical Diagnosis of Adsorbed Intermediates Formed during Redox Reactions at Electrode Surfaces

Previously, we have presented an electrochemical technique wherein an electroactive tracer species is employed to probe the rate-limiting factors governing redox reactions at an electrode surface. In this technique, the electrode is first held potentiostatically to facilitate a redox process (step 1), and then the potential is released to open circuit conditions (step 2) so as to monitor the time-dependent re-equilibration of the electrode potential in the presence of the tracer. The time-dependent potential response in step 2 has been shown to contain information about diffusion—limited or desorption—limited steps, enabling in situ probing of the electrochemistry at the electrode surface during step 1. In the present contribution, a theoretical model governing the transient response in step 2 is developed for two limiting cases: diffusion—limited and desorption—limited recovery of the electrode potential. Mathematical modeling shows that, during re-equilibration, the step 2 potential transient corresponding to a case where step 1 involves surface adsorbed species which undergo desorption in step 2 exhibits a much longer time constant than that when re-equilibration occurs under diffusion limitations. The mathematical framework presented herein provides a sound fundamental basis for applying the aforementioned technique to studying adsorption-desorption processes during electrochemistry. Also, technique limitations are presented in light of the modeling findings.

25 ENERGY STORAGE↗

Absorptive surfaces of extended reaction angle of incidence considerations

The acoustic properties of a porous absorbing surface are characterized to apply the concepts to practical situations. Propagation constants, impedance, incident pressure wave, sound waves in the air of the pores, and general acoustic behavior are presented mathematically. The design equations are applicable for highly porous bulk materials. Modified equations are appropriate for bulk liners with stiff frames or flexible frames of finite depth.

Lambert, R. F.↗

Development of energy-absorbing reaction-sintered Si3N4 surface layers on hot-pressed Si3N4

Energy-absorbing Si3N4 surface layers on dense Si3N4 substrates were formed by in-place nitridation of fine-grained silicon powder. Ballistic impact tests performed on samples with 1-mm thick layers at room temperature and 1370 C showed up to an eightfold increase in the energy necessary to fracture the substrate. For maximum impact resistance, a small amount (about 20 vol %) of residual Si must be present in the reaction-sintered Si3N4 surface layer. Thermal cycling to 1370 C did not affect impact resistance, even though a considerable amount of SiO2 formed within the reaction-sintered Si3N4 layer during cycling. Erosion testing of samples in a Mach 0.8 burner rig at 1370 C resulted in minimal surface recession of the surface layer. Chemically vapor-deposited SiC-coated material similarly tested exhibited no surface recession.

Brennan, J. J.↗

Efficient passivation of n-type and p-type silicon surface defects by hydrogen sulfide gas reaction

An efficient surface defect passivation is observed by reacting clean Si in a dilute hydrogen sulfide-argon gas mixture (< 5% H2S in Ar) for both n-type and p-type Si wafers with planar and textured surfaces. Surface recombination velocities of 1.5 and 8 cm/s are achieved on n-type and p-type Si wafers, respectively, at an optimum reaction temperature of 550oC that are comparable to the best surface passivation quality used in high efficiency Si solar cells. Surface chemical analysis using x-ray photoelectron spectroscopy shows that sulfur is primarily bonded in a sulfide environment, and synchrotron-based soft x-ray emission spectroscopy of the adsorbed sulfur atoms suggests the formation of S-Si bonds. Furthermore, the sulfur surface passivation layer is unstable in air, attributed to surface oxide formation and a simultaneous decrease of sulfide bonds. However, the passivation can be stabilized by a low-temperature (300oC) deposited amorphous silicon nitride (a-Si:NX:H) capping layer.

14 SOLAR ENERGY↗