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Electrical properties of metal-doped pyridine-derived polyimide films

A series of polyimide films containing pyridine coordinating groups doped with cobalt or nickel ions has been examined. Using 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, films were prepared in combination with 4,4'-oxydianiline, 4,4'-dianiline sulfide, 3,3'-bis(aminopyridine) sulfide and 2,2'-dioxyphenelenebis (5,5'-aminopyridine). Room temperature volume resistivities have been found to decrease slightly with sulfur and pyridine containing diamines relative to diamines which do not contain these functionalities. Doping with cobalt and nickel additives results in further lowering of room temperature volume resistivity. Preliminary temperature profiling experiments have shown that volume resistivity decreases as T(g) is approached.

Khor, E.↗

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Thompson, David W.↗

Structure of the Magnetotail Current Sheet

An orbit tracing technique was used to generate current sheets for three magnetotail models. Groups of ions were followed to calculate the resulting cross-tail current. Several groups then were combined to produce a current sheet. The goal is a model in which the ions and associated electrons carry the electric current distribution needed to generate the magnetic field B in which ion orbits were traced. The region -20 R(E) less than x less than -14 R(E) in geocentric solar magnetospheric coordinates was studied. Emphasis was placed on identifying the categories of ion orbits which contribute most to the cross-tail current and on gaining physical insight into the manner by which the ions carry the observed current distribution. Ions that were trapped near z = 0, ions that magnetically mirrored throughout the current sheet, and ions that mirrored near the Earth all were needed. The current sheet structure was determined primarily by ion magnetization currents. Electrons of the observed energies carried relatively little cross-tail current in these quiet time current sheets. Distribution functions were generated and integrated to evaluate fluid parameters. An earlier model in which B depended only on z produced a consistent current sheet, but it did not provide a realistic representation of the Earth's middle magnetotail. In the present study, B changed substantially in the x and z directions but only weakly in the y direction within our region of interest. Plasmas with three characteristic particle energies were used with each of the magnetic field models. A plasma was found for each model in which the density, average energy, cross-tail current, and bulk flow velocity agreed well with satellite observations.

Larson, Douglas J.↗

Crossed, Small-Deflection Energy Analyzer for Wind/Temperature Spectrometer

Determination of neutral winds and ion drifts in low-Earth-orbit missions requires measurements of the angular and energy distributions of the flux of neutrals and ions entering the satellite from the ram direction. The magnitude and direction of the neutral-wind (or ion-drift) determine the location of the maximum in the angular distribution of the flux. Knowledge of the angle of maximum flux with respect to satellite coordinates (pointing) is essential to determine the wind (or ion-drift) vector. The crossed Small-Deflection Energy Analyzer (SDEA) spectrometer (see Figure 1) occupies minimal volume and consumes minimal power. Designed for upper atmosphere/ionosphere investigations at Earth altitudes above 100 km, the spectrometer operates by detecting the angular and energy distributions of neutral atoms/molecules and ions in two mutually perpendicular planes. In this configuration, the two detection planes actually cross at the spectrometer center. It is possible to merge two SDEAs so they share a common optical axis and alternate measurements between two perpendicular planes, and reduce the number of ion sources from two to one. This minimizes the volume and footprint significantly and reduces the ion source power by a factor of two. The area of the entrance aperture affects the number of ions detected/second and also determines the energy resolution. Thermionic emitters require heater power of about 100 mW to produce 1 mA of electron beam current. Typically, electron energy is about 100 eV and requires a 100-V supply for electron acceleration to supply an additional 100 mW of power. Thus, ion source power is at most 200 mW. If two ion sources were to be used, the ion source power would be, at most, 400 mW. Detector power, deflection voltage power, and microcontroller and other functions require less than 150 mW. A WTS (wind/ temperature spectrometer) with two separate optical axes would consume about 650 mW, while the crossed SDEA described here consumes about 350 mW. The entrance aperture has a diameter of 0.004 in. (0.10 mm) to provide the required energy resolution between 0.05 and 0.15. This design (see Figure 2) provides a WTS occupying a volume less than 40 cm(sup 3), on a footprint of diameter about 1.5 in. (38 mm). The Crossed SDEA offers many advantages in the measurements of neutral wind and ion drifts in the Earth's thermosphere. As such, it will be useful in future commercial satellites dedicated to monitoring the ionosphere with a view to improving the integrity and predictability of GPS operations.

Herrero, Federico A.↗

Structure of the Magnetotail Current Sheet

An orbit tracing technique was used to generate current sheets for three magnetotail models. Groups of ions were followed to calculate the resulting cross-tail current. Several groups then were combined to produce a current sheet. The goal is a model in which the ions and associated electrons carry the electric current distribution needed to generate the magnetic field B in which ion orbits were traced. The region -20 R(sub E) less than x less than - 14 R(sub E) in geocentric solar magnetospheric coordinates was studied. Emphasis was placed on identifying the categories of ion orbits which contribute most to the cross-tail current and on gaining physical insight into the manner by which the ions carry the observed current distribution. Ions that were trapped near z = 0, ions that magnetically mirrored throughout the current sheet, and ions that mirrored near the Earth all were needed. The current sheet structure was determined primarily by ion magnetization currents. Electrons of the observed energies carried relatively little cross-tail current in these quiet time current sheets. Distribution functions were generated and integrated to evaluate fluid parameters. An earlier model in which B depended only on z produced a consistent current sheet, but it did not provide a realistic representation of the Earth's middle magnetotail. In the present study, B changed substantially in the x and z directions but only weakly in the y direction within our region of interest. Plasmas with three characteristic particle energies were used with each of the magnetic field models. A plasma was found for each model in which the density, average energy, cross-tail current, and bulk flow velocity agreed well with satellite observations.

Larson, Douglas J.↗

Wind and Temperature Spectrometry of the Upper Atmosphere in Low-Earth Orbit

Wind and Temperature Spectrometry (WATS) is a new approach to measure the full wind vector, temperature, and relative densities of major neutral species in the Earth's thermosphere. The method uses an energy-angle spectrometer moving through the tenuous upper atmosphere to measure directly the angular and energy distributions of the air stream that enters the spectrometer. The angular distribution gives the direction of the total velocity of the air entering the spectrometer, and the energy distribution gives the magnitude of the total velocity. The wind velocity vector is uniquely determined since the measured total velocity depends on the wind vector and the orbiting velocity vector. The orbiting spectrometer moves supersonically, Mach 8 or greater, through the air and must point within a few degrees of its orbital velocity vector (the ram direction). Pointing knowledge is critical; for example, pointing errors 0.1 lead to errors of about 10 m/s in the wind. The WATS method may also be applied without modification to measure the ion-drift vector, ion temperature, and relative ion densities of major ionic species in the ionosphere. In such an application it may be called IDTS: Ion-Drift Temperature Spectrometry. A spectrometer-based coordinate system with one axis instantaneously pointing along the ram direction makes it possible to transform the Maxwellian velocity distribution of the air molecules to a Maxwellian energy-angle distribution for the molecular flux entering the spectrometer. This implementation of WATS is called the gas kinetic method (GKM) because it is applied to the case of the Maxwellian distribution. The WATS method follows from the recognition that in a supersonic platform moving at 8,000 m/s, the measurement of small wind velocities in the air on the order of a few 100 m/s and less requires precise knowledge of the angle of incidence of the neutral atoms and molecules. The same is true for the case of ion-drift measurements. WATS also provides a general approach that can obtain non-equilibrium distributions as may exist in the upper regions of the thermosphere, above 500 km and into the exosphere. Finally, WATS serves as a mass spectrometer, with very low mass resolution of roughly 1 part in 3, but easily separating atomic oxygen from molecular nitrogen.

Herrero, Federico↗

Nuclear electric propulsion for planetary science missions: NASA technology program planning

This paper presents the status of technology program planning to develop those Nuclear Electric Propulsion technologies needed to meet the advanced propulsion system requirements for planetary science missions in the next century. The technology program planning is based upon technologies with significant development heritage: ion electric propulsion and the SP-100 space nuclear power technologies. Detailed plans are presented for the required ion electric propulsion technology development and demonstration. Closer coordination between space nuclear power and space electric propulsion technology programs is a necessity as technology plans are being further refined in light of NEP concept definition and possible early NEP flight activities.

Doherty, Michael P.↗

Wireless Chalcogenide Nanoionic-Based Radio-Frequency Switch

A new nonvolatile nanoionic switch is powered and controlled through wireless radio-frequency (RF) transmission. A thin layer of chalcogenide glass doped with a metal ion, such as silver, comprises the operational portion of the switch. For the switch to function, an oxidizable electrode is made positive (anode) with respect to an opposing electrode (cathode) when sufficient bias, typically on the order of a few tenths of a volt or more, is applied. This action causes the metal ions to flow toward the cathode through a coordinated hopping mechanism. At the cathode, a reduction reaction occurs to form a metal deposit. This metal deposit creates a conductive path that bridges the gap between electrodes to turn the switch on. Once this conductive path is formed, no further power is required to maintain it. To reverse this process, the metal deposit is made positive with respect to the original oxidizable electrode, causing the dissolution of the metal bridge thereby turning the switch off. Once the metal deposit has been completely dissolved, the process self-terminates. This switching process features the following attributes. It requires very little to change states (i.e., on and off). Furthermore, no power is required to maintain the states; hence, the state of the switch is nonvolatile. Because of these attributes the integration of a rectenna to provide the necessary power and control is unique to this embodiment. A rectenna, or rectifying antenna, generates DC power from an incident RF signal. The low voltages and power required for the nanoionic switch control are easily generated from this system and provide the switch with a novel capability to be operated and powered from an external wireless device. In one realization, an RF signal of a specific frequency can be used to set the switch into an off state, while another frequency can be used to set the switch to an on state. The wireless, miniaturized, and nomoving- part features of this switch make it suitable for applications such as integration into garments, RFID (radio-frequency identification) tags, and conformal structures (e.g., aircraft wings, sounding rockets contours, etc). In the case of RFID tags the innovation will provide countermeasures to attempts for identity theft and other uninvited attempts for retrieval of information. It could also be applicable to the automotive industry as well as the aerospace industry for collision avoidance and phased array radar systems, respectively

Nessel, James↗

The Nature of Space Weathering in Samples From Asteroid (162173) Ryugu Revealed By Coordinated Analysis

Space weathering, driven primarily by micrometeorite bombardment and solar wind ion irradiation, alters the morphology, microstructure, and chemistry of the surface regolith on airless bodies. The accumulation of microstructural and chemical space weathering features, including melt deposits, amorphous rims, and nanophase iron-bearing particles (npFe), are associated with alterations of the spectral properties of the regolith. In particular, space weathering changes the spectral slope and reflectance of surface materials, and causes the attenuation of characteristic absorption bands in the visible to near-infrared wave-lengths, as well as a shift towards longer wavelengths of the Christiansen feature (CF)in thermal infrared spectra. Previous studies of space weathering characteristics have focused on siliceous bodies like the Moon and S-type asteroid Itokawa. However, observations of asteroid Ryugu by the JAXA Hayabusa2 spacecraft and subsequent analyses of returned samples revealed carbonaceous and hydrated materials. These samples provided our first opportunity to constrain the effects of space weathering processes on primitive, C-type asteroids. Analyses of returned samples to understand the space weathering of carbonaceous materials are important for accurately interpreting remote sensing observations of carbonaceous asteroids. In addition, the analysis of Hayabusa2 samples from Ryugu paved the way for the analysis of samples from the asteroid Bennu, re-turned by the NASA OSIRIS-REx mission. As space weathering impacts the microstructure, chemistry, and spectral characteristics of asteroidal surfaces, here we report the results of a coordinated analytical study of the micro-and nano-scale signatures of space weathering in samples returned from Ryugu.

L E Melendez↗

Doubly Excited Resonances in the Positronium Negative Ion

The recent theoretical studies on the doubly excited states of the Ps' ion are described. The results obtained by using the method of complex coordinate rotation show that the three-lepton system behaves very much like an XYX tri-atomic molecule. Furthermore, the recent investigation on the positronium negative ion embedded in Debye plasma environments is discussed. The problem is modeled by the use of a screened Coulomb potential to represent the interaction between the charge particles.

Ho, Y.K.↗

Prependicular transport in 1- and 2-dimensional shock simulations

We consider the foundations of 1- and 2-dimensional shock simulations in which the physical quantities are independent of a coordinate which is not parallel to the magnetic field. We show analytically that in such simulations the ions are effectively tied to the convected magnetic lines of force because of the presence of an ignorable spatial coordinate. This conclusion has important consequences. In particular we conclude that the acceleration of energetic charged particles at quasi-perpendicular shocks cannot be properly studied in such simulations because the role of perpendicular diffusion cannot be properly evaluated.

Jokipii, J. R.↗

Chromium Ions Improve Moisure Resistance of Epoxy Resins

Broad spectrum of thermosetting epoxy resins used on commercial and military aircraft, primarily as composite matrices and adhesives. In new technique, chromium-ion containing epoxy with improved resistance to moisture produced where chromium ions believed to prevent absorption of water molecules by coordinating themselves to hydroxyl groups on epoxy chain. Anticipated that improved epoxy formulation useful as composite matrix resin, adhesive, or casting resin for applications on commercial and advanced aircraft. Improvement made without sacrifice in mechanical properties of polymer.

St. Clair, A. K.↗

In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite grains in 3 samples of the ABDP-9 core using a 10 micron spot (2 SD reproducibility = 0.4% for delta S-34 and -0.1% for Delta S-33) show a range of 28.1 % in delta S-34 (-10.3 to 17.8%) and 13.3%0 in Delta S-33 (-3.8 to 9.5%), whereas the range from 132 bulk analyses across 84 m of core is 19.4% for delta S-34 and 11.5% for Delta S-33. Coordinated, in situ carbon and sulfur isotope analyses in one ABDP-9 sample are shown. In situ values from this kerogen-pyrite association are within 0.1% of the bulk value in the case of delta C-13 and higher by several permil in the case of delta S-34 and Delta S-33. Coordinated in situ carbon and sulfur isotope analyses in rocks deposited during key intervals of environmental change (e.g., the Great Oxidation Event) can refine our understanding of the mode and tempo of change. In Earth's oldest sedimentary rocks, and in extraterrestrial samples, these coordinated in situ analyses may reveal biosignatures in the form of isotopic correlations at the scale of individual microorganisms and their microhabitats.

Williford, K. H.↗

The comet rendezvous asteroid flyby mission

The Comet Rendezvous Asteroid Flyby Mission (CRAF) is described. After gravity assists from Venus and Earth, the spacecraft will fly by the asteroid 46 Hestia en route to a rendezvous with P/Tempel 2 in Nov. 1996, when the comet is near aphelion. The scientific experiments for the CRAF mission are: an imaging system; a visual and infrared mapping spectrometer; an infrared radiometer; a penetrator carrying a gamma-ray spectrometer, a scanning differential calorimeter and evolved gas analyzer, accelerometers, and temperature probes; a neutral gas and thermal ion mass spectrometer; a secondary ion mass spectrometer for analyzing dust, gas, and thermal ions; a scanning electron microscope and particle analyzer; an X-ray fluorescence and gas chromatographic analyzer for collected dust and ice samples; a dust counter and velocity analyzer; a retarding potential ion mass spectrometer; a supra-thermal ion mass spectrometer and electron analyzer; a magnetometer; and a coordinated radio, electron, and plasma wave analyzer.

Neugebauer, M.↗

New Modeling Approaches to Study DNA Damage by the Direct and Indirect Effects of Ionizing Radiation

DNA is damaged both by the direct and indirect effects of radiation. In the direct effect, the DNA itself is ionized, whereas the indirect effect involves the radiolysis of the water molecules surrounding the DNA and the subsequent reaction of the DNA with radical products. While this problem has been studied for many years, many unknowns still exist. To study this problem, we have developed the computer code RITRACKS [1], which simulates the radiation track structure for heavy ions and electrons, calculating all energy deposition events and the coordinates of all species produced by the water radiolysis. In this work, we plan to simulate DNA damage by using the crystal structure of a nucleosome and calculations performed by RITRACKS. The energy deposition events are used to calculate the dose deposited in nanovolumes [2] and therefore can be used to simulate the direct effect of the radiation. Using the positions of the radiolytic species with a radiation chemistry code [3] it will be possible to simulate DNA damage by indirect effect. The simulation results can be compared with results from previous calculations such as the frequencies of simple and complex strand breaks [4] and with newer experimental data using surrogate markers of DNA double ]strand breaks such as . ]H2AX foci [5].

Plante, Ianik↗

Model development of supersonic trough wind with shocks

The time dependent one dimensional hydrodynamic equations describe the evolution of the thermal plasma flow along closed magnetic field lines outside of the plasmasphere. The convection of the supersonic polar wind onto a closed fieldline results in the assumed formation of collisionless plasma shocks. These shocks move earthward as the field line with its frozen-in plasma remains fixed or contracts with time to smaller L coordinates. The high equatorial plasma temperature (of the order of electron volts) produced by the shock process decreases with time if the flow is isothermal but it will increase if the contraction is under adiabatic conditions. Assuming adiabaticity a peak in the temperature forms at the equator in conjunction with a depression in the ion density. After an initial contraction, if the flux tube drifts to higher L coordinates the direction of the shock motion can be reversed so that the supersonic region will expand along the field line towards the state characterizing the supersonic polar wind. A rapid expansion will lower the equatorial density while the temperature decreases with time under adiabatic but not isothermal conditions.

Grebowsky, J. M.↗