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NASA NTRS1989

Optical evidence for the metallization of Xenon at 132(5) GPa

Xe has been compressed in a diamond-anvil cell to approximately 200 GPa. The metallization of Xe by band-gap closure was investigated by obtaining optical data in both the metallic and insulating states. In the metallic state, the pressure dependence of the plasma frequency was determined from absorption data fitted with a free-electron model. In the insulating state, the pressure dependence of the band gap was determined from absorption data fitted with an indirect-band-gap model. The optical data indicate that the insulator-to-metal transition in Xe occurs at 132(5) GPa.

Goettel, Kenneth A.↗

NASA NTRS1989

Electrical properties of materials for high temperature strain gage applications

A study was done on the electrical resistance of materials that are potentially useful as resistance strain gages at high temperatures under static strain conditions. Initially a number of binary alloys were investigated. Later, third elements were added to these alloys, all of which were prepared by arc melting. Several transition metals were selected for experimentation, most prepared as thin films. Difficulties with electrical contacts thwarted efforts to extend measurements to the targeted 1000 C, but results obtained did suggest ways of improving the electrical resistance characteristics of certain materials.

Brittain, John O.↗

NASA NTRS1989

Accurate quantum chemical calculations

An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1991

Characterization of magneto-optical media

Amorphous rare earth-transition metal (RE-TM) alloys and compositionally modulated TM/TM films were characterized in terms of their magnetic, magneto-optic, and galvanomagnetic properties. The loop tracer, vibrating sample magnetometer (VSM), and Rutherford Backscattering (RBS) facility were used to characterize and analyze the various properties of these magneto-optical storage media. Kerr effect, ellipticity, coercivity, and anisotropy at various temperatures, magnetoresistance, and resistivity are among the properties measured in Co/Pt films, Co/Pd films, and TbFeCo films.

Hajjar, Roger A.↗

NASA NTRS1992

Oxidation processes in magneto-optic and related materials

The surface oxidation processes of thin films of magneto-optic materials, such as the rare-earth transition metal alloys have been studied, starting in ultrahigh vacuum environments, using surface analysis techniques, as a way of modeling the oxidation processes which occur at the base of a defect in an overcoated material, at the instant of exposure to ambient environments. Materials examined have included FeTbCo alloys, as well as those same materials with low percentages of added elements, such a Ta, and their reactivities to both O2 and H2O compared with materials such as thin Fe films coated with ultrathin adlayers of Ti. The surface oxidation pathways for these materials is reviewed, and XPS data presented which indicates the type of oxides formed, and a critical region of Ta concentration which provides optimum protection.

Lee, Paul A.↗

NASA NTRS1992

Search for new high temperature thermoelectric materials

Although important efforts are actually devoted to improve Si-Ge materials, their thermoelectric energy conversion efficiency remains relatively low and the nondimensional ZT value does not exceed 1. Higher values can be obtained by investigating new materials. A search for new high temperature thermoelectric materials identified a certain number of compounds between transition metals and bismuth, antimony and germanium as potential candidates. Results of the preliminary synthesis of samples by a variety of techniques (Bridgman, mechanical alloying) are presented as well as some electrical measurements. Some compounds showed interesting properties and need to be investigated in more details.

Caillat, Thierry↗

NASA NTRS1992

Evaluation of capillary electrophoresis for in-flight ionic contaminant monitoring of SSF potable water

Until 1989, ion chromatography (IC) was the baseline technology selected for the Specific Ion Analyzer, an in-flight inorganic water quality monitor being designed for Space Station Freedom. Recent developments in capillary electrophoresis (CE) may offer significant savings of consumables, power consumption, and weight/volume allocation, relative to IC technology. A thorough evaluation of CE's analytical capability, however, is necessary before one of the two techniques is chosen. Unfortunately, analytical methods currently available for inorganic CE are unproven for NASA's target list of anions and cations. Thus, CE electrolyte chemistry and methods to measure the target contaminants must be first identified and optimized. This paper reports the status of a study to evaluate CE's capability with regard to inorganic and carboxylate anions, alkali and alkaline earth cations, and transition metal cations. Preliminary results indicate that CE has an impressive selectivity and trace sensitivity, although considerable methods development remains to be performed.

Mudgett, Paul D.↗

NASA NTRS1993

Magneto-optic superlattice thin films: Fabrication, structural and magnetic characterization

During this quarter studies were extended to determine the electronic contribution to the perpendicular interface anisotropy in Co-based multilayers. Using in situ Kerr effect measurements, the influences of different transition metals (TM = Ag, Au, Cu, and Pd) on the magnetic properties of single-crystal Co films grown on Pd (111) and Au (111) surfaces are investigated. Last quarter the discovery of a large peak in the perpendicular anisotropy when approximately one monolayer of Cu or Ag is deposited on the Co surface was reported. We now have added a computer-controlled stepper-motor drive to our MBE sample transfer mechanism. The motor allows us to move the sample at a constant velocity from behind a shutter during deposition. The film, therefore, is deposited as a wedge with a linear variation of thickness across the substrate. In this way, a continuous range of coverage on a single sample is studied. The stepper motor also provides the necessary control for precisely positioning the sample in the laser beam for Kerr effect measurements at the different coverages.

Falco, C. M.↗

NASA NTRS1992

Optical fiber spectroscopy: A study of the luminescent properties of the europium ion for thermal sensors

Recently, there has been interest in developing a distributed temperature sensor integrated into an optical fiber. Such a system would allow embedding of the optical fiber within or on a structural material to provide for continuous monitoring of the material's temperature. Work has already begun on the development of a temperature sensor using the temperature dependent emission spectra from the lanthanide rare earths doped into crystalline hosts. The lifetime, the linewidth and the integrated intensity of this emission are each sensitive to changes in the temperature and can provide a basis for thermometry. One concept for incorporating this phenomena into an optical fiber based sensor involves bonding the optically active material to the cladding of an optical fiber and allowing the luminescent light to couple into the the fiber by the evanescent wave. Experimental work developing this concept has already been reported. Measurements of the linewidth of Eu3+:Y2O3, diffused into a fiber, made by Albin clearly show a strong and regular dependence on temperature over the range of 300 to 1000 K. We report here on a study of the temperature dependence of the lineshape of the emission at 611 nm using the data in references. We focus attention on understanding the general behavior of the Eu3+:Y2O3 system. Building upon understanding of this system we will be able to establish the physical criterial for a good optical fiber based temperature sensor and then to examine available data on other lanthanide rare earths and transition metal ions to determine the best luminescent system for temperature sensing in an optical fiber.

Buoncristiani, A. Martin↗

NASA NTRS1993

Wavelength dispersive analysis with the synchrotron x ray fluorescence microprobe

A wavelength dispersive spectrometer (WDS) was tested on the synchrotron x ray fluorescence microprobe at Brookhaven National Laboratory. Compared to WDS spectra using an electron microprobe, the synchrotron WDS spectra have much better sensitivity and, due to the absence of bremsstrahlung radiation, lower backgrounds. The WDS spectrometer was successfully used to resolve REE L fluorescence spectra from standard glasses and transition metal K fluorescence spectra from kamacite.

Rivers, M. L.↗

NASA NTRS1992

Optical luminescence spectroscopy as a probe of the surface mineralogy of Mars

Optical luminescence (OpL) spectroscopy is an attractive use of a visible-near-IR spectrometer on a Mars lander because mineral products of atmosphere-surface interactions on Mars will probably have characteristic OpL spectra. Optical luminescence spectra would be taken at night, when a spectrometer might otherwise sit idle. Also needed would be a source of exciting radiation, which could be shared with other experiments. Optical luminescence is emission of nonthermal optical photons (near-UV through near-IR) as a response to energy input. On absorption of energy, an atom (or ion) will enter an excited state. The favored decay of many such excited states involving valence-band electrons is emission of an optical photon. Optical luminescence spectra can be useful in determining mineralogy and mineral composition. Optical luminescence in crystals can arise from essential elements (or ions), trace-element substituents (activators), or defects. Common activators in salts of alkali and alkaline earth elements include Mn(2+)(VI), other transition metals, the rare earths, and the actinides. Trace substituents of other species can enhance or quench OpL (e.g., Pb(2+) vs. Fe(3+)). Optical luminescence can also arise from defects in crystal structures, including those caused by radiation and shock.

Treiman, A. H.↗

NASA NTRS1994

Overcharge and overdischarge protection of ambient temperature secondary lithium cells

A cathode additive is provided for protecting an ambient temperature secondary lithium cell from overcharging or overdischarging. The cathode additive is chosen to create an upper voltage plateau which is slightly higher than a characteristic charge cutoff voltage of the cathode of the cell. The cathode additive additionally creates a lower voltage plateau which is slightly lower than the characteristic discharge cutoff voltage of the cell. Preferably, the cathode additive is a transition metal oxide or a sulfide and may, for example, include a mixture of Li2Mn2O4 and Li(0.1)MoO2.

Huang, Chen-Kuo↗

NASA NTRS1994

High temperature sorbents for oxygen

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C comprising a porous alumina silicate support, such as zeolite, containing from 1 to 10 percent by weight of ion exchanged transition metal, such as copper or cobalt ions, and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum is described. The activation temperature, oxygen sorption, and reducibility are all improved by the presence of the platinum activator.

Sharma, Pramod K.↗

NASA NTRS1994

Day 640 infrared line and continuum measurements: Dust formation in SN 1987A

We have measured day 640-645 line and continuum spectra of (Ni II) 6.6 micrometer (Ne II) 12.8 micrometer (line emission was not detected), and (Fe II) 17.9 and 26.0 micrometer from SN 1987A. The high velocity feature at v(sub HVF) approximately 3900 km/sec found in both of our day 410 (Fe II) spectra is again detected in the day 640 (Ni II) spectrum, although the signal-to-noise of the day 640 (Fe II) spectra is insufficient to show this feature. The continuum fluxes provide clear evidence for the formation of dust between day 410 and day 640 and are best fitted by a graybody spectrum with a temperature of 342 +/- 17 K at day 640 and a surface area corresponding to a minimum dust velocity v(sub dust) = 1910 +/- 170 km/sec. Optically thin dust emissivity laws proportional to lambda(exp -1) or lambda(exp -2) are inconsistent with the data. Either the dust grains are large (radius a much greater than 4 micrometer and radiate like individual blackbodies, or else they are located in clumps optically thick in the 6-26 micrometer range. The (Ni II) 6.6 micrometer line flux yields a minimum Ni(+) mass of 5.8 +/- 1.6 x 10(exp -4) solar mass and a Ni/Fe abundance ratio of 0.06 +/- 0.02, equal to the solar value. The ratio of the two (Fe II) line profiles implies a gas temperature 2600 +/- 700 K, a drop of 1800 +/- 800 K from our day 410 measurement. The (Fe II) 26.0 micrometer line flux has decreased by a factor of 2 and the day 640 (Ni II) profile is blueshifted by -440 +/- 270 km/sec, relative to observations before day 500. We show that the decrease in the (Fe II) flux and the blueshift are not produced by a decrease in electron scattering optical depth, electron density, or temperature, but rather are probably due to obscuration by the same dust which produces the infrared continuum. This supports the interpretation that the dust spectrum is produced by optically thick clumps. We discuss possible explanations for the discrepancy between the mass of Fe(+) detected and the total iron mass required to power the light curve. The decrease in the (Fe II) fluxes relative to the decrease required to account for the blueshifts of optical lines from non-iron-group elements and the similarity between v(sub dust) and the Ni(+) expansion velocity imply a spatial association between the dust clumps and the iron-group elements. In addition, the larger blueshift observed for the near and far-infrared, heavy metal transitions relative to non-iron-group lines suggests that the iron-group elements are somewhat segregated from lighter elements such as the Mg(sup 0) and O(sup 0) responsible for shorter wavelength lines. We speculate that FeS may be an important constituent of the dust. A comparison of our line profiles with radiative transfer models shows that while power law and exponential density distributions yield reasonable fits to the data, polytrope distributions provided significantly worse agreement. The best fits require a substantial fraction of the iron to be undetectable, and are consistent with maximum expansion velocities of v(sub max) approximately 3000 km/sec.

Colgan, Sean W. J.↗

NASA NTRS1993

Critical review of electrical conductivity measurements and charge distribution analysis of magnesium oxide

The electrical conductivity sigma of MgO single crystals shows a sharp increase at 500-800 C, in particular of sigma surface, generally attributed to surface contamination. Charge Distribution Analysis (CDA), a new technique providing information on fundamental properties that was previously unavailable, allows for the determination of surface charges, their sign and associated internal electric field. Data on 99.99% purity, arc-fusion grown MgO crystals show that mobile charge carriers start to appear in the bulk of the MgO crystals between 200 and 400 C when sigma (measured by conventional techniques) is in t he 10(exp -14) to 10(exp -16) /omega/cm range. Above 500 C, as sigma increases to 10(exp -6) to 10(exp -7)/omega/cm, more charges appear giving rise to a strong positive surface charge supported by a strong internal field. This indicates that charges are generated in the bulk and diffuse to the surface by an internally controlled process. On the basis of their positive sign they are identified as holes (defect electrons). Because of the low cation content of these very pure MgO crystals, theses holes cannnot be associated with transition metal impurties. Instead, they are associated with the O(2-) sublattice, e.g. consist of O(-) states or positive holes. This conclusion is supported by magnetic susceptibility data showing the appearance of 1000 +/- 500 ppm paramagnetic species between 200-500 C. The magnetic data are consistent with strongly coupled, diamagnetic O(-) pairs below 200-500 C, chemically equivalent to peroxy anions, O2(2-), and probably associated with cation vacancies in the MgO matrix. The formation of O2(2-) in arc-fusion grown MgO crystals is very unexpected because of the highly reducing growth conditions. Their presence implies an internal redox reaction involving dissolved 'water' by which OH(-) pairs convert to O2(2-) plus H2 molecules. This redox conversion is supported by mass spectroscopic measurements of the H2 release from highly OH(-)-doped, finely divided MgO and by wet-chemical analysis of its oxidant concentration.

Freund, Friedemann↗

NASA NTRS1994

Snythesis and characterization of the first main group oxo-centered trinuclear carboxylate

The synthesis and structural characterization of the first main group oxo-centered, trinuclear carboxylato-bridged species is reported, namely (Ga3(mu(sub 3)-O) (mu-O2CC6H5)6 (4-Mepy)3) GaCl4 center dot 4-Mepy (compound 1), where 4-Mepy is 4-methylpyridine. Compound 1 is a main group example of a well-established class of complexes, referred to as 'basic carboxylates' of the general formula (M3(mu(sub 3)-O)(mu-O2CR)6L3)(+), previously observed only for transition metals.

Duraj, Stan A.↗

NASA NTRS1995

Magnetic properties of iron-bearing graphite fibers

Carbon fibers containing ferromagnetically-ordered iron or other transition metals could be used in a variety of lightweight magnetic composites. Intercalation of bulk graphite with CoCl2 or FeCl3, followed by reduction with butyl lithium, did indeed produce magnetic samples; however, the observed room temperature permeabilities (mu) were less than 2 G/Oe. Magnetic data are presented on carbon fibers containing large amounts of elemental iron, which were prepared by a new method. In this method Amoco P-75 fibers were intercalated with Br2 and I2 followed by fluorination, forming CF(0.75). This product was then intercalated with FeCl3. Subsequent heat treatments in oxidizing and reducing atmospheres converted most of the iron to the pure alpha phase. Room temperature permeabilities as large as 40 G/Oe are observed.

Ferrante, R.↗

NASA NTRS1996

High Temperature Sorbents for Oxygen

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C is introduced. The sorbent comprises a porous alumina silicate support such as zeolite containing from 1 to 10 percent by weight of ion exchanged transition metal such as copper or cobalt ions and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum. The activation temperature, oxygen sorption and reducibility are all improved by the presence of the platinum activator.

Sharma, Pramod K.↗