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At least 145 records · Page 8

Quadrupolar Kondo effect in uranium heavy-electron materials?

The possibility of an electric quadrupole Kondo effect for a non-Kramers doublet on a uranium (U) ion is a cubic metallic host is demonstrated by model calculations showing a Kondo upturn in the resistivity, universal quenching of the quadrupolar moment, and a heavy-electron anomaly in the electronic specific heat. With inclusion of excited crystal-field levels, some of the unusual magnetic-response data in the heavy-electron superconductor UBe13 may be understood. Structural phase transitions at unprecedented low temperatures may occur in U-based heavy-electron materials.

Cox, D. L.↗

Effects of tensile stress on the R lines of Cr(3+) in a sapphire fiber

The spectroscopic properties of a crystalline sapphire fiber unintentionally dOed with Cr(3+) are investigated. It is found that tensile stress produces blue shifts of the R lines and changes in their radiative lifetimes and integrated intensities that can be correlated to stress-induced changes of the crystal-field parameters.

Liu, Huimin↗

Imaging spectroscopy of Mars (0.4-1.1 micron) during the 1988 opposition

The paper presents imaging spectroscopic data and preliminary interpretations acquired during the 1988 perihelic opposition of Mars at the highest spatial resolution achieved from earth for spectrometric measurements (all contiguous spatial sampling for nearly 70 percent of the planet) and at a higher spectral resolution (R = 350) than most previous measurements in the (0.4-1.1)-micron wavelength range. Absorption features appearing near 0.6-0.7 and 0.80-0.95 micron are attributed to Fe(3+) crystal field transitions, confirming previously made measurements at lower spectral resolution. It is shown that attempts to reconcile the overall spectral shape with those of laboratory minerals or Mars analog soils spectra affirm the recent interpretations that hematite may account for nearly all of the 18 wt pct Fe2O3 measured by Viking Landers.

Bell, J. F., III↗

Remote compositional mapping of lunar titanium and surface maturity

Lunar ilmenite (FeTiO3) is a potential resource capable of providing oxygen for life support and spacecraft propellant for future lunar bases. Estimates of TiO2 content in mature mare soils can be made using an empirical relation between the 400/500 nm reflectance ratio and TiO2 wt percent. A TiO2 abundance map was constructed for the entire near-side lunar maria accurate to + or - 2 wt percent TiO2 using CCD images obtained at the Tumamoc Hill 0.5 m telescope in Tucson, employing bandpass filters centered at 400 and 560 nm. Highest TiO2 regions in the maria are located in western Mare Tranquillitatis. Greater contrast differences between regions on the lunar surface can be obtained using 400/730 nm ratio images. The relation might well be refined to accommodate this possibly more sensitive indicator of TiO2 content. Another potential lunar resource is solar wind-implanted He-3 which may be used as a fuel for fusion reactors. Relative soil maturity, as determined by agglutinate content, can be estimated from 950/560 nm ration images. Immature soils appear darker in this ratio since such soils contain abundant pyroxene grains which cause strong absorption centered near 950 nm due Fe(2+) crystal field transitions. A positive correlation exists between the amount of He-3 and TiO2 content in lunar soils, suggesting that regions high in TiO2 should also be high in He-3. Reflectance spectrophotometry in the region 320 to 870 nm was also obtained for several regions. Below about 340 nm, these spectra show variations in relative reflectance that are caused by as yet unassigned near-UV absorptions due to compositional differences.

Johnson, J. R.↗

Spectral mineralogy of terrestrial planets - Scanning their surfaces remotely

Information on the surface mineralogy, chemical composition, and lithology of terrestrial planets, as well as on their atmospheres, that can be obtained by earth-based from visible and NIR spectra of light reflected from planetary surfaces is discussed. Such reflectance spectra may have absorption bands in the 1- and 2-micron wavelength regions which originate from crystal field transitions within Fe(2+) ions. Since pyroxenes with Fe(2+) in M2 positions usually dominate the spectra, the resulting 1-micron vs 2-micron spectral determinative curves can be used to identify compositions and structural types of pyroxenes on the surface of a planet or an asteroid. Future spececraft missions to solar system objects will concentrate on remote-sensing experiments using visible and NIR reflectance spectra. These include the Galileo mission to Jupiter; the Mars Orbiter mission to Phoebus; the Comet Rendezvous Asteroid Flyby mission; the Cassini mission to Saturn; the Lunar Geoscience Observer; and the Mars Rover/Sample Return mission.

Burns, Roger G.↗

UV, visible, and near-IR reflectivity data for magnetic soils/rocks from Brazil

The objective is to obtain UV, visible, and near-IR reflectivity spectra for several magnetic Brazilian soils/rocks and compare them to corresponding data for Mars to see if these materials satisfy both magnetic and spectral constraints for Mars. Selected physical properties of the magnetic Brazilian soils/rocks are presented. In general, the spectral features resulting from ferric crystal-field transitions are much better defined in the spectra of the magnetic Brazilian soils/rocks than in Martian spectral data. Presumably, this results from a relatively higher proportion of crystalline ferric oxides for the former. The apparent masking of the spectral signature of maghemite by hematite or goethite for the Brazilian samples implies the magnetic and spectral constraints for Mars can be decoupled. That is, maghemite may be present in magnetically-significant but optically-insignificant amounts compared to crystalline hematite.

Vempati, R. K.↗

Spectroscopic analyses of Fe and water in clays: A Martian surface weathering study

Martian surface morphology suggests the presence of liquid H2O on Mars in the past. Reflectance spectra of the Martian surface include features which correspond to the crystal field transitions of iron, as well as features supporting the presence of ice and minerals containing structural OH and surface water. Researchers initiated further spectroscopic studies of surface iron and water and structural OH in clays in order to determine what remotely obtained spectra can indicate about the presence of clays on Mars based on a clearer understanding of the factors influencing the spectral features. Current technology allows researchers to better correlate the low frequency fundamental stretching and bending vibrations of O-H bonds with the diagnostic near infrared overtone and combination bands used in mineral characterization and identification.

Bishop, J. L.↗

Thermal processing of omicron-terphenyl - A Raman study

Raman spectra from omicron-terphenyl sealed in glass capillary tubes were acquired over temperatures ranging from 233 to 343 K. Over this temperature range, omicron-terphenyl can exist in the solid-crystalline, molten, supercooled-liquid, and amorphous-glassy states. Representative structure-sensitive spectra are presented along with a qualitative description. The lattice spectral feature occurring at a Raman shift of 123/cm displays abrupt changes in profile and intensity as melting and glass transition occur. The intensity ratio of the C-C stretching 996/cm line and C-H stretching line at 1008/cm displays a change related to the transformation of the ordered-crystalline phase to the disordered-liquid or glassy state. At a Raman shift of 1162/cm the solid-crystalline state shows a splitting due to the effect of the crystal field. The possibility of using these structure-sensitive Raman characteristics for in situ diagnostics during materials processing is discussed.

Biswas, A.↗

Variations in the Fe mineralogy of bright Martian soil

Bright regions on Mars are interpreted as 'soil' derived by chemical alteration of crustal rocks, whose main pigmentary component is ferric oxide or oxyhydroxide. The mineralogy and mineralogic variability of ferric iron are important evidence for the evolution of Martian soil: mineralogy of ferric phases is sensitive to chemical conditions in their genetic environments, and the spatial distributions of different ferric phases would record a history of both chemical environments and physical mixing. Reflectance spectroscopic studies provide several types of evidence that discriminate possible pigmentary phases, including the position of a crystal field absorption near 0.9 microns and position and strengths of absorptions in the UV-visible wavelength region. Recent telescopic spectra and laboratory measurements of Mars soil analogs suggest that spectral features of bright soil can be explained based on a single pigmentary phase, hematite (alpha-Fe2O3), occurring in both 'nanophase' and more crystalline forms. Here we report on a systematic investigation of Martian bright regions using ISM imaging spectrometer data, in which we examined spatial variations in the position and shape of the approximately 0.9 microns absorption. We found both local and regional heterogeneities that indicate differences in Fe mineralogy. These results demonstrate that bright soils do not represent a single lithology that has been homogenized by eolian mixing, and suggest that weathering of soils in different geologic settings has followed different physical and chemical pathways.

Murchie, Scott↗

Porphyrins in the interstellar medium (in grains)

Spectral sensitivity of the chromophores to their immediate chemical environment establishes some of the chemical constituents of the grains in which they reside. These are: (1) Paraffins, such as, octane, nonane, decane, and others...(needed for Shpolskii matrices and producing quasilines); and (2) Pyridine. The presence of pyridine is required not only to produce the spectral DIB matching, but also to produce the 36 cm(sup -1) crystal field splitting of the S(sub 1) electronic state. The presence of pyridine in the grains can be confirmed spectroscopically. Pyridine produces a transmission window at 2175 A, matching exactly the well known UV hump. On grain reflection, some of the incoming UV radiation is absorbed into the grain's outer layers. Spikes in the lab and in the astronomical data are due to vibronic transitions in pyridine. The lab spectroscopy reported here clearly establishes the presence of MgTBP, H2TPB, and pyridine in the interstellar grains. The high fluorescence efficiency of MgTBP (being optically pumped in the visible) apparently accounts for all the observed UIR emissions.

Johnson, Fred M.↗

Mineralogic variations in fluvial sediments contaminated by mine tailings as determined from AVIRIS data, Coeur D'Alene River Valley, Idaho

The success of imaging spectrometry in mineralogic mapping of natural terrains indicates that the technology can also be used to assess the environmental impact of human activities in certain instances. Specifically, this paper describes an investigation into the use of data from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) for mapping the spread of, and assessing changes in, the mineralogic character of tailings from a major silver and base metal mining district. The area under investigation is the Coeur d'Alene River Valley in northern Idaho. Mining has been going on in and around the towns of Kellogg and Wallace, Idaho since the 1880's. In the Kellogg-Smelterville Flats area, west of Kellogg, mine tailings were piled alongside the South Fork of the Coeur d'Alene River. Until the construction of tailings ponds in 1968 much of these waste materials were washed directly into the South Fork. The Kellogg-Smelterville area was declared an Environmental Protection Agency (EPA) Superfund site in 1983 and remediation efforts are currently underway. Recent studies have demonstrated that sediments in the Coeur d'Alene River and in the northern part of Lake Coeur d'Alene, into which the river flows, are highly enriched in Ag, Cu, Pb, Zn, Cd, Hg, As, and Sb. These trace metals have become aggregated in iron oxide and oxyhydroxide minerals and/or mineraloids. Reflectance spectra of iron-rich tailing materials are shown. Also shown are spectra of hematite and goethite. The broad bandwidth and long band center (near 1 micron) of the Fe(3+) crystal-field band of the iron-rich sediment samples combined with the lack of features on the Fe(3+) -O(2-) charge transfer absorption edge indicates that the ferric oxide and/or oxyhydroxide in these sediments is poorly crystalline to amorphous in character. Similar features are seen in poorly crystalline basaltic weathering products (e.g., palagonites). The problem of mapping and analyzing the downriver occurrences of iron rich tailings in the Coeur d'Alene (CDA) River Valley using remotely sensed data is complicated by the full vegetation cover present in the area. Because exposures of rock and soil were sparse, the data processing techniques used in this study were sensitive to detecting materials at subpixel scales. The methods used included spectral mixture analysis and a constrained energy minimization technique.

Farrand, W. H.↗

Remote determination of exposure degree and iron concentration of lunar soils using VIS-NIR spectroscopic methods

On the Moon, space weathering processes such as micrometeorite bombardment alter the optical properties of lunar soils. As a consequence, lunar soil optical properties are a function not only of composition, but of degree of exposure on the lunar surface as well. In order to accurately assess the compositional properties of the lunar surface using remotely acquired visible and near-infrared spectroscopic data, it is thus necessary either (1) to compare optical properties only of soils characterized by similar degrees of exposure or (2) to otherwise normalize or remove the optical effects due to exposure. Laboratory spectroscopic data for lunar soils are used to develop and test remote spectrocopic methods for determining degree of exposure and for distinguishing between the optical effects due to exposure and those due to composition. A method employing a ratio between reflectances within and outside of the 1 micrometer Fe(2+) crystal field absorption band was developed for remotely identifying highland soils that have reached a steady-state maturity. The relative optical properties of these soils are a function solely of composition and as such can be directly compared. Spectroscopic techniques for accurate quantitative determination of iron content for lunar highland soils are investigated as well. It is shown that approximations of the 1 micrometer Fe(2+) absorption band depth using few to several channel multispectral data or spectroscopic data of inadequate spectral range cannot be used with confidence for compositional analysis. However, band depth measurements derived from continuum-removed high spectral resolution data can be used to calculate the weight percent FeO and relative proportion of iron-bearing silicates in mature lunar highland and mare/highland mixture soils. A preliminary effort to calibrate telescopic band depth to laboratory soil measurements is described.

Fischer, Erich M.↗

Near Infrared Luminescence Properties of Mn(5+): Ca5(PO4)3F

We report a spectroscopic investigation of Mn(5+) doped Ca5(PO4)(sub 3)F or FAP. Mn(5+) doped crystals have recently attracted world wide attention for potential solid-state laser applications. Following optical excitation of Mn: FAP with the 600 nm output of a Nd: YAG OPO laser system, we observed a strong near infrared luminescence centered at around 1150 nm. The room temperature luminescence decay time was measured to be approximately 635 microseconds. We attribute the infrared luminescence to the(1)E yields (3)A2 transition of tetrahedrally coordinated Mn5+ ions located in a strong crystal field environment. Absorption, luminescence and lifetime data of Mn: FAP will be presented and discussed.

Davis, Valetta R.↗

Three Paradigms of Lunar Regolith Evolution

Integration of diverse datasets on the Moon may render some paradigms of lunar science either better-defended or vulnerable. We will consider three paradigms commonly used for understanding the processes of lunar regolith evolution in light of new and accumulated data. Our premise is that all data-sets should converge to a single interpretation if a concept or model is to be accepted as a paradigm. If a convergence is lacking, the paradigm needs fresh scrutiny. SteadyState: Lunar regolith evolution is currently understood in terms of comminution, agglutination, and replenishment as described by McKay and coworkers). Briefly, the model envisages continued micrometeoritic bombardment to comminute exposed soil particles to finer sizes while continued agglutination consumes finer sizes to produce larger constructional particles. Eventually, a balance between these two opposing processes achieves a steady state; soils at steady state maintain their mean grain size (M(sub z)). Episodic higher-energy impacts excavate fresh coarse material from below the soil cover, disturb the steady state, and restart the process to achieve a new steady state. It follows that the thickness of the regolith at any site would control the frequency of replenishment; indeed, the thickness of the regolith at Apollo landing sites was predicted by McKay et al. from the average M(sub z) of local soils. However, replenishment may come also from disintegrating boulders and cobbles at the lunar surface, and rates of comminution and agglutination may depend on the properties of target material. Regression between M(sub z) and I(sub s)/Fe(sup 0) (a measure of maturity or total surface exposure) of Apollo soils at different sites shows the following relations and estimated M(sub z) at a high maturity of I(sub s)/Fe(sup 0)= 100. It is possible that Apollo 12 and 15 sites have the thickest regolith and the Apollo 16 site has the thinnest. It is also possible that Apollo 12 and 15 basalts are comminuted faster than Apollo 16 highland rocks and Apollo 14 and 17 soils are products of mixed parentage. If a soil becomes continually finer as it matures until agglutination catches up, and if comminution is differential-dependent on the physical properties of the constituents, then the composition of the bulk soil has to match the composition of some "fulcrum" grain size fraction, say X Grain size fractions >X and <X will complement each other; their mass balance is the bulk soil. It appears that the 10-20-micron size fraction may be the fulcrum. In general, trace-element chemistry and IR reflectance spectra of this size fraction are closest to that of the bulk soil, regardless of maturity that is surprising. Disaggregated products of regolith breccias may also show similar relationships. If the 10-20 gm is the fulcrum (i.e., X as above) for many soil properties (e.g., major element composition, FMR, solar-wind-implanted elements), then this may be the ultimate mean grain size of lunar soils at steady state. However, different properties of soils may find steady states at different grain size fractions. The steady state of solar-wind-implanted elements, on the other hand, will climb up the grain-size scale as agglutinates transfer surface-correlated components into volume correlated components until a saturation level is reached or the rates of replenishment and implantation become equal. The same will be the case with vapor-deposited reduced metals as they too are incorporated inside constructional particles. Properties that are directly affected by soil-maturation processes will thus have different pathways of achieving steady states. Maturity, i.e., cumulative surface exposure, of lunar soils is best quantified by the amount of nanophase superparamagnetic Fe(sup 0) (np-Fe(sup 0)) normalized to Fe content (=I(sub s)/Fe(sup 0). The majority consensus (paradigm?) for the production of np-Fe(sup 0) is associated with the production of agglutinates. Because large doses of solar-wind H are implanted in all lunar soils upon exposure, any melting (e.g., during agglutinate production) triggers a chemical reduction of Fe-bearing minerals resulting in np-Fe(sup 0) production. The quantity of np-Fe(sup 0) is thus dependent on melting events, (i.e., exposure), and limited by the Fe content of the soil. All freshly produced np-Fe(sup 0) resides in agglutinitic glass, as new TEM images show. Apparently, the correction procedure developed by Lucey et al. to estimate the Fe content of the lunar surface from IR-reflectance spectra depends on accepting the above. However, the process of producing np-Fe(sup 0) may be physical rather than chemical. All np-Fe(sup 0) could be deposits from a vapor produced by micrometeoritic impact on lunar soils. If metal-O bonds in target phases are broken, O being "most volatile" will escape leaving an O-deficient vapor to facilitate the production of np-Fe(sup 0). If so, the quantity of np-Fe(sup 0) is dependent on the vaporizing events, (i.e., exposure), and limited by the efficiency of breaking metal-O bonds and the escape of 0. To the extent that strengths of metal-O bonds are dependent on the local crystal field, production of np-Fe(sup 0) may be limited by the mineral composition of target soils and not by their total Fe content. According to this model, vapor-deposited np-Fe(sup 0) should be found at any retentive sites on lunar soil grains. Indeed, TEM images show np-Fe(sup 0) on plagioclase and ilmenite. Incorporation of such pre-irradiated np-Fe(sup 0)-bearing grains into agglutinates may account for eventual increased emplacement of np-Fe(sup 0) in agglutinates. Such a paradigm shift in understanding the origin of np-Fe(sup 0) will raise questions ranging from the unquestionable use of Is/FeO as the universal maturity parameter of lunar soils to global elemental maps of the Moon from remote-sensing data. Additional information is contained in the original.

Basu, A.↗

Characterization of iron, manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy

The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.

NASA Center JSC↗

Theoretical Investigations of Clouds and Aerosols in the Stratosphere and Upper Troposphere

support of the Atmospheric Chemistry Modeling and Data Analysis Program. We investigated a wide variety of issues involving ambient stratospheric aerosols, polar stratospheric clouds or heterogeneous chemistry, analysis of laboratory data, and particles in the upper troposphere. The papers resulting from these studies are listed below. In addition, I participated in the 1999-2000 SOLVE mission as one of the project scientists and in the 2002 CRYSTAL field mission as one of the project scientists. Several CU graduate students and research associates also participated in these mission, under support from the ACMAP program, and worked to interpret data. During the past few years my group has completed a number of projects under the

Toon, Owen B.↗

Temperature Sensing Above 1000 C Using Cr-Doped GdAlO3 Spin-Allowed Broadband Luminescence

Cr-doped GdAlO3 (Cr:GdAlO3) is shown to produce remarkably high-intensity spin-allowed broadband luminescence with sufficiently long decay times to make effective luminescence-decay-time based temperature measurements above 1000 C. This phosphor is therefore an attractive alternative to the much lower luminescence intensity rare-earth-doped thermographic phosphors that are typically utilized at these elevated temperatures. In particular, Cr:GdAlO3 will be preferred over rare-earth-doped phosphors, such as Dy:YAG, at temperatures up to 1200 C for intensity-starved situations when the much lower emission intensity from rare-earth-doped phosphors is insufficient for accurate temperature measurements in the presence of significant radiation background. While transition-metal-doped phosphors such as Cr:Al2O3 (ruby) are known to exhibit high luminescence intensity at low dopant concentrations, quenching due to nonradiative decay pathways competing with the (sup 2)E to (sup 4)A(sub 2) radiative transition (R line) has typically restricted their use for temperature sensing to below 600 C. Thermal quenching of the broadband (sup 4)T(sub 2) to (sup 4)A(sub 2) radiative transition from Cr:GdAlO3, however, is delayed until much higher temperatures (above 1000 C). This spin-allowed broadband emission persists to high temperatures because the lower-lying (sup 2)E energy level acts as a reservoir to thermally populate the higher shorter-lived (sup 4)T(sub 2) energy level and because the activation energy for nonradiative crossover relaxation from the (sup 4)T(sub 2) level to the (sup 4)A(sub 2) ground state is high. The strong crystal field associated with the tight bonding of the AlO6 octahedra in the GdAlO3 perovskite structure is responsible for this behavior.

Eldridge, Jeffrey I.↗

Temperature-Dependent Changes in the Normal Albedo of the Lunar Surface at 1064 nm

Over the extreme temperature variations experienced in a single lunar day (∆T≈300 K), particular minerals common to the lunar surface show spectral changes at near-infrared wavelengths in laboratory settings (Singer and Roush, 1985; Roush and Singer, 1986, 1987). Variations in temperature can cause variations in the size and shape of crystallographic sites, which control the position, shape, and depth of crystal field absorptions. At an observation wavelength of 1064 nm, the Lunar Orbiter Laser Altimeter (LOLA) should be highly sensitive to temperature-dependent changes of orthopyroxene. Here we analyze temperature-dependent spectral changes of the lunar surface as measured from orbit by LOLA. We couple LOLA measurements of normal albedo with measurements of surface temperature from the Diviner Lunar Radiometer Experiment, analyzing the maria and highlands terranes between ±50° in 1°x1° spatial bins. We provide the first evidence of temperature-dependent spectral changes on the lunar surface from orbital observations, finding that the majority of the lunar surface between 50°N and 50°S demonstrates a small, yet measurable, negative change in normal albedo at 1064 nm with temperature (-∆R/∆T). The measurable effect is on the order of a few percent change in reflectance per ~80 K, indicating temperature changes do not have a large effect on measurements of albedo at the sensitivity of the LOLA instrument. Stronger -∆R/∆T values tend to be associated with the maria, and regions with elevated orthopyroxene levels. Our results suggest that single-wavelength lasers may be powerful tools for understanding the distribution of particular minerals on the lunar surface.

Ariel N Deutsch↗