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All sourcesNASA NTRSDOE OSTI
NASA NTRS2008

Experimental Constraints on the Partitioning and Valence of V and Cr in Garnet and Coexisting Glass

A series of experiments with garnet and coexisting melt have been carried out across a range of oxygen fugacities (near hematite-magnetite (HM) to below the iron-wustite (IW) buffers) at 1.7 GPa to study the partitioning and valence of Cr and V in both phases. Experiments were carried out in a non end loaded piston cylinder apparatus, and the run products were analyzed with electron microprobe and xray absorption near edge structure (XANES) analysis at beamline 13-ID at the Advanced Photon Source of Argonne National Lab. The valence of vanadium and chromium were determined using the position and intensity of the Ka pre-edge peaks, calibrated on a series of Cr and Vbearing standard glasses. This technique has been applied to V and Cr in glasses and V in spinels previously, and in these isotropic phases there are no orientational effects on the XANES spectra (Righter et al., 2006, Amer. Mineral. 91, 1643-1656). We also now demonstrate this to be true for V and Cr in garnet. Also, previous work has shown that V has a higher valence in the glass (or melt) than in the coexisting spinel. This is also true for V in garnet-glass pairs in this study. Vanadium valence in garnets varies from 2.7 below the IW buffer to 3.7 near HM, and for coexisting glass it varies from 3.2 to 4.3. Vanadium valence measured in some natural garnets from mantle localities indicates V in the more reduced range at 2.5. Comparisons will be made between fO2 estimated from V valence and other methods for garnet-bearing mantle samples. In contrast, Cr valence measured in garnet and coexisting glass for all experimental and natural samples is 2.9- 3.0, suggesting that the valence of Cr does not vary within either phase across a large fO2 range. These results demonstrate that while V varies from 2+ to 3+ to 4+ in garnet-melt systems, Cr does not, and this will ultimately affect the partitioning behavior of these two elements in natural systems. Garnet/melt D(Cr) are between 12 and 17 across this range of fO2, whereas D(V) has the highest partition coefficient approx.3, near the IW buffer where the valence of V is almost entirely 3+.

Righter, K.↗
NASA NTRS2003

Analyzing Discrepancies in a Software Development Project Change Request (CR) Assessment Process and Recommendations for Process Improvements

The Change Request (CR) assessment process is essential in the display development cycle. The assessment process is performed to ensure that the changes stated in the description of the CR match the changes in the actual display requirements. If a discrepancy is found between the CR and the requirements, the CR must be returned to the originator for corrections. Data was gathered from each of the developers to determine the type of discrepancies and the amount of time spent assessing each CR. This study sought to determine the most common types of discrepancies, and the amount of time required to assessing those issues. The study found that even though removing discrepancy before an assessment would save half the time needed to assess an CR with a discrepancy, the number of CR's found to have a discrepancy was very small compared to the total number of CR's assessed during the data gathering period.

Cunningham, Kenneth James↗
NASA NTRS2011

High-Temperature Thermometer Using Cr-Doped GdAlO3 Broadband Luminescence

A new concept has been developed for a high-temperature luminescence-based optical thermometer that both shows the desired temperature sensitivity in the upper temperature range of present state-of-the-art luminescence thermometers (above 1,300 C), while maintaining substantial stronger luminescence signal intensity that will allow these optical thermometers to operate in the presence of the high thermal background radiation typical of industrial applications. This objective is attained by using a Cr-doped GdAlO3 (Cr:GdAlO3) sensor with an orthorhombic perovskite structure, resulting in broadband luminescence that remains strong at high temperature due to the favorable electron energy level spacing of Cr:GdAlO3. The Cr:GdAlO3 temperature (and pressure) sensor can be incorporated into, or applied onto, a component s surface when a non-contact surface temperature measurement is desired, or alternatively, the temperature sensor can be attached to the end of a fiber-optic probe that can then be positioned at the location where the temperature measurement is desired. In the case of the fiber-optic probe, both the pulsed excitation and the luminescence emission travel through the fiber-optic light guide. In either case, a pulsed light source provides excitation of the luminescence, and the broadband luminescence emission is collected. Real-time temperature measurements are obtain ed using a least-squares fitting algorithm that determines the luminescence decay time, which has a known temperature dependence established by calibration. Due to the broad absorption and emission bands for Cr:GdAlO3, there is considerable flexibility in the choice of excitation wavelength and emission wavelength detection bands. The strategic choice of the GdAlO3 host is based on its high crystal field, phase stability, and distorted symmetry at the Cr3+ occupation sites. The use of the broadband emission for temperature sensing at high temperatures is a key feature of the invention and is novel since broadband luminescence emission normally shows severe thermal quenching. The tightly bound AlO6 octahedra in GdAlO3 results in a larger energy barrier to nonradiative decays than in other materials and therefore makes using broadband emission for temperature sensing possible at high temperatures. This approach results in a substantial increase in temperature capability. For example, the most commonly used Cr-doped crystal used for luminescence-based temperature measurements, ruby, has only been demonstrated up to 600 C, whereas the Cr:GdAlO3 optical thermometer under development has already been shown to exhibit useful luminescence up to 1,300 C. Because GdAlO3 is non-reactive and is stable in harsh, high-temperature environments, sensors composed of Cr:GdAlO3 will be very well suited for remote high-temperature measurements in engine or industrial environments where its intense high-temperature luminescence will stand out above significant thermal radiation background levels.

Eldridge, Jeffrey↗
NASA NTRS2005

The Mn-53-Cr-53 System in CAIs: An Update

High precision techniques have been developed for the measurement of Cr isotopes on the Triton mass spectrometer, at JPL. It is clear that multiple Faraday cup, simultaneous ion collection may reduce the uncertainty of isotope ratios relative to single Faraday cup ion collection, by the elimination of uncertainties from ion beam instabilities (since ion beam intensities for single cup collection are interpolated in time to calculate isotope ratios), and due to a greatly increased data collection duty cycle, for simultaneous ion collection. Efforts to measure Cr by simultaneous ion collection have not been successful in the past. Determinations on Cr-50-54Cr, by simultaneous ion collection on the Finnigan/ MAT 262 instrument at Caltech, resulted in large variations in extrinsic precision, for normal Cr, of up to 1% in Cr-53/Cr-52 (data corrected for mass fractionation, using Cr-50/Cr-52).

Papanastassiou, D. A.↗
NASA NTRS1984

The effects of Cr, Co, Al, Mo and Ta on the cyclic oxidation behavior of a prototype cast Ni-base superalloy based on a 2(5) composite statistically designed experiment

A series of cast Ni-base superalloys were systematically varied at selected levels of Co, Cr, Mo, Ta, and Al. The elemental levels varied were Mo, 0 to 4 percent; Cr, 6 to 18 percent; Co, 0 to 20 percent, Ta, 0 to 8 percent; and Al, 3.25 to 6.25 percent. The cyclic oxidation resistance was determined from specific weight change data as a function of time for 1 hr cycles in static air at 1100 C. The significant terms in decreasing order of their importance were Al, Ta, Cr2, Al-Cr, Cr-Co, Co2, Al-Mo, Cr-Mo, Al-Al, and Mo-Ta. The Al term alone accounted for close to 82 percent of the explained variability. The estimating equation showed that the Al level was the most important and should be at its 6.25 wt % maximum value. The Mo and Ta levels should also be at their maximum 4 and 8 wt % respectively. The cobalt composition should be as low as possible, i.e., 0 wt%. The Cr level optimum varies depending on the other 4 levels. The X-ray diffaction results indicate the most protective scales are alumina/aluminate spinel stabilizized with a tri-rutile oxide high in Ta and Mo.

Barrett, C. A.↗
NASA NTRS1989

Development of flashlamp-pumped Q-switched Ho:Tm:Cr:YAG lasers for mid-infrared LIDAR application

A flashlamp-pumped 2.1 micron Ho:Tm:Cr:YAG laser was studied for both normal mode and Q-switched operations under a wide variety of experimental conditions in order to optimize performance. Laser output energy, slope efficiency, threshold and pulselength were determined as a function of operating temperature, output mirror reflectivity, input electrical energy and Q-switch opening time. The measured normal-mode laser thresholds of a Ho(3+) (0.45 atomic percent):Tm(3+) (2.5 atomic percent):Cr(3+) (0.8 atomic percent):YAG crystal ranged form 26 to 50 J between 120 and 200 K with slope efficiencies up to 0.36 percent with a 60 percent reflective output mirror. Under Q-switched operation the slope efficiency was 90 percent of the normal-mode result. Development of solid state lasers with Ho(3+), Tm(3+) and/or Er(3+) doped crystals has been pursued by NASA for eye-dafe mid-infrared LIDAR (light detection and ranging) application. As a part of the project, the authors have been working on evaluating Ho(3+):Tm(3+):Cr(3+):YAG crystals for normal-mode and Q-switched 2.1 micron laser operations in order to determine an optimum Tm(3+) concentration under flashlamp pumping conditions. Lasing properties of the Ho(3+) in the mid-infrared region have been studied by many research groups since the early 1960's. However, the technology of those lasers is still premature for lidar application. In order to overcome the inefficiency related to narrow absorption bands of the Ho(3+), Tm(3+) and Er(3+), the erbium has been replaced by chromium. The improvement in flashlamp-pumped Ho(3+) laser efficiency has been demonstrated recently by several research groups by utilizing the broad absorption spectrum of Cr(3+) which covers the flashlamp's emission spectrum. Efficient energy transfer to the Tm(3+) and then the Ho(3+) occurs subsequently. It is known that high Tm(3+) concentration and low Ho(3+) concentration are preferred to achieve a quantum efficiency approaching two and to avoid large reabsorption losses. However, determination of the optimum Tm(3+) concentration required to ensure efficient energy transfer from Cr(3+) to Tm(3+) and from Tm(3+) to Ho(3+) has not been made in the Ho:Tm:CR:YAG crystal. The results obtained so far are given.

Choi, Young S.↗
NASA NTRS1978

A feasibility study of a diffusion barrier between Ni-Cr-Al coatings and nickel-based eutectic alloys

Coating systems have been proposed for potential use on eutectic alloy components in high-temperature gas turbine engines. In a study to prevent the deterioration of such systems by diffusion, a tungsten sheet 25 microns thick was placed between eutectic alloys and an Ni-Cr-Al layer. Layered test specimens were aged at 1100 C for as long as 500 h. Without the tungsten barrier the delta phase of the eutectic deteriorated by diffusion of niobium into the Ni-Cr-Al. Insertion of the tungsten barrier stopped the diffusion of niobium from the delta phase. Chromium diffusion from the Ni-Cr-Al into the gamma/gamma-prime phase of the eutectic was greatly reduced by the barrier. However, the barrier thickness decreased with time, and tungsten diffused into both the Ni-Cr-Al and the eutectic. When the delta platelets were aligned parallel rather than perpendicular to the Ni-Cr-Al layer, diffusion into the eutectic was reduced.

Young, S. G.↗
NASA NTRS1986

A comparison of the bonding in Cr(NO)4 and Ni(CO)4

The bonding in Cr(NO)4 is very ionic, with about 1.5 electrons donated from the Cr to the NO 2pi orbitals. There is also a NO sigma donation of about 0.5 electrons to the Cr, yielding a net charge of Cr of about 1. A large MCSCF expansion is needed to describe both the ionic and covalent contributions to the Cr 3d-NO 2pi bonding. This bonding is compared to that in the isoelectronic Ni(CO)4.

Bauschlicher, C. W., Jr.↗
NASA NTRS1992

Novel Cr(4+)-based tunable solid-state lasers

Spectroscopic and laser properties of chromium-doped forsterite (Cr:Mg2SiO4) are reviewed and future directions in development of other Cr(4+)-doped tunable solid-state lasers are discussed. The unique property of chromium-doped forsterite is that the lasing center was identified as tetravalent chromium (Cr(4+)) substituting for tetrahedrally coordinated Si(4+). Development of chromium-doped forsterite laser may stimulate the generation of a new class of tunable solid state lasers based on tetravalent chromium as a laser active ion for the near-IR eyesafe spectral range. The criteria for the development of new Cr(4+)-based tunable solid-state laser crystals are discussed. We also present current research efforts to identify potential low field host crystals, such as silicates, titanites, and germanates, that may be doped with Cr(4+) as an active ion. These new laser materials are expected to cover the wavelength region from 1 - 2 microns, which may be of great technological importance.

Petricevic, V.↗
NASA NTRS1994

Observations of enhanced sub-iron (Sc-Cr) to Iron abundance ratios in the low energy galactic cosmic rays in Spacelab-3 and their implications

The Anuradha cosmic ray experiment in Spacelab-3, flown in the orbit at 350 km with an inclination of 57 deg for about six days, was used to measure the low energy galactic cosmic ray (GCR) heavy ions using a specially designed CR-39 detector module incorporating the arrival time information of the particles. The abundances of sub-iron (Sc-Cr) and iron particles in the low energy interval of 30-300 MeV/N were determined from the measurements made in four different depths of the Cr-39 detector module of 150 layers. From these studies we obtained sub-iron (Sc-Cr) to iron abundance ratios of 0.8 to 1.2 in 30-300 MeV/N energy range. It is found that these ratios are enhanced by a factor of two as compared to interplanetary ratios of about 0.5. It is shown that the enhancement of the ratio inside the earth's magnetosphere is probably due to the degree of ionization of low energy Sc to Cr and Fe ions in the galactic cosmic rays and to the rigidity filtering effects of the geomagnetic field. Further studies are needed to understand fully the phenomena and their implications.

Biswas, S.↗
NASA NTRS1995

Influence of Cr and W alloying on the fiber-matrix interfacial shear strength in cast and directionally solidified sapphire NiAl composites

Sapphire-reinforced NiAl matrix composites with chromium or tungsten as alloying additions were synthesized using casting and zone directional solidification (DS) techniques and characterized by a fiber pushout test as well as by microhardness measurements. The sapphire-NiAl(Cr) specimens exhibited an interlayer of Cr rich eutectic at the fiber-matrix interface and a higher interfacial shear strength compared to unalloyed sapphire-NiAl specimens processed under identical conditions. In contrast, the sapphire-NiAl(W) specimens did not show interfacial excess of tungsten rich phases, although the interfacial shear strength was high and comparable to that of sapphire-NiAl(Cr). The postdebond sliding stress was higher in sapphire-NiAl(Cr) than in sapphire-NiAl(W) due to interface enrichment with chromium particles. The matrix microhardness progressively decreased with increasing distance from the interface in both DS NiAl and NiAl(Cr) specimens. The study highlights the potential of casting and DS techniques to improve the toughness and strength of NiAl by designing dual-phase microstructures in NiAl alloys reinforced with sapphire fibers.

Asthana, R.↗
NASA NTRS2000

Creep and Toughness of Cryomilled NiAl Containing Cr

NiAl-AlN + Cr composites were produced by blending cryomilled NiAl powder with approx. 10 vol % Cr flakes. In comparison to the as-consolidated matrices, hot isostatically pressed Cr-modified materials did not demonstrate any significant improvement in toughness. Hot extruded NiAl-AlN+10.5Cr, however, possessed a toughness twice that determine for the base NiAl-AlN alloy. Measurement of the 1200 to 1400 K plastic flow properties revealed that the strength of the composites was completely controlled by the properties of the NiAl-AlN matrices. This behavior could be successfully modeled by the Rule-of-Mixtures, where load is shed from the weak Cr to the strong matrix.

Whittenberger, J. Daniel↗
NASA NTRS2002

Constraining the Material that Formed the Moon: The Origin of Lunar V, CR, and MN Depletions

The mantles of the Earth and Moon are similarly depleted in V, Cr, and Mn relative to chondritic values. Core formation deep within the Earth was suggested by as the origin of the depletions. Following Earth's core formation, the Moon was proposed to have inherited its mantle from the depleted mantle of the Earth by a giant impact event. This theory implied the Moon was primarily composed of material from the Earth's mantle. Recent systematic metal-silicate experiments of V, Cr, and Mn evaluated the behavior of these elements during different core formation scenarios. The study found that the V, Cr, and Mn depletions in the Earth could indeed be explained by core formation. The conditions of core formation necessary to deplete V, Cr, and Mn in the Earth's mantle were consistent with the deep magma ocean proposed to account for the Earth's mantle abundances of Ni and Co. Using the parameterizations of for the metal-silicate partition coefficients (D) of V, Cr, and Mn, we investigate here the conditions needed to match the depletions in the silicate Moon and determine if such conditions could have been present on the giant impactor.

Chabot, N. L.↗
NASA NTRS2003

Fe-Ti-Cr-Oxides in Martian Meteorite EETA79001 Studied by Point-counting Procedure Using Raman Spectroscopy

Fe-Ti-Cr-Oxide minerals contain much information about rock petrogenesis and alteration. Among the most important in the petrology of common intrusive and extrusive rocks are those of the FeO-TiO2-Cr2O3 compositional system chromite, ulv spinel-magnetite, and ilmenite-hematite. These minerals retain memories of oxygen fugacity. Their exsolution into companion mineral pairs give constraints on formation temperature and cooling rate. Laser Raman spectroscopy is anticipated to be a powerful technique for characterization of materials on the surface of Mars. A Mars Microbeam Raman Spectrometer (MMRS) is under development. It combines a micro sized laser beam and an automatic point-counting mechanism, and so can detect minor minerals or weak Raman-scattering phases such as Fe- Ti-Cr-oxides in mixtures (rocks & soils), and provide information on grain size and mineral mode. Most Fe-Ti-Cr-oxides produce weaker Raman signals than those from oxyanionic minerals, e.g. carbonates, sulfates, phosphates, and silicates, partly because most of them are intrinsically weaker Raman scatters, and partly because their dark colors limit the penetration depth of the excitation laser beam (visible wavelength) and of the Raman radiation produced. The purpose of this study is to show how well the Fe-Ti-Cr-oxides can be characterized by on-surface planetary exploration using Raman spectroscopy. We studied the basic Raman features of common examples of these minerals using well-characterized individual mineral grains. The knowledge gained was then used to study the Fe-Ti-Cr-oxides in Martian meteorite EETA79001, especially effects of compositional and structural variations on their Raman features.

Wang, Alian↗
NASA NTRS2004

Thermal Effects on a Low Cr Modification of PS304 Solid Lubricant Coating

PS304 is a high temperature composite solid lubricant coating composed of Ni-Cr, Cr2O3, BaF2-CaF2 and Ag. The effect of reducing chromium content on the formation of voids in the Ni-Cr particles after heat treatment in PS304 coating was investigated. Coatings were prepared with Ni-20Cr or Ni-10Cr powder and in various combinations with the other constituents of PS304 (i.e., chromia, silver and eutectic BaF2-CaF2 powders) and deposited on metal substrates by plasma spray. Specimens were exposed to 650 C for 24 hr or 1090 C for 15 hr and then examined for changes in thickness, coating microstructure and adhesion strength. Specimens with Ni-10Cr generally had less thickness increase than specimens with Ni-20Cr, but there was great variance in the data. Reduction of chromium concentration in Ni-Cr powder tended to reduce the appearance of voids in the Ni-Cr phase after heat exposure. The presence of BaF2-CaF2 resulted in a significant increase in coating adhesion strength after heat treatment, while coatings without BaF2-CaF2 had no significant change. Chemical composition analysis suggested that the void formation was due to oxidation of chromium in the Ni-Cr constituent.

Stanford, Malcolm K.↗
NASA NTRS2006

Mn-53-Cr-53 Systematics of R-Chondrite NWA 753

Chondrules and chondrites are interpreted as objects formed in the early solar system, and it is important to study them in order to elucidate its evolution. Here, we report the study of the Mn-Cr systematics of the R-Chondrite NWA753 and compare the results to other chondrite data. The goal was to determine Cr isotopic and age variations among chondrite groups with different O-isotope signatures. The Mn-53-Cr-53 method as applied to individual chondrules [1] or bulk chondrites [2] is based on the assumption that 53Mn was initially homogeneously distributed in that portion the solar nebula where the chondrules and/or chondrites formed. However, different groups of chondrites formed from regions of different O-isotope compositions. So, different types of chondrites also may have had different initial Mn-53 abundances and/or Cr isotopic compositions. Thus, it is important to determine the Cr isotopic systematics among chondrites from various chondrite groups. We are studying CO-chondrite ALH83108 and Tagish Lake in addition to R-Chondrite NWA753. These meteorites have very distinct O-isotope compositions (Figure 1).

Jogo, K.↗
NASA NTRS2002

Descriptive Study Analyzing Discrepancies in a Software Development Project Change Request (CR) Assessment Process and Recommendations for Process Improvements

The Change Request (CR) assessment process is essential in the display development cycle. The assessment process is performed to ensure that the changes stated in the description of the CR match the changes in the actual display requirements. If a discrepancy is found between the CR and the requirements, the CR must be returned to the originator for corrections. Data will be gathered from each of the developers to determine the type of discrepancies and the amount of time spent assessing each CR. This study will determine the most common types of discrepancies and the amount of time spent assessing those issues. The results of the study will provide a foundation for future improvements as well as a baseline for future studies.

Cunningham, Kenneth J.↗
NASA NTRS2012

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.↗