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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Magnetic and magnetocaloric properties of bulk dysprosium chromite

In this work, a polycrystalline bulk DyCrO{sub 3} sample was prepared by a solution route and the structural and magnetic properties were investigated. The phase purity and ionic valence state of the DyCrO{sub 3} sample were determined by x-ray diffraction/Raman spectroscopy and x-ray photoelectron spectroscopy, respectively. The AC and DC magnetization measurements revealed the onset of antiferromagnetic order at 146 K with an effective moment of 8.88 μ{sub B}. Isothermal magnetization measurements of this material are presented for the first time, showing a peak in the coercive field at 80 K that is explained by the competition between the paramagnetic Dy{sup 3+} and Cr{sup 3+} sublattices. DyCrO{sub 3} was found to display a large magnetocaloric effect (8.4 J/kg K) and relative cooling power (217 J/kg) at 4 T applied field, which renders DyCrO{sub 3} useful for magnetic refrigeration between 5 K and 30 K.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Structural and electronic properties of rare-earth chromites: A computational and experimental study

Here, in this work, the structural, optical, and electronic properties of rare-earth perovskites of the general formula R⁢ CrO 3 , where R⁢ represents the rare-earth Gd, Tb, Dy, Ho, Er, and Tm, have been studied in detail. These compounds were synthesized through a facile citrate route. X-ray diffraction, Raman spectroscopy, and UV-Visible spectroscopy were utilized to reveal the structural evolutions in R⁢ ⁢CrO 3 . The lattice parameters, Cr 3+ –O 2 –Cr 3+ bond angle, and CrO 6 octahedral distortions were found to strongly depend on the ionic radii of R⁢ . First-principles calculations based on density-functional theory within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) and strongly constrained and appropriately normed (SCAN) meta-GGA were also employed to calculate the structural and electronic properties of R⁢ ⁢CrO 3 . The ground-state energy, lattice constants, electronic structures, and density of states of R⁢ ⁢CrO 3 were calculated. These provide some insights into the electronic characteristics of the R⁢ ⁢CrO 3 compounds. The calculated values of lattice parameters and band gaps with Hubbard U correction (SCAN+ U ) agree well with values measured experimentally and show more accuracy in predicting the ground-state crystal structure and band structure compared to PBE+ U approximation. The band gap of R⁢ ⁢CrO 3 is found to be independent of the ionic radii of R⁢ from both experiments and calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1972

Iron-titanium-chromite, a possible new carrier of remanent magnetization in lunar rocks.

Magnetic measurements of synthetic titanchromites reveal a characteristic transition at low temperature, making it possible to identify the presence of titanchromites in lunar rocks 12063, 14321 (dark clasts), and 14310. It is shown that titanchromites with a high chromium content could be the carriers of intermediate stability natural remanent magnetization observed in lunar rocks. Such natural remanent magnetization is acquired by transition thermoremanent magnetization at low temperature and cannot be duplicated by laboratory thermoremanent magnetization imparted above room temperature. The latter process will not yield the correct lunar paleointensity.

Banerjee, S. K.↗
NASA NTRS1984

Achondrite ALHA77005 - Alteration of chromite and olivine

The olivine crystals of the 77005 achondrite are brown except for colorless shock lamellae, mottled patches, and grains adjacent to pools of impact melt. Sporadic dark alteration patches in brown olivine and Cr-rich spinel gave the following average electron-microprobe analyses: (olivine) P2O5 0.9, SiO2 57.9, TiO2 0, Al2O3 0.7, Cr2O3 0.4, V2O3 0, Fe2O3 (assumed oxidation state) 17.0, MgO 1.6, CaO 0.2, Na2O 0, K2O 1.8, SO3 (assumed oxidation state) 9.2, Cl 0.1, sum 89.8 wt pct; (spinel) P2O5 3.5, SiO2 2.1, TiO2 2.2, Al2O3 2.1, Cr2O3 13.4, V2O3 0.8, Fe2O3 40.7, MgO 0.9, CaO 0.1, Na2O 0, K2O 2.0, SO3 11.1, Cl 0.1, sum 79.0 wt pct. Ion-microprobe analyses revealed H in both. Rare orange patches in brown olivine from another area gave SiO2 33-35, FeO 30-28, MgO 28-32, sum 93 wt pct. Thermal metamorphism under dry oxidizing conditions is discussed as a possible alternative to shock-induced oxidation for generation of the brown olivine (McSween and Stoeffler, 1980). Because alteration patches transgress shock lamellae, and because sulfatic alteration occurs in fusion crusts of Antarctic meteorites (Gibson et al., 1983), alteration of the 77005 achondrite at the Antarctic surface is preferred to a complex series of processes needed for preterrestrial alteration.

Smith, J. V.↗
NASA NTRSDate not supplied

Tin-Essako 001: A Metal-Rich Ureilite?

Introduction: Metal-rich achondrites include a variety of types, and likely have a variety of origins. Models range from gravitational mixing at the core-mantle boundaries of differentatiated asteroids, to complex impact mixing scenarios. We describe a new type of metal-rich achondrite that might be the first metal-rich ureilite. Sample: Tin-Essako (TE) 001 (~4.3 g) was found in Mali in 2020 and purchased by Jay Piatek in 2021. It was classified as a metal-rich ungrouped achondrite, with olivine and oxygen isotope (d18O=8.2810‰, d17O=3.718‰, avg. 3) compositions suggesting affinity to ureilites [1]. We studied one polished section (~187.7 mm2) of TE 001. Petrography: TE 001 consists of ~60% metal and 40% silicates, heterogeneously distributed. The metal is largely fresh, but iron oxides (presumably terrestrial) occur along one edge and in some patches and veins in the interior. The silicates are dominantly olivine (≥90%), with melt-textured areas of plagioclase + Si-rich glass. Minor phases include chromite and carbon. Olivine occurs as rounded grains (up to ~2.5 mm) in metal, commonly with rims of melt-textured plagioclase + glass. Olivine also occurs in more massive areas having a “honeycomb” texture, with rounded olivine “cells” surrounded by an interstitial network of reduced olivine riddled with tiny metal grains, plus melt-textured plagioclase + Si-rich glass. Chromite occurs as subhedral to rounded grains; smaller grains (30-250 mm) are included in olivine and a few larger grains (400-500 mm) are isolated within metal. A carbon phase occurs as lacy-textured rims around olivine grains in metal, or small patches within metal. Mineral Compositions: The olivine (excluding interstitial areas) is Fo 73.9±0.5, with 0.25±0.02 wt.% CaO, 0.31±0.01 wt% Cr2O3, 0.01 wt.% NiO, and molar Fe/Mn=49.8±2.2 (53 analyses). Olivine in interstitial areas has Fo up to at least 91. Smaller chromite grains have Fe# (molar Fe/[Fe+Mg]) = 0.54±0.01, Cr# (molar Cr/[Cr+Al]) = 0.52±0.01, 0.52±0.02 wt.% V2O3 and 0.21±0.04 wt% ZnO (28 analyses). One larger grain is zoned from Fe# = 0.45, Cr# =0.52 to Fe# = 0.40, Cr# =0.57, and contains thin Al-rich lamellae not resolved by EMPA. One irregularly shaped patch of chromite included in olivine has Fe# =0.26 and contains no ZnO. Plagioclase laths are An ~53-60, with ≤0.01 wt.% K2O. Glass contains 75-76 wt% SiO2 and ~16 wt% Al2O3. The metal contains 5.2±0.2 wt% Ni, 0.46±0.02 wt.% Co, and 0.01±0.01 wt.% Cr, with Si and P below detection (168 analyses). Discussion: The olivine + chromite assemblage in TE 001 is similar to the most ferroan ureilites (Fo ~75-79 [2]), as are the oxygen isotopes [1]. The presence of a carbon phase supports this, although the identity of this phase (graphite as in ureilites?) remains to be determined. The “honeycomb” textured areas, in particular, the presence of olivine “reduction rims,” resemble shock-smelted olivine areas in ureilites [3], but interstitial melt-textured plagioclase laths + glass like those in TE 001 have not been reported in such (or any) ureilites. Olivine in TE 001 is marginally more ferroan than in the most FeO-rich ureilite, with Fe-Mg-Mn composition offset from the trend of olivine + low-Ca pyroxene ureilites similar to augite-bearing ureilites [4]. CaO and Cr2O3 contents are in the range of those in ureilite olivine [ ] , though Cr2O3 is at the extreme low end of the range [5]. Chromites (except the unusual one) have similar Fe# to the most ferroan primary chromites in ureilites [2], but distinctly lower Cr# (0.52 vs. 0.71). Metal compositions are with the range for metal in ureilites [7]. The absence of pyroxene and sulfide, and the high abundance of metal in TE 001, are unlike ureilites. One possibility is that a ferroan, chromite-bearing, pyroxene-poor ureilite was invaded (possibly due to impact) by a metallic liquid (low S content suggests very high temperature), resulting in complete melting of pyroxene and smelting of olivine, with rapid recrystallization of melted silicate as plagioclase + glass. Alternatively, a pre-existing metal-rich ureilite assemblage may have been impact melted. Additional types of data will be obtained to evaluate these hypotheses (i.e., is the metal indigenous?) and assess affinity to ureilites.

olivine↗
DOE OSTI2017

The Miller Range 090340 and 090206 meteorites: Identification of new brachinite-like achondrites with implications for the diversity and petrogenesis of the brachinite clan

Miller Range (MIL) 090340 and MIL 090206 are olivine-rich achondrites originally classified as ureilites. We investigate their petrography, mineral compositions, olivine Cr valences, equilibration temperatures, and (for MIL 090340) oxygen isotope compositions, and compare them with ureilites and other olivine-rich achondrites. We conclude that they are brachinite-like achondrites that provide new insights into the petrogenesis of brachinite clan meteorites. MIL 090340,6 has a granoblastic texture and consists of ~97 modal % by area olivine (Fo = molar Mg/[Mg+Fe] = 71.3 ± 0.6). It also contains minor to trace augite, chromite, chlorapatite, orthopyroxene, metal, troilite, and terrestrial Fe-oxides. Approximately 80% by area of MIL 090206,5 has a granoblastic texture of olivine (Fo 72.3 ± 0.1) plus minor augite and chromite, similar to MIL 090340 but also containing minor plagioclase. The rest of the section consists of a single crystal of orthopyroxene (~11 × 3 mm), poikilitically enclosing rounded grains of olivine (Fo = 76.1 ± 0.6), augite, chromite, metal, and sulfide. Equilibration temperatures for MIL 090340 and MIL 090206, calculated from olivine-spinel, olivine-augite, and two-pyroxene thermometry range from ~800 to 930 °C. In both samples, symplectic intergrowths of Ca-poor orthopyroxene + opaque phases (Fe-oxides, sulfide, metal) occur as rims on and veins/patches within olivine. Before terrestrial weathering, the opaques were probably mostly sulfide, with minor metal. All petrologic properties of MIL 090340 and MIL 090206 are consistent with those of brachinite clan meteorites, and largely distinct from those of ureilites. Oxygen isotope compositions of olivine in MIL 090340 (δ 18 O = 5.08 ± 0.30‰, δ 17 O = 2.44 ± 0.21‰, and Δ 17 O = -0.20 ± 0.12‰) are also within the range of brachinite clan meteorites, and well distinguished from ureilites. Olivine Cr valences in MIL 090340 and the granoblastic area of MIL 090206 are 2.57 ± 0.06 and 2.59 ± 0.07, respectively, similar to those of three brachinites also analyzed here (Brachina, Hughes 026, Nova 003). They are higher than those of olivine in ureilites, even those containing chromite. The valence systematics of MIL 090340, MIL 090206, and the three analyzed brachinites (lower Fo = more oxidized Cr) are consistent with previous evidence that brachinite-like parent bodies were inherently more oxidized than the ureilite parent body. The symplectic orthopyroxene + sulfide/metal assemblages in MIL 090340, MIL 090206, and many brachinite clan meteorites have superficial similarities to characteristic “reduction rims” in ureilites. However, they differ significantly in detail. They likely formed by reaction of olivine with S-rich fluids, with only minor reduction. MIL 090340 and the granoblastic area of MIL 090206 are similar in modal mineralogy and texture to most brachinites, but have higher Fo values typical of brachinite-like achondrites. The poikilitic pyroxene area of MIL 090206 is more typical of brachinite-like achondrites. The majority of their properties suggest that MIL 090340 and MIL 090206 are residues of low-degree partial melting. The poikilitic area of MIL 090206 could be a result of limited melt migration, with trapping and recrystallization of a small volume of melt in the residual matrix. Finally, these two samples are so similar in mineral compositions, Cr valence, and cosmic ray exposure ages that they could be derived from the same lithologic unit on a common parent body.

58 GEOSCIENCES↗
NASA NTRS2005

Process Developed for Generating Ceramic Interconnects With Low Sintering Temperatures for Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) have been considered as premium future power generation devices because they have demonstrated high energy-conversion efficiency, high power density, and extremely low pollution, and have the flexibility of using hydrocarbon fuel. The Solid-State Energy Conversion Alliance (SECA) initiative, supported by the U.S. Department of Energy and private industries, is leading the development and commercialization of SOFCs for low-cost stationary and automotive markets. The targeted power density for the initiative is rather low, so that the SECA SOFC can be operated at a relatively low temperature (approx. 700 C) and inexpensive metallic interconnects can be utilized in the SOFC stack. As only NASA can, the agency is investigating SOFCs for aerospace applications. Considerable high power density is required for the applications. As a result, the NASA SOFC will be operated at a high temperature (approx. 900 C) and ceramic interconnects will be employed. Lanthanum chromite-based materials have emerged as a leading candidate for the ceramic interconnects. The interconnects are expected to co-sinter with zirconia electrolyte to mitigate the interface electric resistance and to simplify the processing procedure. Lanthanum chromites made by the traditional method are sintered at 1500 C or above. They react with zirconia electrolytes (which typically sinter between 1300 and 1400 C) at the sintering temperature of lanthanum chromites. It has been envisioned that lanthanum chromites with lower sintering temperatures can be co-fired with zirconia electrolyte. Nonstoichiometric lanthanum chromites can be sintered at lower temperatures, but they are unstable and react with zirconia electrolyte during co-sintering. NASA Glenn Research Center s Ceramics Branch investigated a glycine nitrate process to generate fine powder of the lanthanum-chromite-based materials. By simultaneously doping calcium on the lanthanum site, and cobalt and aluminum on the chromium site, we could sinter the materials below 1400 C. The doping concentrations were adjusted so that the thermal expansion coefficient matched that of the zirconia electrolyte. Also, the investigation was focused on stoichiometric compositions so that the materials would have better stability. Co-sintering and chemical compatibility with zirconia electrolyte were examined by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy (line scanning and dot map). The results showed that the materials bond well, but do not react, with zirconia electrolyte. The electric conductivity of the materials measured at 900 C in air was about 20 S/cm.

Zhong, Zhi-Min↗
NASA NTRS1974

Spinel-silicate co-crystallization relations in sample 15555

The results on the crystallization history of medium-grained mare basalt sample 15555,171, based on microprobe analyses (Dalton, 1973) of host and inclusion mineral pairs are summarized with emphasis placed on that part of the crystallization history during which chromite and ulvospinel were crystallizing. Compositional data on pyroxene olivine, chromite and ulvospinel in 15555,171 were collected using microprobe; data are based on corrected counts ratios for nine elements. It is concluded that systematic chemical relations between host and inclusion minerals suggest continuous in situ nucleation and growth of these minerals; that the data allow the possibility of some minerals, especially chromite, settling out of the melt during crystallization; and that the chromite to ulvospinel transition is correlated with a compositional change of the melt resulting from nucleation and growth of plagioclase.

Dalton, J.↗
NASA NTRS1980

XPS and STEM studies of Allende acid insoluble residues

Data on Allende acid residues obtained both before and after etching with hot HNO3 are presented. X-ray photoelectron spectra show predominantly carbonaceous material plus Fe-deficient chromite in both cases. The HNO3 oxidizes the carbonaceous material to some extent. The small chromites in these residues have a wide range of compositions somewhat paralleling those observed in larger Allende chromites and in Murchison chromites, especially in the high Al contents; however, they are deficient in divalent cations, which makes them metastable and indicates that they must have formed at relatively low temperatures. It is suggested that they formed by precipitation of Cr(3+) and Fe(3+) from olivine at low temperature or during rapid cooling.

Housley, R. M.↗
NASA NTRSDate not supplied

IIAB IRON METEORITES: FORMATION AND RELATION TO OTHER METEORITE GROUPS.

The IIAB iron meteorites are one of the largest iron meteorite groups that formed by fractional crystallization [1]. Iron meteorites formed over a range of oxygen fugacities (fO2)[2], most formed relatively reduced at~ IW–4to –2.5 (IABs), where IW= iron-wüstite buffer, to relatively oxidized at IW–1(IVBs) [2,3]. While the IIABs contain reduced mineral phases (daubré elite [1]),the fO2for IIABs is poorly constrained. The fO2of iron meteorites may have become more reducing during cooling, with oxidized phases (i.e., chromite) forming at higher temperatures and daubré elite forming at lower temperatures [4]. The O-and Cr-isotope compositions of silicates and chromite in meteorites, including iron meteorites, can determine potential genetic links to other meteorite sand con-strain if a meteorite is from the non-carbonaceous (NC) or carbonaceous (CC) group [e.g., 5–8]. Iron meteorite groups have been identified as being in the NCor CC group using Mo[9]and Ni [10] isotope compositions of their metallic component. Numerous iron meteorites contain minor amounts of silicates and oxides [e.g., 11], but most have not been analyzed for their Cr or Ti isotope compositions, with some exceptions (e.g., IIIABs [6,7],a IIG, and a IIAB[7]). We analyzed the compositions of silicates and chromite in six IIAB iron meteorites to investigate the relationship between IIABs and known meteorite groups, the fO2of IIABs, and the origin of chromite in the IIABs. *full abstract in document

Meteorite↗
NASA NTRS1973

Oxide minerals in lithic fragments from Luna 20 fines.

One hundred seventy-six oxide mineral grains in the Luna 20 samples were analyzed by electron microprobe. Spinel is the most abundant oxide, occurring in troctolite fragments. Next most abundant is ilmenite, which occurs in all rock types except those containing spinel. Chromite also occurs in all rock types except those containing spinel. Minor amounts of ulvospinel, armalcolite, zirkelite, baddeleyite and an unidentified TiO2-rich phase were also found. Spinel grains are predominantly spinel-hercynite solid solutions, commonly with very minor chromite. The Fe/(Fe + Mg) ratio is generally lower than in spinel from Apollo 14 rocks. Chromites in non-mare rocks are similar to those from mare rocks. Ilmenite of mare origin is Mg-poor and Zr-rich compared to non-mare ilmenite; these elements may therefore be useful in determining the origin of ilmenite grains. Phase equilibria considerations suggest that spinel troctolite crystallized from a melt high in alumina; a likely candidate is the high-alumina basalt of Prinz et al. (1973).

Brett, R.↗
NASA NTRS1973

Selected Apollo 17 soils - Mineralogy and geochemistry of opaque and non-opaque phases

Soil samples 74220 ('orange soil'), 74241 and 75081 were sized, and the compositions of the opaque and silicate phases were determined. The ilmenites, particularly in 74241, contain up to 7.8 wt % MgO and display higher bireflectance than low-Mg ilmenites. They commonly contain exsolution-like chromite and rutile and occasionally are in association with native Fe in an assemblage probably resulting from reduction. The chromian ulvospinels are similar to Apollo 11 spinels in that they contain near-equal amounts of chromite and ulvospinel molecules. No primary chromites were observed. Most native Fe has No and Co contents of less than 1 wt %; some in 74220 contained 5-6% Ni and less than 1% Co in association with schreibersite.

Taylor, L. A.↗