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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Highly efficient removal and sequestration of Cr(VI) in confined MoS 2 interlayer Nanochannels: Performance and mechanism

Environmental contamination by Cr(VI) is of particular concern because of its severe toxicity and high mobility. In this study, we employed two-dimensional MoS 2 nanosheets in the removal of Cr(VI), with an emphasis on revealing the removal mechanisms, and how the compositional and structural uniqueness of 2D MoS 2 nanomaterials intrinsically impact the Cr removal efficiency. Through batch experiments with dispersed nanosheets, we found that MoS 2 nanosheets exhibited a high Cr(VI) removal capacity at ~1100 mg/g via a phase-dependent mechanism. Particularly, the 1T polymorph in the MoS 2 nanosheets removed Cr(VI) through a redox-reaction mechanism, which was different from the adsorptive removal of Cr(VI) by MoS 2 reported previously, highlighting the compositional effects on the removal mechanism and performance. More importantly, the reduced product Cr(III) was concurrently removed via precipitation and adsorption onto the MoS 2 nanosheets, which could avoid the additional pH-elevation step that is typically needed in the conventional treatment. The unique 2D flake-like structure of MoS 2 nanosheets enabled the formation of aligned and ion-accessible nanochannels, where Cr(VI) species were accommodated, reduced and sequestered. The irreversible shrinking of the nanochannels under drying modified the interior of the layer-stacked structure into confined compartments preventing the release and re-oxidation of the immobilized Cr(III). In conclusion, the compiled results highlight the effects of MoS 2 composition and structure on the Cr removal efficiency and mechanism, which has substantial implications on future studies tailoring these unique features of 2D nanomaterials for various remediation scenarios.

42 ENGINEERING↗
DOE OSTI2023

Cr silicate as a prototype for engineering magnetic phases in air-stable two-dimensional transition-metal silicates

Abstract Identifying environmentally inert, ferromagnetic two-dimensional (2D) materials with high Curie temperatures ( T c ) down to the single layer limit has been an obstacle to fundamental studies of 2D magnetism and application of 2D heterostructures to spin-polarized devices. To address this challenge, the growth, structure and magnetic properties of a 2D Cr-silicate single layer on Pt(111) was investigated experimentally and theoretically. The layer was grown by sequentially depositing SiO and Cr followed by annealing in O 2 . Scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and low energy electron microscopy all indicated a well-ordered layer that uniformly covered the surface, with STM and LEED indicating that the silicate relaxed to its favored lattice constant. Further experimental characterizations demonstrated that the Cr was nominally 3+ but with a lower electron density than typical trivalent Cr compounds. Comparison with theory identified a Cr 2 Si 2 O 9 structure that resembles a single layer of a dehydrogenated dioctahedral silicate. Magnetic circular dichroism in x-ray absorption spectroscopy revealed a ferromagnetically ordered state up to at least 80 K. Theoretical analysis revealed that the Cr in a dehydrogenated Cr-silicate/Pt(111) is more oxidized than Cr in freestanding Cr 2 Si 2 O 9 H 4 layers. This greater oxidation was found to enhance ferromagnetic coupling and suggests that the magnetism may be tuned by doping. The 2D Cr-silicate is the first member of a broad series of possible layered first-row transition metal silicates with magnetic order; thus, this paper introduces a new platform for investigating 2D ferromagnetism and the development of magnetoelectronic and spintronic devices by stacking 2D atomic layers.

2D materials↗
DOE OSTI2025

Magnetic semiconductors from functionalized Cr 2 ⁢C MXenes

Here, we report an ab initio investigation of functionalized and 3⁢𝑑-electron-doped Cr 2 ⁢C MXenes. Upon functionalization, the Cr 2⁢ C becomes chemically, dynamically, and mechanically stable, and it exhibits magnetic semiconducting behavior. Cr 2 ⁢CF 2 stands out as a wide band gap semiconductor, possessing superexchange interaction mediated by F atoms within the layer; however, the applied strain transforms it from an indirect to a direct band gap semiconductor. Strong spin-phonon coupling found in Cr 2 ⁢CH 2 is supported by the distorted Cr spin density due to the hydrogen environment. Two magnon branches, associated with two sublattice spins, are found in the ferromagnetic Cr 2 ⁢CO 2 and antiferromagnetic Cr 2 ⁢CF 2 . Depending on the types of 3⁢𝑑-electron dopants and functionalization, Cr 2 ⁢C MXenes (except for Cr 2 ⁢CO 2 ) change from an indirect band gap magnetic semiconductor to different states of electronic and magnetic matter, including an exotic direct band gap magnetic bipolar semiconductor. In addition, we reveal a band inversion between the two highest valence bands in the Fe-doped Cr 2 ⁢CCl 2 .

2D materials↗
DOE OSTI2023

High-temperature ferromagnetism in Cr 1+x Pt 5-x P

In this work, we present the growth and basic magnetic and transport properties of Cr 1+x Pt 5-x P. We show that single crystals can readily be grown from a high-temperature solution created by adding dilute quantities of Cr to Pt-P based melts. Like other 1-5-1 compounds, Cr 1+x Pt 5-x P adopts a tetragonal P4/mmm, structure composed facesharing CrPts like slabs that are broken up along the c-axis by sheets of P atoms. EDS and X-ray diffraction measurements both suggest Cr 1+x Pt 5-x P has mixed occupancy between Cr and Pt atoms, similar to what is found in the closely related compound CrPtg, giving real compositions of Cr 1.5 Pt 4.5 P (x = 0.5). We report that Cr 1.5 Pt 4.5 P orders ferromagnetically at T c = 464.5 K with a saturated moment of ≈ 2.1 μs/Cr at 1.8 K. Likely owing to the strong spin-orbit coupling associated with the large quantity of high Z, Pt atoms, Cr 1.5 Pt 4.5 P has exceptionally strong planar anisotropy with estimated anisotropy fields of 345 kOe and 220 kOe at 1.8 K and 300 K respectively. The resistance of Cr 1.5 Pt 4.5 P has a metallic temperature dependence with relatively weak magnetoresistance. Electronic band structure calculations show that CrPt 5 P has a large peak in the density of states near the Fermi level which is split into spin majority and minority bands in the ferromagnetic state. Furthermore, the calculations suggest substantial hybridization between Cr-3d and Pt-5d states near the Fermi level, in agreement with the experimentally measured anisotropy.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Optical, electrical, and EPR studies of polycrystalline Al:Cr:ZnSe gain elements

Transition metal-doped II-VI (TM:II-VI) chalcogenides are well-known laser materials for optically pumped middle-infrared lasers. Cr:ZnSe is a key representative of this class of transition metal doped II-VI gain media and is arguably considered the material of choice for optically pumped middle-infrared lasers. In addition to effective mid-IR lasing under optical excitation, these crystals, being wide-band semiconductors, hold the potential for direct electrical excitation. One way to form n-type conductivity in ZnSe crystals is by annealing them in a melt of Zn-Al alloy. However, this annealing of Cr:ZnSe crystals results in their purification and transfer of chromium to the melt of Zn-Al alloy. In this article, we report on optimizing the doping technique for providing n-type conductivity in Al:Cr:ZnSe crystals while preserving the chromium concentration. Al:Cr:ZnSe samples with resistivities ranging from 10.8 to 992 Ω-cm were fabricated. While the 2 + valence state of Cr is typically dominant in Cr:ZnSe, both Cr 2+ and Cr + were detected in Al:Cr:ZnSe samples. The maximum level of Cr + concentration was measured to be 4 × 10 18 cm -3 .

36 MATERIALS SCIENCE↗
NASA NTRS1985

Chemical and electrochemical behavior of the Cr(III)/Cr(II) half-cell in the iron-chromium redox energy storage system

The Cr(III) complexes present in the acidified chromium solutions used in the iron-chromium redox energy storage system have been isolated and identified as Cr(H2O)6(3+) and Cr(H2O)5Cl(2+) by ion-exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles have been followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations of the Cr(III) species calculated using Beer's law. During the charge mode, Cr(H2O)5Cl(2+) is reduced to Cr(H2O)5Cl(+), and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(2+). Electrode potential measurements also support this interpretation. Hysteresis effects in the charge-discharge curves can be explained by the slow attainment of equilibrium between Cr(H2O)6(3+) and Cr(H2O)5Cl(2+).

Johnson, D. A.↗
DOE OSTI2020

Materials Data on Cr(ClO2)3 by Materials Project

Cr(O2Cl)2ClO2 crystallizes in the monoclinic C2/c space group. The structure is two-dimensional and consists of four hypochlorous acid;hydrate molecules and two Cr(O2Cl)2 sheets oriented in the (1, 0, 0) direction. In each Cr(O2Cl)2 sheet, Cr is bonded in a distorted octahedral geometry to four O and two equivalent Cl atoms. There is two shorter (1.69 Å) and two longer (2.04 Å) Cr–O bond length. Both Cr–Cl bond lengths are 2.46 Å. There are two inequivalent O sites. In the first O site, O is bonded in a single-bond geometry to one Cr atom. In the second O site, O is bonded in a bent 120 degrees geometry to one Cr and one Cl atom. The O–Cl bond length is 1.66 Å. Cl is bonded in a bent 120 degrees geometry to one Cr and one O atom.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The Co-Transport of PFAS and Cr(VI) in porous media

PFAS and Cr are present at some sites as co-contaminants. Here, the objective of this research was to investigate the co-transport behavior of per- and polyfluoroalkyl substances (PFAS) and hexavalent chromium (Cr(VI)) in porous media. Miscible-displacement experiments were conducted using two soils and an aquifer sediment with different geochemical properties. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were employed as model PFAS. The retardation of PFOS was decreased in the presence of Cr(VI). Conversely, the transport and retardation of PFOA was not affected by the presence of Cr(VI). The reduction of PFOS retardation caused by Cr(VI) is likely due to sorption competition for both organic-carbon and inorganic (metal-oxides and clay minerals) domains. The relative contributions of the three soil constituents to PFOS sorption and the potential for competition between PFOS and Cr(VI) is a function of the geochemical composition of the porous media (i.e., organic carbon, metal-oxides and clay minerals). The PFAS had minimal impact on the retention and transport of Cr(VI). To our knowledge, the results presented herein represent the first reported data for PFOS and Cr(VI) co-transport in porous media. The results of this study indicate that the presence of Cr(VI) has the potential to increase the migration potential of PFOS in soil and groundwater, which should be considered when characterizing electroplating facilities, leather tanning facilities, and other co-contaminated sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Oxidation behavior of Fe-Cr-2Si alloys in high temperature steam

FeCrSi alloys have been proposed as alternatives to FeCrAl alloys for accident-tolerant fuel cladding in light water reactors. Experiments on the oxidation resistance of three Fe-Cr-2Si alloys in high-temperature steam, with 12, 16, and 20 wt. % Cr, show that ≥16 % Cr is sufficient to form a thin, passivating, binary oxide layer. Additionally, at 1200 °C, only Cr 2 O 3 and SiO 2 form on Fe 16 Cr 2 Si and Fe 20 Cr 2 Si, while additional ternary Fe oxides form on Fe 12 Cr 2 Si. Decohesion and spalling of oxide were observed on Fe-Cr-Si alloys exposed to steam at 900 °C and above. Fe 20 Cr 2 Si exhibits the best oxidation resistance of the three in high-temperature steam.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High-temperature lean Cu alloys with Cr-to-Nb atomic ratio of 2

Two Cu-Cr-Nb alloys, denoted as alloy 1 (comprising Cu-0.89 at% Cr-0.42 at% Nb) and alloy 2 (comprising Cu-1.84 at% Cr-0.99 at% Nb), were produced through a series of manufacturing processes including vacuum induction melting, melt spinning, consolidation, brazing, and baking, with both alloys aimed at achieving a nominal Cr-to-Nb atomic ratio of 2. Microstructural characterization using transmission electron microscopy and X-ray diffraction identified the cubic C15 Laves-phase Cr 2 Nb as the dominant precipitate in both alloys, cross-validated by thermodynamic calculations and atomistic simulation-based density functional theory (DFT). Besides cubic C15 Cr 2 Nb, hexagonal C14-phase Cr 2 Nb and α-BiF3 cubic structured Cr 3 Nb were also observed in the alloys, including a coherent interface formed between the Cr 3 Nb precipitate and the Cu matrix. The hardness of the alloys increases, and the electrical conductivity decreases with increasing alloying addition content; two practical equations described the trends. Further DFT simulations revealed that the electrical conductivity (conductance) of the Cu/Cr 2 Nb interface is an order of magnitude higher than the intrinsic Cu high-angle grain boundaries.

36 MATERIALS SCIENCE↗
DOE OSTI2023

(Fe, Cr)(OH) 3 Coprecipitation in Solution and on Soil: Roles of Surface Functional Groups and Solution pH

The simultaneous precipitation of (Fe, Cr)(OH) 3 nanoparticles in solution (homogeneous) and on soil surfaces (heterogeneous), which controls Cr transport in soil and aquatic systems, was quantified for the first time in the presence of model surfaces, i.e., bare and natural organic matter (NOM)-coated SiO 2 and Al 2 O 3 . Various characterization techniques were combined to explore the surface-ion-precipitate interactions and the controlling mechanisms. (Fe, Cr)(OH) 3 accumulation on negatively charged SiO 2 was mainly governed by electrostatic interactions between hydrolyzed ion species or homogeneous (Fe, Cr)(OH) 3 and surfaces. The elevated pH through protonation of Al 2 O 3 surface hydroxyls resulted in higher Cr/Fe ratios in both homogeneous and heterogeneous coprecipitates. Here, due to ignorable NOM adsorption onto SiO 2 , the amounts of (Fe, Cr)(OH) 3 precipitates on bare/NOM-SiO 2 were similar; contrarily, attributed to favored NOM adsorption onto Al 2 O 3 and consequently carboxyl association with metal ions or (Fe, Cr)(OH) 3 nanoparticles, remarkably more heterogeneous precipitates harvested on NOM-Al 2 O 3 than bare-Al 2 O 3 . With the same solution supersaturation, the total amounts of homogeneous and heterogeneous precipitates were similar irrespective of the substrate type. With lower pH, decreased electrostatic forces between substrates and precipitates shifted (Fe, Cr)(OH) 3 distribution from heterogeneous to homogeneous phases. The quantitative knowledge of (Fe, Cr)(OH) 3 distribution and the controlling mechanisms can assist in better Cr sequestration in natural and engineered settings.

(Fe, Cr)(OH)3 distribution↗
DOE OSTI2021

Direct and Indirect Reduction of Cr(VI) by Fermentative Fe(III)-Reducing Cellulomonas sp. Strain Cellu-2a

Hexavalent chromium (Cr(VI)) is recognized to be carcinogenic and toxic and registered as a contaminant in many drinking water regulations. It occurs naturally and is also produced by industrial processes. The reduction of Cr(VI) to Cr(III) has been a central topic for chromium remediation since Cr(III) is less toxic and less mobile. In this study, fermentative Fe(III)-reducing bacterial strains (Cellu-2a, Cellu-5a, and Cellu-5b) were isolated from a groundwater sample and were phylogenetically related to species of Cellulomonas by 16S rRNA gene analysis. One selected strain, Cellu-2a showed its capacity of reduction of both soluble iron (ferric citrate) and solid iron (hydrous ferric oxide, HFO), as well as aqueous Cr(VI). The strain Cellu-2a was able to reduce 15 μM Cr(VI) directly with glucose or sucrose as a sole carbon source under the anaerobic condition and indirectly with one of the substrates and HFO in the same incubations. The heterogeneous reduction of Cr(VI) by the surface-associated reduced iron from HFO by Cellu-2a likely assisted the Cr(VI) reduction. Fermentative features such as large-scale cell growth may impose advantages on the application of bacterial Cr(VI) reduction over anaerobic respiratory reduction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Natural and enriched Cr target development for production of Manganese-52

52 Mn is a promising PET radiometal with a half-life of 5.6 days and an average positron energy of 242 keV. Typically, chromium of natural isotope abundance is used as a target material to produce this isotope through the nat/52 Cr(p,n) 52 Mn reaction. While natural Cr is a suitable target material, higher purity 52 Mn could be produced by transitioning to enriched 52 Cr targets to prevent the co-production of long-lived 54 Mn (t 1/2 = 312 day). Unfortunately, 52 Cr targets are not cost-effective without recycling processes in place, therefore, this work aims to explore routes to prepare Cr targets that could be recycled. Natural Cr foils, metal powder pellets, enriched chromium-52 oxide and Cr(III) electroplated targets were investigated in this work. Each of these cyclotron targets were irradiated, and the produced 52 Mn was purified, when possible, using a semi-automated system. An improved purification by solid-phase anion exchange from ethanol-HCl mixtures resulted in recoveries of 94.5 ± 2.2% of 52 Mn. The most promising target configuration to produce a recyclable target was electroplated Cr(III). This work presents several pathways to optimize enriched Cr targets for the production of high purity 52 Mn.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2024

Exploring the impact of Cr-doping on the crystallographic and magnetic structure of Mn 5 Si 3 antiferromagnetic alloy

Here, the role of Cr-doping on the structural and magnetic ground states of Mn 5 Si 3 alloy has been investigated through temperature-dependent neutron powder diffraction (NPD) and X-ray absorption fine structure (XAFS) techniques. All the Cr-doped alloys of nominal composition Mn 5-x Cr x Si 3 (for x = 0.05, 0.1, and 0.2) undergo two first-order magneto-structural phase transitions from hexagonal (space group: P6 3 /mcm) paramagnetic → orthorhombic (space group: Ccmm) collinear antiferromagnetic → orthorhombic (space group: Cc2m) non-collinear antiferromagnetic phase on cooling from room temperature. NPD studies at different constant temperatures indicate that both anti ferromagnetic phases are commensurate in nature and can be represented by q = (0,1,0) magnetic propagation vector for all the Cr-doped alloys. Such doping at the Mn-site results in a significant modification of the non-collinear antiferromagnetic structure (both moment size and orientation) and hence affects the unusual magnetic properties, like inverted hysteresis loop, thermomagnetic irreversibility, etc. The XAFS measurements were performed to interpret the local environment of doped Cr atoms in detail, which is critical for a microscopic understanding of the unusual properties of this class of Cr-doped Mn 5 Si 3 alloys. The analysis confirms the elemental state of Cr in the doped alloys and indicates a high degree of preservation of local crystallographic structure with varying Cr concentration and sample temperature. Doping induces intriguing changes in XAFS patterns, elucidated through different types of scattering mechanisms associated with the central absorbing Cr atom.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1975

Directionally solidified pseudo-binary eutectics of Ni-Cr-(Hf, Zr)

A pseudo-binary eutectic, in which the intermetallic Ni7Hf2 reinforces the Ni-Cr solid solution phase, was previously predicted in the Ni-Cr-Hf system by a computer analysis. The experimental determination of pseudo binary eutectic compositions and the directional solidification of the Ni-Cr-Hf, Zr, and Ni-Cr-Zr eutectic alloys are discussed. To determine unknown eutectics, chemical analyses were made of material bled from near eutectic ingots during incipient melting. Nominal compositions in weight percent of Ni-18.6Cr-24.0HF, Ni19.6Cr-12.8Zr-2.8Hf, and Ni-19.2Cr-14.8Zr formed aligned pseudo-binary eutectic structures. The melting points were about 1270 C. The reinforcing intermetallic phases were identified as noncubic (Ni,Cr)7Hf2 and (Ni,Cr)7(Hf,Zr)2, and face centered cubic (Ni,Cr)5Zr. The volume fraction of the reinforcing phases were about 0.5.

Kim, Y. G.↗
NASA NTRS1982

Chemical and electrochemical behavior of the Cr(3)/Cr(2) half cell in the NASA Redox Energy Storage System

The Cr(III) complexes in the NASA Redox Energy Storage System were isolated and identified as Cr(H2O)6(+3) and Cr(H2O)5Cl(+2) by ion exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles were followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations calculated using Beer's Law. During the charge mode Cr(H2O)5Cl(+2) is reduced to Cr(H2O)5Cl(+) and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(+2). Both electrode reactions occur via a chloride-bridge inner-sphere reaction pathway. Hysteresis effects can be explained by the slow attainment of equilibrium between Cr(H2O)6(+3) and Cr(H2O)5Cl(+2).

Johnson, D. A.↗
NASA NTRS1993

The origin of chromitic chondrules and the volatility of Cr under a range of nebular conditions

We characterize ten chromatic chondrules, two spinelian chondrules andd one spinel-bearing chondrule and summarize data for 120 chromitic inclusions discovered in an extensive survey of ordinary chondrites. Compositional and petrographic evidence suggests that chromitic chondrules and inclusions are closely related. The Cr/(Cr + Al) ratios in the spinal of these objects range from 0.5 to 0.9 and bulk Al2O3 contents are uniformly high (greater than 10 wt%, except for one with 8 wt%). No other elements having comparable solar abundances are so stongly enriched, and alkali feldspar and merrillite are more common than in normal chondrules. The Cr/Mg ratios in chromitic chondrules are 180-750 times the ratios in the bulk chondrite. With the possible exception of magnetic clumping of chromite in the presolar cloud, mechanical processes cannot account for this enrichment. Examination of nebular equilibrium processes shows that 50%-condensation temperatures of Cr at pH2/pH2O of 1500 are several tens of degrees below those of Mg as Mg2SiO4; the condensation of Cr is primarily as MgCr2O4 dissolved in MgAl2O4 at nebular pressures of 10(exp -4) atm or below. At pH2 = 10(exp -3) atm condesation as Cr in Fe-Ni is favored. Making the nebula much more oxidizing reduces the difference in condensation temperatures but Mg remains more refractory. We conclude that nebular equilibrium processes are not responsible for the enhanced Cr/Mg ratios. We propose that both Cr and Al became enriched in residues formed by incomplete evaporation of presolar lumps. We suggest that spinals remained as solid phases when the bulk of the silicates were incorporated into the evaporating melt; vaporization of Al and Cr were inhibited by the slow kinetics of diffusion. Subsequent melting and crystallization of these residues fractionated Cr from Al. The resulting materials constituted major components in the precursors of chromitic chondrules. Our model implies that chromitic chondrules and inclusions preserve the Cr isotopic record of presolar sources.

Krot, Alexander↗
DOE OSTI2020

Materials Data on Cr(ClO2)3 by Materials Project

Cr(O2Cl)3 crystallizes in the monoclinic C2/c space group. The structure is one-dimensional and consists of two Cr(O2Cl)3 ribbons oriented in the (1, 0, 1) direction. Cr is bonded in a distorted octahedral geometry to four O and two equivalent Cl atoms. There is two shorter (1.71 Å) and two longer (1.95 Å) Cr–O bond length. Both Cr–Cl bond lengths are 2.48 Å. There are three inequivalent O sites. In the first O site, O is bonded in a single-bond geometry to one Cr atom. In the second O site, O is bonded in a distorted bent 120 degrees geometry to one Cr and one Cl atom. The O–Cl bond length is 1.72 Å. In the third O site, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.55 Å. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a linear geometry to two equivalent O atoms. In the second Cl site, Cl is bonded in a water-like geometry to one Cr and one O atom.

36 MATERIALS SCIENCE↗