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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Carbon Nanotube Formation on Cr-Doped Ferrite Catalyst during Water Gas Shift Membrane Reaction: Mechanistic Implications and Extended Studies on Dry Gas Conversions

A nanocrystalline chromium-doped ferrite (FeCr) catalyst was shown to coproduce H2 and multiwalled carbon nanotubes (MWCNTs) during water gas shift (WGS) reaction in a H2-permselective zeolite membrane reactor (MR) at reaction pressures of ~20 bar. The FeCr catalyst was further demonstrated in the synthesis of highly crystalline and dimensionally uniform MWCNTs from a dry gas mixture of CO and CH4, which were the apparent sources for MWCNT growth in the WGS MR. In both the WGS MR and dry gas reactions, the operating temperature was 500 °C, which is significantly lower than those commonly used in MWCNT production by chemical vapor deposition (CVD) method from CO, CH4, or any other precursor gases. Extensive ex situ characterizations of the reaction products revealed that the FeCr catalyst remained in partially reduced states of Fe3+/Fe2+ and Cr6+/Cr3+ in WGS membrane reaction while further reduction of Fe2+ to Fe0 occurred in the CO/CH4 dry gas environments. The formation of the metallic Fe nanoparticles or catalyst surface dramatically improved the crystallinity and dimensional uniformity of the MWCNTs from dry gas reaction as compared to that from WGS reaction in the MR. Reaction of the CO/CH4 mixture containing 500 ppmv H2S also resulted in high-quality MWCNTs similar to those from the H2S-free feed gas, demonstrating excellent sulfur tolerance of the FeCr catalyst that is practically meaningful for utilization of biogas and cheap coal-derived syngas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

2022 Accomplishments Report Template

Chromium-doped UO 2 fuels is an industrially important Accident Tolerant Fuel (ATF) due to the ability to increase the average grain size relative to standard UO 2 . However, there is a lack of knowledge of the thermophysical properties of these doped fuels, which is necessary for accurately modeling the in-pile performance. The work accomplished this FY focused on developing large grain Cr-doped UO 2 pellets as a function of Cr content and subsequently measuring the thermophysical and mechanical properties. The microstructural variations were also investigated to evaluate chromium formation within the microstructure of the sintered pellets.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Designing Spin‐Crossover Systems to Enhance Thermopower and Thermoelectric Figure‐of‐Merit in Paramagnetic Materials

Thermoelectric materials, capable of converting temperature gradients into electrical power, have been traditionally limited by a trade‐off between thermopower and electrical conductivity. This study introduces a novel, broadly applicable approach that enhances both the spin‐driven thermopower and the thermoelectric figure‐of‐merit (zT) without compromising electrical conductivity, using temperature‐driven spin crossover. Our approach, supported by both theoretical and experimental evidence, is demonstrated through a case study of chromium doped‐manganese telluride, but is not confined to this material and can be extended to other magnetic materials. By introducing dopants to create a high crystal field and exploiting the entropy changes associated with temperature‐driven spin crossover, we achieved a significant increase in thermopower, by approximately 136 μV K −1 , representing more than a 200% enhancement at elevated temperatures within the paramagnetic domain. Our exploration of the bipolar semiconducting nature of these materials reveals that suppressing bipolar magnon/paramagnon‐drag thermopower is key to understanding and utilizing spin crossover‐driven thermopower. These findings, validated by inelastic neutron scattering, X‐ray photoemission spectroscopy, thermal transport, and energy conversion measurements, shed light on crucial material design parameters. We provide a comprehensive framework that analyzes the interplay between spin entropy, hopping transport, and magnon/paramagnon lifetimes, paving the way for the development of high‐performance spin‐driven thermoelectric materials.

magnons↗

Supercontinuum generation in oxide and semiconductor materials (InP, Si, GaN, GaAs, PbMoO 4 , YVO 4 , ZGP, TiO 2 , diamond) pumped by radiation of the Cr:ZnS fs-MOPA system

Ultrashort light sources in the middle-infrared range are highly beneficial for applications such as gas molecular spectroscopy, remote sensing, atmospheric science, medical treatments, and light–matter interaction studies. Ultrafast lasers utilizing chromium-doped ZnS/Se (Cr:ZnS/Se) have proven to be robust and stable solutions within this spectral region. Nonlinear spectral broadening is fundamentally important, as it pushes the pulse duration limits imposed by the bandwidth of laser media. In this study, we demonstrate the spectral broadening and supercontinuum generation in several bulk materials, including InP, Si, GaN, GaAs, PbMoO 4 , YVO 4 , diamond, and TiO 2 , using pump radiation with up to 4 W average power centered at 2.35 µm from a Cr:ZnS femtosecond MOPA system. Some of the investigated materials have excellent potential as effective media for middle-infrared supercontinuum generation, demonstrating the feasibility of developing a single-cycle pulse middle-infrared laser system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Single-pass Cr:ZnSe amplifier for broadband infrared undulator radiation

An amplifier based on a highly-doped chromium zinc-selenide (Cr:ZnSe) crystal is proposed to increase the pulse energy emitted by an electron bunch after it passes through an undulator magnet. The primary motivation is a possible use of the amplified undulator radiation emitted by a beam circulating in a particle accelerator storage ring to increase the particle beam’s phase-space density—a technique dubbed optical stochastic cooling (OSC). This paper uses a simple four energy level model to estimate the single-pass gain of Cr:ZnSe and presents numerical calculations combined with wave-optics simulations of undulator radiation to estimate the expected properties of the amplified undulator wave-packet.

43 PARTICLE ACCELERATORS↗

High Level Gap Analysis for Accident Tolerant and Advanced Fuels for Storage and Transportation

This initial gap analysis considers proposed accident tolerant fuel (ATF) options currently being irradiated in commercial reactors, since these are most likely for future batch implementation. Also, advanced fuel (AF) options that may be likely for use in advanced reactors are considered. The cladding technologies considered were chromium-coated zirconium-based alloys, FeCrAl, and both monolithic and matrix composite Silicide carbide (SiC). The fuel technologies considered were chromium-doped uranium dioxide fuel, uranium alloys, uranium nitride, and uranium silicide. Numerous national labs, industry, and countries are performing significant testing and modeling on these proposed technologies to establish performance, but at this time none of the prototypes being irradiated have achieved end-of-life (EOL) burnup. There are some testing results after one burnup cycle to verify in-reactor performance, but little data beyond that. As the ATF prototypes acquire more burnup, data will be produced that is relevant to storage and transportation. The DOE:NE Spent Fuel and Waste Science and Technology (SWFST) Storage and Transportation (ST) Control Account will evaluate the performance data as it becomes available for application to the identified gaps for ST.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The electrical properties of 60 keV zinc ions implanted into semi-insulating gallium arsenide

The electrical behavior of zinc ions implanted into chromium-doped semiinsulating gallium arsenide was investigated by measurements of the sheet resistivity and Hall effect. Room temperature implantations were performed using fluence values from 10 to the 12th to 10 to the 15th power/sq cm at 60 keV. The samples were annealed for 30 minutes in a nitrogen atmosphere up to 800 C in steps of 200 C and the effect of this annealing on the Hall effect and sheet resistivity was studied at room temperature using the Van der Pauw technique. The temperature dependence of sheet resistivity and mobility was measured from liquid nitrogen temperature to room temperature. Finally, a measurement of the implanted profile was obtained using a layer removal technique combined with the Hall effect and sheet resistivity measurements.

Littlejohn, M. A.↗

Laser action in chromium-activated forsterite for near infrared excitation

This paper reports on laser action in chromium-doped forsterite (Cr:Mg2SiO4) for 1064-nm excitation of the crystal's double-hump absorption band spanning the 850-1200-nm wavelength range. The cavity arrangement used for obtaining laser action in Cr:Mg2SiO2 was similar to that described by Petricevic et al. (1988). The fundamental and second harmonic emissions from a Q-switched Nd:YAG laser operating at a 10-Hz repetition rate were used for excitation of the NIR and visible bands, respectively. Pulsed laser action was readily observed for both the 1064-nm and 532-nm pumping at or above the respective thresholds. The laser parameters of the 532-nm and 1064-nm excitations were similar, indicating that the IR band is responsible for laser action for both excitations.

Petricevic, V.↗

Tetravalent chromium (Cr(4+)) as laser-active ion for tunable solid-state lasers

Generation of femtosecond pulses from a continuous-wave mode-locked chromium-doped forsterite (Cr(4+):Mg2SiO4) laser has been accomplished. The forsterite laser was actively mode-locked using an acousto-optic modulator operating at 78 MHz with two Brewster high-dispersion glass prisms for intra-cavity chirp compensation. Transform-limited sub-100-fs pulses were routinely generated in the TEM(sub 00) mode with 85 mW of continuous power (with 1 percent output coupler), tunable over 1230-1280 nm. The shortest pulses of 60-fs pulsewidth were measured.

Seas, A.↗

Tetravalent chromium (Cr(4+)) as laser-active ion for tunable solid-state lasers

Major accomplishments under NASA grant NAG-1-1346 are summarized. (1) numerical modeling of the four mirror astigmatically compensated, Z-fold cavity was performed and several design parameters to be used for the construction of a femtosecond forsterite laser were revealed by simulation. (2) femtosecond pulses from a continuous wave mode-locked chromium doped forsterite laser were generated. The forsterite laser was actively mode-locked using an acousto-optic modulator operating at 78 MHz with two Brewster high dispersion glass prisms for intra-cavity chirp compensation. Transform-limited sub-100-fs pulses were routinely generated in the TEM(sub 00) mode with 85 mW of continuous power tunable over 1230-1280 nm. The shortest pulses of 60-fs pulsewidth were measured. (3) Self-mode-locked operation of the Cr:forsterite laser was achieved. Synchronous pumping was used to mode lock the forsterite laser resulting in picosecond pulses, which in turn provided the starting mechanism for self-mode-locking. The pulses generated had an FWHM of 105 fs and were tunable between 1230-1270 nm. (4) Numerical calculations indicated that the pair of SF 14 prisms used in the cavity compensated for quadratic phase but introduced a large cubic phase term. Further calculations of other optical glasses indicated that a pair of SFN 64 prisms can introduce the same amount of quadratic phase as SF 14 prisms but introduce a smaller cubic phase. When the SF 14 prisms were replaced by SFN 64 prisms the pulsewidth was reduced to 50 fs. Great improvement was observed in the stability of the self mode-locked forsterite laser and in the ease of achieving mode locking. Using the same experimental arrangement and a new forsterite crystal with improved FOM the pulse width was reduced to 36 fs.

Seas, A.↗

Radiolytic Production of Radical Species in Gibbsite Doped with Iron and Chromium Ions

Gibbsite (aluminum hydroxide, Al(OH) 3 ) nanoparticles, synthesized from aluminum chloride or aluminum nitrate, were doped with metal ions, Cr(III) or Fe(III), and then irradiated with γ rays to determine the effect of the dopants on radiolytic hydrogen (H 2 ) production and radical generation. The addition of Cr(III) and Fe(III) ions at concentrations of 0.5% or 5% decreased the concentration of stable oxygen-centered radicals, with the strongest suppression in Cr(III) doped samples. A decrease in H 2 yields was observed with increasing Cr(III) or Fe(III) concentrations, with the greatest effect observed for the Fe(III)-doped samples. Reduction of the Cr(III) to Cr(II) and Fe(III) to Fe(II) was also observed, probably due to scavenging of radiolytically produced electrons. However, further processes differ for Fe(III)- and Cr(III)-doped systems. Both ions are reduced by the free electrons, leading to a decrease in H 2 production, but they react differently with the oxygen radicals. Cr(III) can be oxidized by oxygen radicals, whereas Fe(III) cannot. Fe(II) can interact with peroxides, possible products of intermediate oxygen oxidation, converting back to Fe(III) and leaving oxygen radicals behind. These oxidation reactions lead to a difference in the observed relative effects on H 2 yields and oxygen radical production between Cr(III)- and Fe(III)-doped gibbsite. In conclusion, the connection between electron scavenging and H 2 production indicates that radiolytically produced electrons are precursors to H 2 .

Anions↗

Investigating Effects of Operational Parameters on the Rate of Electrochemical Cleaning of Chromium Deposits on Strontium-Doped Lanthanum Manganite Cathodes in Solid Oxide Fuel Cells

Chromium poisoning of the cathode remains a significant obstacle to the stable long-term performance of solid oxide fuel cells. This study reports, a quick, in-situ mitigation method, called electrochemical cleaning. By applying a mild anodic bias, the electrochemical deposition reactions of chromium-containing species are reversed. Chromium vapor species are formed, freeing active electrochemical sites in the air electrode. An LSM/YSZ-based cell was exposed to Cr vapors at 800ºC and then subjected to electrochemical cleaning. Cell performance recovery was evidenced by current-voltage and EIS measurements. Chromium removal was verified using SEM and EDS analyses. The cyclability of the electrochemical cleaning was tested by repeated poisoning and cleaning of another cell. Investigation into the effect of cell operating parameters (current density and cell temperature) on the rate of cleaning is discussed.

30 DIRECT ENERGY CONVERSION↗

Thermal effects on cavity stability of chromium- and neodymium-doped gadolinium scandium gallium garnet laser under solar-simulator pumping

Results are presented on testing a Cr- and Nd-codoped Gd-Sc-Ga-garnet (Cr:Nd:GSGG) crystal and a Nd:YAG crystal (both of 3.2 mm diam and 76-mm long) for pulsed and CW laser operations using a flashlamp and solar simulator as pumping sources. Results from experiments with the flashlamp show that, at pulse lengths of 0.11, 0.28, and 0.90 ms, the slope efficiency of the Cd:Nd:GSGG crystal was higher than that of the Nd:YAG crystal and increased with pulse width. With the solar simulator, however, the CW laser operation of the Cr:Nd:GSGG crystal was limited to intensities not greater than 1500 solar constants, while the Nd:YAG laser successfully performed for all pump beam intensities available. It was found that the exposure for several minutes of the Cr:Nd:GSGG crystal to pump beam intensity of 3000 solar constants led to its damage by thermal cracking, indicating that a better solar-pumped CW laser performance may be difficult to realize with rod geometry.

Kim, Kyong H.↗

Lattice dynamics of 119 Sn impurity in a bcc-Cr crystal

The chromium crystal doped with 119 Sn isotope was studied using the nuclear resonance inelastic x-ray scattering and first principles calculations. The Sn partial phonon density of states (PDOS) was obtained for three temperatures that correspond to different magnetic states of Cr. At all temperatures, the energy spectrum consists of a broad band around 18 meV and a narrow peak at 43 meV. The additional peak around 39 meV is observed only in the magnetically ordered phases, indicating the influence of magnetic order in chromium on lattice dynamics. The partial PDOS calculated with the antiferromagnetic order on Cr atoms show a very good agreement with the experimental data. It is revealed that the high-energy peak is lying above the phonon spectra of the pure bcc-Cr crystal. These are the local modes with the increased energies due to a strongly reduced distance between Sn and the nearest-neighbor Cr atoms.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Diffusion in undoped and Cr-doped amorphous UO 2

UO 2 fuel pellets are often doped with chromium oxide to obtain favourable properties such as higher density, improved thermal stability, large grain sizes, improved pellet-clad interaction margins, and increased fission gas retention during transients. Chromium has a low solubility limit in UO 2 , with past experimental work reporting solubility limits ranging between 0.004 to 0.06 wt.% Cr. Due to its low solubility, segregation of Cr ions to the grain boundary may occur. Further, the complexity of these boundaries may be high as observed in other ceramics resulting in disordered or amorphous regions along the boundary, affecting a range of material and operational properties of the fuel pellet. To assess these disordered regions, in this work we study amorphous undoped and Cr doped UO 2 systems (containing 10–50 at.% Cr 3+ ) that have been modelled using classical molecular dynamics methods incorporating Cr 3+ into the well-used CRG potential library. Diffusion coefficients, pre-exponential factors, and activation energies for diffusion were computed for oxygen ions, assessing the impact of structure and extrinsic species on migration. Oxygen diffusion was observed to be much faster in the undoped amorphous system compared to its crystalline counterpart. Oxygen diffusion in doped systems decreased with increasing Cr concentration, highlighting the importance of additives to retain fission products and other migratory species.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Improved thermoelectric performance in Cr-doped two-dimensional Bi 2 Te 3

Thermoelectric materials with high electrical conductivity and low thermal conductivity (e.g., Bi 2 Te 3 ) can efficiently convert waste heat into electricity. However, despite favorable theoretical predictions, individual Bi 2 Te 3 nanostructures such as two-dimensional (2D) nanoplates tend to underperform bulk Bi 2 Te 3 . We report a novel surface doping technique to synthesize highly n-type Bi 2 Te 3 nanoplates using an external Cr coating followed by a thermal annealing process in a reducing atmosphere, as well as the mechanism by which this surface coating – only a few atoms or less in thickness – can observably impact the thermoelectric performance of 2D Bi 2 Te 3 . The Cr atoms act as n-type carrier donors by directly incorporating into the Bi 2 Te 3 structure during thermal annealing, enhancing electrical conductivity by ∼ 70 % while increasing thermal conductivity by only ∼ 5 % at room temperature. Compared to the uncoated Bi 2 Te 3 nanoplate, the Cr-doped Bi 2 Te 3 nanoplate exhibits a doubled thermoelectric figure of merit (zT), which is still relatively low. Raman spectroscopy and chemical potential simulations further confirm that Cr atoms are incorporated into the Bi 2 Te 3 structure.

36 MATERIALS SCIENCE↗

The First National Student Conference: NASA University Research Centers at Minority Institutions

The conference includes contributions from 13 minority universities with NASA University Research Centers. Topics discussed include: leadership, survival strategies, life support systems, food systems, simulated hypergravity, chromium diffusion doping, radiation effects on dc-dc converters, metal oxide glasses, crystal growth of Bil3, science and communication on wheels, semiconductor thin films, numerical solution of random algebraic equations, fuzzy logic control, spatial resolution of satellite images, programming language development, nitric oxide in the thermosphere and mesosphere, high performance polyimides, crossover control in genetic algorithms, hyperthermal ion scattering, etc.

Daso, Endwell O.↗