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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 433 records · Page 24

Magnetic Properties and Photocatalytic Behavior of Co Co-doped BiFeO{sub 3}:Er

The multiferroic materials Bi{sub 0.95}Er{sub 0.05}Fe{sub 1−x}Co{sub x} O{sub 3} (x = 0, 0.01, 0.03, and 0.05) are synthesized by solvothermal method. X-ray diffraction pattern is used to confirm the formation of rhombohedral crystal structure. TEM images show agglomerated nanosize particles. With the concentration of Co, a red shift is observed in the charge transfer transition of O{sub 2p}-Fe{sub 3d} band and band gap decreases. At higher concentration of Co, the saturation magnetization enhances and coercivity also varies with the concentration of Co. The photocatalytic degradation of methylene blue is evaluated under the visible light with the assistance of H{sub 2}O{sub 2}. With the increase in Co concentration, the photocatalytic activity decreases. The main species responsible for the degradation is found out using scavengers like ammonium oxalate, silver nitrate, p-benzoquinone, and tert-butyl-alcohol. The possible mechanism for the degradation of dye is explained.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synchrotron micro-scale study of trace metal transport and distribution in Spartina alterniflora root system in Yangtze River intertidal zone

This study is focused on micro-scale measurement of metal (Ca, Cl, Fe, K, Mn, Cu, Pb, and Zn) distributions in Spartina alterniflora root system. The root samples were collected in the Yangtze River intertidal zone in July 2013. Synchrotron X-ray fluorescence (XRF), computed microtomography (CMT), and X-ray absorption near-edge structure (XANES) techniques, which provide micro-meter scale analytical resolution, were applied to this study. Although it was found that the metals of interest were distributed in both epidermis and vascular tissue with the varying concentrations, the results showed that Fe plaque was mainly distributed in the root epidermis. Other metals (e.g., Cu, Mn, Pb, and Zn) were correlated with Fe in the epidermis possibly due to scavenge by Fe plaque. Relatively high metal concentrations were observed in the root hair tip. As a result, this micro-scale investigation provides insights of understanding the metal uptake and spatial distribution as well as the function of Fe plaque governing metal transport in the root system.

36 MATERIALS SCIENCE↗

Evaluation of the Structure and Biological Activities of Condensed Tannins from Acanthus ilicifolius Linn and Their Effect on Fresh-Cut Fuji Apples

Condensed tannins (CT{sub S}) have been isolated and purified from leaves of Acanthus ilicifolius Linn. And their structures were investigated by three methods: {sup 13}C nuclear magnetic resonance ({sup 13}C NMR), reversed-phase high-performance liquid chromatography (RP-HPLC), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The results showed that the CT{sub S} were a mixture of catechin/epicatechin, galatechin/epicatechin, and amphicin/epigalin, and that the polymer chain lengths were 3-mers to 14-mers. Antityrosinase activities and antioxidant activities of the CT{sub S} from A. ilicifolius leaves were further studied. The IC{sub 50} of the CT{sub S} on mushroom tyrosinase activity was determined to be 19.7 ± 0.13 μg/mL, and inhibition type analyses indicated that the CT{sub S} were mixed type inhibitors and their inhibition CT{sub S} was reversible. The CT{sub S} from A. ilicifolius leaves also exhibited potential antioxidant activity. The IC{sub 50} of DPPH and ABTS scavenging activities were 104 ± 0.894 μg/mL and 86 ± 0.616 μg/mL, respectively. And the FRAP value was 758.28 ± 2.42 mg AAE/g. In addition, we found that the CT{sub S} from A. ilicifolius leaves had an excellent effect on preserving the quality of fresh-cut apples by preventing apples from browning through reducing polyphenol oxidase activities in apples.

60 APPLIED LIFE SCIENCES↗

ToF-SIMS Depth Profiling of Organic Delta Layers with Low-Energy Cesium Ions: Depth Resolution Assessment

The advent of cluster ion beams has paved the way to the routine 3D analysis of organic heterojunctions. Alternatively, organic thin layers have also been successfully depth profiled with a low-energy cesium ion beam (Cs{sup +}), to exploit the high chemical reactivity of cesium atoms, acting as free-radical scavengers. Despite of this, little is known about the depth resolution associated with low-energy Cs{sup +} sputtering on organic multilayers. In this work, amino acids multilayers, consisting of phenylalanine delta layers alternated with tyrosine spacers, were used as model systems to assess the depth resolution associated with 500 eV Cs{sup +} depth profiles. High yields were obtained for quasi-molecular ions from both amino acids, and no significant chemical alteration was noticed under the monoatomic bombardment. A depth resolution as low as 4 nm is demonstrated without sensible degradation on a rather long profile depth (300 nm). Limited depth resolution (> 10 nm) along with high molecular degradation was previously reported on similar systems by combining low-energy Cs{sup +} with Ga{sup +} analysis beam. The use of the Bi{sub 3}{sup +} analysis beam results in a dramatic improvement of both the characteristic molecular signal intensities and the depth resolution. Even though the analysis beam fluence is very low compared to the sputtering beam fluence, data suggest that further reducing the analysis Bi{sub 3}{sup +} fluence could improve the depth resolution by ~ 1 nm. .

74 ATOMIC AND MOLECULAR PHYSICS↗

Additively-manufactured Al-0.3Zr-0.2Ce-0.2Cu alloy with high creep resistance and electrical conductivity

Here, a new, solute-lean Al-0.3Zr-0.2Ce-0.2Cu (wt.%) alloy is developed for additive manufacturing that overcomes the classical tradeoff between conductivity and creep resistance. The rapid-cooling-enabled supersaturation of Zr, and its uniform distribution in α-Al matrix, along with formation of submicron (Ce,Cu)-rich intermetallic particles on solidification lead to unusually high creep resistance at 200 °C. Near-zero secondary creep rates are achieved up to the alloy yield stress (YS) of 65 MPa at 200 °C in as-fabricated state. The Zr-solute-induced dislocation-climb suppression mechanism underlying this improvement also restricts dynamic recovery above YS, as noted from appreciable primary creep and its transitioning to near-zero secondary creep rates. A combination of relatively coarse, epitaxially-grown α-Al grains, low Zr concentration in α-Al, and the impurity-scavenging effect of Ce to purify α-Al matrix produces high electrical conductivity of ∼48 %IACS. Aging precipitation of L1 2 -Al 3 Zr nanoprecipitates doubles the YS (to ∼150 MPa) at room temperature and increases alloy conductivity to ∼58 %IACS, but loss of solid-solution Zr out of α-Al matrix leads to activation of dislocation climb, degrading the creep properties as compared to the supersaturated Al-Zr solid solution in the as-fabricated state. Compared to L1 2 -Al 3 Zr nanoprecipitates, submicron (Ce,Cu)-rich particles formed on solidification are more effective at impeding dislocation climb, producing a threshold stress for dislocation creep of ∼ 50 MPa at 200 °C. The new alloy design concepts, especially solute-induced dislocation-climb suppression for creep resistance, explored here may pave way for the design of new metallic alloys for thermal/electrical conductors and other high-temperature applications.

Additive Manufacturing↗

High temperature stabilization of ultrafine grain tungsten alloys through synergistic compositional complexities

Thermally-stabilized fine-grained microstructures in tungsten provide a pathway to harnessing enhanced properties such as a reduced ductile-to-brittle transition temperature and improved strength while mitigating the adverse effects of grain growth and recrystallization. Here, in this study, we employ a material design strategy that relies on grain boundary segregation in the nanocrystalline state driven by alloy thermodynamics balanced with impurity scavenging through in situ formation of kinetically-stabilizing metal carbides. A W-Ti-Cr alloy is designed through lattice Monte Carlo methods and subsequently synthesized in a single-phase nanocrystalline state, which upon annealing, evolves into an ultrafine grained microstructure containing chromium grain boundary segregation collectively with a dispersed TiX (X=C,O) phase through the reaction of titanium with carbon and oxygen impurities. In situ synchrotron X-ray diffraction experiments demonstrate that increased Ti promotes stabilization across a larger temperature range but with diminishing returns above 10 at.% Ti. Long-term stability was confirmed through the retention of the ultrafine grained microstructure for a total of 8 days (192 h) at 1300 °C without grain/carbide growth and/or recrystallization. Our results demonstrate that, through strategic tailoring of composition and microstructure, one can harness the benefits of both thermodynamic and kinetic stabilization mechanisms, opening pathways for future alloy formulations that expand the window of stability.

36 MATERIALS SCIENCE↗

Oxygen stress mitigation for microalgal biomass productivity improvement in outdoor raceway ponds

Dissolved oxygen (DO) concentrations at supersaturated levels are commonly observed in outdoor microalgae cultures due to photosynthesis during periods of rapid growth. Paradoxically, the photosynthetically generated oxygen is inhibitory and lowers biomass productivity, therefore, increasing the cost of microalgal biofuels. In this study, photosynthetic rates of Monoraphidium minutum 26B-AM and Scenedesmus obliquus UTEX393, two of the top DISCOVR strains, were compared at three DO levels, 0, 8, and 30 mg L -1 . Increasing DO from 0 to 30 mg L -1 caused a 36.6% and 26.1% reduction in photosynthetic rate for M. minutum 26B-AM and S. obliquus UTEX393, respectively. To improve the outdoor pond biomass productivity of each strain, three oxygen stress mitigation methods were tested. The first method raised the dissolved bicarbonate concentration by an order of magnitude to favor bicarbonate transport into the cell, increasing the CO 2 :O 2 ratio near RuBisCO, thus reducing photorespiration. Although this method increased the observed photosynthesis rate of M. minutum 26B-AM by 26% and S. obliquus UTEX393 by 13% in laboratory testing, it failed to improve biomass productivity under outdoor pond conditions for both strains. The second method added sodium sulfite as an oxygen scavenger to chemically lower the DO concentration in the culture. Chemical reduction of dissolved molecular oxygen did not significantly improve the biomass productivity of M. minutum 26B-AM; however, a 10% improvement in biomass productivity for S. obliquus UTEX393 was observed. The final method sparged cultures with air to strip oxygen out of the liquid medium. This did not improve the biomass productivity of M. minutum 26B-AM, likely due to unfavorable weather conditions during cold season cultivation; however, an improvement of 36% in biomass productivity was achieved for S. obliquus UTEX393 during the warm season cultivation. Of the three tested methods, air-sparging was the most effective and practical for improving outdoor biomass production.

59 BASIC BIOLOGICAL SCIENCES↗

Marine algae growth and carbon capture augmentation by antioxidant nanozymes

Large scale commercial cultivation of microalgae year-round is limited by seasonal stress conditions. The rapid growth and high CO 2 capture of the marine microalga Picochlorum celeri is largely inhibited under winter stress conditions of low temperature and high light. Herein, we demonstrated a nanotechnology approach to enhance the biomass productivity and CO 2 capture of P. celeri under abiotic stress by interfacing with antioxidant cerium oxide nanozymes (nanoceria). Antioxidant nanoceria catalytically scavenged reactive oxygen species (ROS) generated under stress conditions, reducing damage to the microalgae photosynthetic machinery in chloroplasts. Negatively charged poly-acrylic acid-coated nanoceria (PNC, 10 μM) were biocompatible in microalgae cells and colocalized with chloroplasts. In contrast, positively charged aminated nanoceria (ANC) resulted in microalgae aggregation (>50 μM) and were toxic at all concentrations tested (≥10 μM). PNC reduction of ROS levels in microalgae (78%) and superoxide levels (26%), enhanced microalgae growth (65%), photosynthetic performance (130%), and CO 2 uptake rate (380%) under low-temperature stress (15 °C) and high light (500 μmol/m 2 /s PAR) stress relative to controls without nanoceria. Nanoceria augmentation of microalgae provides a rapid and facile technology to increase algae CO 2 capture and biomass under stress conditions.

09 BIOMASS FUELS↗

Photo-generated reactive oxygen species assisted tandem amine homocoupling and amine-alcohol cross-coupling reaction on mesoporous spinel cobalt oxide

Mesoporous spinel cobalt oxide (Co 3 O 4 ) with fine-tuned pore size distributions (9.6–17.6 nm) and different surface areas (33–85 m 2 /g) were synthesized using a series of nonionic surfactants. A direct influence of the chemical composition of the surfactants and calcination temperature on crystallite size, morphology, pore size/volume, surface area, valance band edge, and Co 2+ /Co 3+ ratio was recognized. Correlation between the aforementioned factors, transition metal ion incorporation and benzylamine homocoupling reaction was discussed. Shape-specific binding of amine on the cobalt oxide active sites was proposed based on substrate scope study. Tandem synthesis strategy to selectively synthesize amine (aliphatic/aromatic) homo-coupled imines and amine-alcohol cross-coupled imines was introduced. Low-intensity light-induced singlet oxygen and hydroxyl radical-mediated reaction mechanism was proposed based on the EPR, XPS, photoreactor, and reactive oxygen species scavenger tests. Selective and switchable synthesis of homo-coupled (yield 85%) and cross-coupled (yield 87%) products was achieved with sodium azide and mannitol additives.

54 ENVIRONMENTAL SCIENCES↗

Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

impedance↗

A regenerative concept for thermoelectric power generation

Here this paper presents a regenerative concept for thermoelectric (TE) based waste heat recovery systems called thermoelectric generators (TEGs). TEG is usually a modified heat exchanger with the addition of thermoelectric modules (TEMs) to recover waste heat for power generation. To utilize heat from high temperature heat sources, current researches have largely been focused on the development of high temperature TE materials. In this study, we describe a regeneration concept in which a precooler is used to lower the temperature of the hot gas and at the same time regenerate hot air from the cold air supply for Bi 2 Te 3 -based TEGs, avoiding the use of high-temperature thermoelectric materials. It is found that the regenerative TEGs can achieve a similar power output compared with TEGs using high temperature TE materials such as filled-skutterudites (combined filled skutterudites and Bi 2 Te 3 TE materials) through obtaining a higher heat scavenging rate. Thus, the regenerative TEGs also have a similar absolute efficiency, defined according to the total available enthalpy from the hot gas. This could represent a paradigm shift in the TEG research and development, that much lower-cost, reliable, and readily available TE materials and modules can be used for high temperature applications, and will ultimately enable wide spread deployment of TEGs for real world waste heat recovery applications.

42 ENGINEERING↗

Low pressure direct injection strategies effect on a small SI natural gas two-stroke engine’s energy distribution and emissions

This paper examines methods to simultaneously improve efficiency and reduce emissions from a 34 cc air-cooled two-stroke engine configured to operate on natural gas, using tuned intake plus exhaust resonators designed from Helmholtz resonance theory to promote effective scavenging. The engine was developed for novel application in a small, free piston engine for decentralized power generation. Operation occurred at wide-open-throttle at a speed of 5400 RPM for both port injection (PI) and low-pressure direct injection (LPDI). In both cases, the electronic ignition timing was adjusted for maximum brake torque, while the fuel was adjusted such that both rich and lean combustion were examined. The LPDI engine was then operated over a variety of engine speeds. An energy balance was completed for both PI and LPDI operation, which quantified all energy pathways, as engine operating regimes changed. Results showed that exhaust chemical energy (ECE) for LPDI was reduced significantly when compared to PI, mostly due to less fuel slip. The fuel slip rate ranged from 35 to 40% for PI operation while it was in the range of 6–20% for LPDI operation. However, mixture stratification with LPDI operation increased carbon monoxide emissions. The start-of-injection (SOI) was also examined, targeting a SOI to provide the highest trapping efficiency and most stable combustion. For LPDI operation, trapping efficiency, which is function of engine speed, showed significant effects on overall efficiency and fuel slip. Air volumetric efficiency increased due to the absence of gaseous fuel within the intake manifold. It was shown that, relative to PI, the overall engine indicated efficiency increased by 90% to a maximum indicated efficiency of 30% for LPDI operation with a SOI of 180 CAD BTDC.

42 ENGINEERING↗

Geochemical and Mineralogical Investigation of Uranium in Multi–element Contaminated, Organic–rich Subsurface Sediment

Alluvial sediments characterized by an abundance of refractory or lignitic organic carbon compounds and reduced Fe and S bearing mineral phases have been identified through drilling activities at the U.S. Department of Energy’s (DOE) Integrated Field Research Challenge (IFRC) site at Rifle, CO. Regions of the subsurface from which such sediments are derived are referred to as Naturally Reduced Zones (NRZ). We conducted a study with NRZ sediments with the objective to: i.) Characterize solid phase contamination of U and other co-contaminants; ii.) Document the occurrence of potential U host minerals; iii.) Determine U valence state and micron scale spatial association with co-contaminants. Macroscopic (wet chemical batch extractions and a column experiment), microscopic (SEM-EDS), and spectroscopic (Mössbauer, µ-XRF and XANES) techniques were employed. Results showed that sediments’ solid phase had significant concentrations of U, S, As, Zn, V, Cr, Cu and Se, and a remarkable assortment of potential U hosts (sorbents and/or electron donors), such as Fe oxides (hematite, magnetite, Al-substituted goethite), siderite, reduced Fe(II) bearing clays, sulfides of different types, Zn sulfide framboids and multi – element sulfides. Multi-contaminants, micron size (ca. 5 to 30 µm) areas of mainly U(IV) and some U(VI), and/or other electron scavengers or donors such as Se, As, Cr, and V were discovered in the sediments, suggesting complex micron-scale system responses to transient redox conditions, and different extent and rates of competing U redox reactions than those of single contaminant systems. Collectively, the results improve our understanding and ability to predict U and NRZ’s complex behavior and will delineate future research directions to further study both the natural attenuation and persistence of contaminant plumes and their contribution to groundwater contamination.

bioavailability↗

High resolution variability in wet deposition in the southeastern United States

Rainwater chemistry is determined by atmospheric pollutants and particles which vary spatially and temporally. Industrial and agricultural activities and meteorological events (e.g. sea breezes, severe weather, blowing dust) alter atmospheric particle and trace gas compositions. These gases and particles are scavenged by cloud and rain droplets that drive wet deposition. During an Intensive Operation Period (IOP) from April to October 2021, rainwater was collected at higher frequency intervals, usually daily, after precipitation events at three locations on the Savannah River Site (SRS). The farthest locations were separated by approximately 20 km. The mean concentration (μeq/L) of seven ions followed the Cl⁻ > SO 4 2− > Na⁺ > NO 3 ⁻ > K⁺ > Mg 2+ > Ca 2+ downward trend. Ion concentrations were compared to background ion concentrations from the National Atmospheric Deposition Program (NADP). The high frequency monthly averaged SRS data compared well with the monthly averaged NADP background but demonstrated extensive variability. In some months in 2021, the high frequency data compared better to the NADP site near the coast while in other months inland sites compared better. Strong spatial variability for ion concentrations was observed across SRS which was attributed to localized impacts in rainfall spatial variability. High frequency measurements allowed for comparison to regional weather patterns indicating influences from the Atlantic Ocean, Gulf of Mexico, and cities. This can account for spatial variability in the wet deposition flux. Sea breezes, Saharan dust, and anthropogenic sources were shown to impact wet deposition flux variability. Higher frequency precipitation chemistry sampling at numerous locations better captures ion concentration variability and improves measurement representativeness.

54 ENVIRONMENTAL SCIENCES↗

Disentangling interlayer confinement and pore surface adsorption in functionalized smectites for tunable ethylene gas capture

Smectite-based adsorbents are increasingly being studied as sustainable packaging materials for scavenging ethylene, a plant hormone that accelerates fruit ripening. However, the mechanisms governing their uptake and retention remain poorly understood. Here, to tackle this question we systematically investigate ethylene gas-solid interactions in pristine, acid-activated, and choline-functionalized montmorillonites using a complementary combination of structural, gravimetric, and spectroscopic techniques, including inelastic neutron scattering. We experimentally distinguish ethylene populations associated with interlayer confinement, mesopore, and external surface adsorption. We show that chemical functionalization distinctly controls adsorption pathways: acid activation enhances total uptake by generating mesoporous adsorption sites and promoting partial interlayer intercalation, yielding capacities comparable to those of leading smectite-based adsorbents, while choline functionalization promotes preferential confinement and stabilization of guest molecules within the interlayer galleries. Advanced spectroscopic analysis provides molecular-level insight into confinement environments and interaction strengths. We also establish clear structure-property relationships by correlating uptake values derived from independent techniques, linking chemical modification, accessible adsorption domains, and retention behavior. These findings provide general design principles for tuning gas-solid interactions in functionalized layered silicates and highlight their potential as adaptable platforms for sustainable ethylene gas capture and selective adsorption technologies.

Ethylene adsorption mechanism↗

Hydrogen gas treatment prolongs replicative lifespan of bone marrow multipotential stromal cells in vitro while preserving differentiation and paracrine potentials

Cell therapy with bone marrow multipotential stromal cells/mesenchymal stem cells (MSCs) represents a promising approach in the field of regenerative medicine. Low frequency of MSCs in adult bone marrow necessitates ex vivo expansion of MSCs after harvest; however, such a manipulation causes cellular senescence with loss of differentiation, proliferative, and therapeutic potentials of MSCs. Hydrogen molecules have been shown to exert organ protective effects through selective reduction of hydroxyl radicals. As oxidative stress is one of the key insults promoting cell senescence in vivo as well as in vitro, we hypothesized that hydrogen molecules prevent senescent process during MSC expansion. Addition of 3% hydrogen gas enhanced preservation of colony forming early progenitor cells within MSC preparation and prolonged the in vitro replicative lifespan of MSCs without losing differentiation potentials and paracrine capabilities. Interestingly, 3% hydrogen gas treatment did not decrease hydroxyl radical, protein carbonyl, and 8-hydroxydeoxyguanosine, suggesting that scavenging hydroxyl radical might not be responsible for these effects of hydrogen gas in this study.

60 APPLIED LIFE SCIENCES↗

Cardiolipin modulates allosterically peroxynitrite detoxification by horse heart cytochrome c

Research highlights: {yields} Cardiolipin binding to cytochrome c. {yields} Cardiolipin-dependent peroxynitrite isomerization by cytochrome c. {yields} Cardiolipin-cytochrome c complex plays pro-apoptotic effects. {yields} Cardiolipin-cytochrome c complex plays anti-apoptotic effects. -- Abstract: Upon interaction with bovine heart cardiolipin (CL), horse heart cytochrome c (cytc) changes its tertiary structure disrupting the heme-Fe-Met80 distal bond, reduces drastically the midpoint potential out of the range required for its physiological role, binds CO and NO with high affinity, and displays peroxidase activity. Here, the effect of CL on peroxynitrite isomerization by ferric cytc (cytc-Fe(III)) is reported. In the absence of CL, hexa-coordinated cytc does not catalyze peroxynitrite isomerization. In contrast, CL facilitates cytc-Fe(III)-mediated isomerization of peroxynitrite in a dose-dependent fashion inducing the penta-coordination of the heme-Fe(III)-atom. The value of the second order rate constant for CL-cytc-Fe(III)-mediated isomerization of peroxynitrite (k{sub on}) is (3.2 {+-} 0.4) x 10{sup 5} M{sup -1} s{sup -1}. The apparent dissociation equilibrium constant for CL binding to cytc-Fe(III) is (5.1 {+-} 0.8) x 10{sup -5} M. These results suggest that CL-cytc could play either pro-apoptotic or anti-apoptotic effects facilitating lipid peroxidation and scavenging of reactive nitrogen species, such as peroxynitrite, respectively.

60 APPLIED LIFE SCIENCES↗