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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
All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Carbonate Species Using a Stepped Acid Extraction Procedure

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five Ordinary Chondrite (OC) meteorites collected in Antarctica. These samples were identified and requested from NASA based upon their size, alteration history, and collection proximity to known Martian meteorites. They are also assumed to be carbonate-free before falling to Earth. This research addresses two questions involving Mars carbonates: 1) characterize terrestrial, secondary carbonate isotope values to apply to Martian meteorites for isolating in-situ carbonates, and 2) increase understanding of carbonates formed in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each approximately 0.5 grams, were crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) R times 0 for 1 hour at 30 degrees Centigrade (fine calcite extraction), b) R times 1 for 18 hours at 30 degrees Centigrade (course calcite extraction), and c) R times 2 for 3 hours at 150 degrees Centigrade (siderite and/or magnesite extraction). CO (sub 2) was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6 foot 2 millimeter stainless column, and then analyzed on a Thermo MAT 253 Isotope Ratio Mass Spectrometer (IRMS) in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof-tested with known carbonate standards to develop procedures, assess yield, and quantify expected error bands. Two distinct species of carbonates are found: 1) calcite, and 2) non-calcite carbonate (future testing will attempt to differentiate siderite from magnesite). Preliminary results indicate the terrestrial carbonates are formed at approximately sigma (sup 13) C equal to plus 5 per mille, which is consistent with atmospheric CO (sub 2) sigma (sup 13) C equal to minus 7 per mille and fractionation of plus12 per mille based upon polar temperature of -20 degrees Centigrade. The oxygen values fractionate sigma (sup 18) O equal to minus 10-20 per mille lighter between the R times 0 and R times 1 reactions at 30 degrees Centigrade. The carbonate oxygen isotope measurements are consistently heavier than expected with meteoric water and temperatures from Antarctica, perhaps due to secondary carbonate formation during curation in Houston, TX.

Evans, Michael E.↗
NASA NTRS2015

Investigations of Methane Production in Hypersaline Environments

The recent reports of methane in the atmosphere of Mars, as well as the findings of hypersaline paleo-environments on that planet, have underscored the need to evaluate the importance of biological (as opposed to geological) trace gas production and consumption. Methane in the atmosphere of Mars may be an indication of life but might also be a consequence of geologic activity and/or the thermal alteration of ancient organic matter. Hypersaline environments have now been reported to be extremely likely in several locations in our solar system, including: Mars, Europa, and Enceladus. Modern hypersaline microbial mat communities, (thought to be analogous to those present on the early Earth at a period of time when Mars was experiencing very similar environmental conditions), have been shown to produce methane. However, very little is known about the physical and/or biological controls imposed upon the rates at which methane, and other important trace gases, are produced and consumed in these environments. We describe here the results of our investigations of methane production in hypersaline environments, including field sites in Chile, Baja California Mexico, California, USA and the United Arab Emirates. We have measured high concentrations of methane in bubbles of gas produced both in the sediments underlying microbial mats, as well as in areas not colonized by microbial mats in the Guerrero Negro hypersaline ecosystem, Baja California Mexico, in Chile, and in salt ponds on the San Francisco Bay. The carbon isotopic (δ13C) composition of the methane in the bubbles exhibited an extremely wide range of values, (ca. -75 per mille ca. -25 per mille). The hydrogen isotopic composition of the methane (δ2H) ranged from -60 to -30per mille and -450 to -350per mille. These isotopic values are outside of the range of values normally considered to be biogenic, however incubations of the sediments in contact with these gas bubbles reveals that the methane is indeed being produced by these sediments. Substrate limitation of methanogenesis in these environments, and not methane oxidation, would explain the isotopic values of the methane in these environments. Incubations with both isotopically labeled and unlabeled putative substrates for methanogenesis have shown that the substrates most important for methanogenesis in these environments are the so-called non-competitive substrates, e.g., methylamines, dimethylsulfide, and methanol. Acetate and bicarbonate appear not to be important substrates for methanogens in these environments. Extraction of DNA and analysis of a gene used for methane production (mcrA) has revealed that the community composition of methanogens is consistent with organisms known to use non-competitive substrates. Our work has shown that hypersaline environments have the potential to both produce and preserve methane for analysis, e.g., by capable rovers. Our work expends the range of methane isotopic values now known to be produced by active methanogenesis

hypersaline paleo-environments↗
DOE OSTI2023

Formation and Consolidation of UN Nanostructures in U-Mo Fuel via Mechanical Alloying and Spark Plasma Sintering

Uranium-molybdenum (U-Mo) alloys show promise as a nuclear fuel system due to their high thermal conductivity and high fuel loading capability. However, U-Mo systems suffer from irradiation induced swelling ultimately affecting the cladding via mechanical and chemical interaction. To address these shortcomings, this thesis investigated the formation of uranium mononitride (UN) nanoparticles within a U-10Mo matrix. To promote the formation of UN, U-10Mo powders were mechanically alloyed under a high purity nitrogen cover gas (99.9995%) atmosphere. Variations were made in stainless steel milling media size, duration of milling, and number of times the milling jar was re-aerated with nitrogen gas. UN nanoparticulates were successfully formed within the U-Mo matrix and was characterized utilizing light element analysis, X-ray diffractometry, scanning and transmission-electron microscopy, electron energy loss spectroscopy, and atom probe tomography. Presence of the UN nanoparticles was found as early as 1-hour into the mechanical alloying process, and significant iron contamination found after 10-hours of milling. The U-Mo/UN powders were compacted using spark plasma sintering techniques in order to stabilize the nanostructure. U-Mo/UN compacts containing small amounts of neodymium and helium were analyzed to observe the defect migration tendencies of fission products within the fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Metal-ceramic composite powders

A process for manufacturing metal-ceramic composite material powder comprising ball milling metal powder and ceramic nanoparticles to yield a metal-ceramic composite powder comprising ceramic nanoparticles embedded in a metal matrix powder particles; wherein the ball milling is performed using a ceramic milling media and a milling vessel having a ceramic interior surface. Metal matrix nanocomposite powders comprising ceramic nanoparticles imbedded in metal matrix powder particles; wherein the metal matrix powder particles have a spherical shape; wherein there is uniform distribution the ceramic nanoparticles; wherein the nanocomposite powders have good flowability.

Chen, Lianyi↗
DOE OSTI2024

VOPO 4 cathode for sodium ion batteries

An electrode comprising a space group Pna2 1 VOPO 4 lattice, capable of electrochemical insertion and release of alkali metal ions, e.g., sodium ions. The VOPO 4 lattice may be formed by solid phase synthesis of KVOPO 4 , milled with carbon particles to increase conductivity. A method of forming an electrode is provided, comprising milling a mixture of ammonium metavanadate, ammonium phosphate monobasic, and potassium carbonate; heating the milled mixture to a reaction temperature, and holding the reaction temperature until a solid phase synthesis of KVOPO 4 occurs; milling the KVOPO 4 together with conductive particles to form a conductive mixture of fine particles; and adding binder material to form a conductive cathode. A sodium ion battery is provided having a conductive NaVOPO 4 cathode derived by replacement of potassium in KVOPO 4 , a sodium ion donor anode, and a sodium ion transport electrolyte. The VOPO 4 , preferably has a volume greater than 90 Å 3 per VOPO 4 .

Whittingham, M. Stanley↗
DOE OSTI2020

Canonsburg, Pennsylvania, UMTRCA Title I Disposal Site 35 Years Postclosure (1985-2020) - 20288

The DOE Office of Legacy Management (LM) Canonsburg, Pennsylvania, Disposal Site is a former uranium ore-processing site located in the borough of Canonsburg and an important part of US history. For 46 years (1911-1957), the site processed ore, for vanadium, radium and then uranium. Soils and groundwater beneath the site were contaminated by the milling operations. The 15-hectare (37-acre) site is owned by the US government and managed by LM, which serves as the federal land manager and steward of cultural, historical, and natural resources at Cold War legacy sites that have been successfully cleaned up to remedial standards. In 1978 Congress directed DOE to remediate 22 inactive uranium-ore processing sites under the Uranium Mill Tailings Radiation Control Act (UMTRCA), in accordance with standards promulgated by the US Environmental Protection Agency in Title 40 CFR Part 192 (40 (CFR 192). Subpart B of 40 CFR 192 regulates the cleanup of contaminated groundwater at the processing sites. The radioactive materials were encapsulated in US Nuclear Regulatory Commission (NRC)-approved disposal cells, and the NRC general license for UMTRCA Title I sites is established in 10 CFR 40.27. Canonsburg was the first site to be remediated under UMTRCA. From 1983 to 1985, the Canonsburg site underwent cleanup under this US law that provides for the safe and environmentally sound disposal, long-term stabilization, and control of uranium mill tailings in a manner that minimizes or eliminates radiation health hazards to the public. The site is unique in that it is one of only two UMTRCA Title I sites in the eastern half of the United States, the other site being the Burrell, Pennsylvania, Title I Disposal Site, a vicinity property to the Canonsburg site. It has been 35 years since the disposal cell at the Canonsburg site was completed. This paper discusses the many efforts that have been taken to maintain the site and presents some of the lessons learned concerning the long-term care of the site. The discussion includes but is not limited to the following: (1) Preserving site history so the community can better appreciate and understand the site. (2) Community outreach efforts, and the importance of maintaining transparency of environmental monitoring results with the community. (3) Pursuing reuse opportunities that offer the potential for improving the community. (4) Remaining engaged with the local community. (5) Remaining proactive in the long-term care of the site. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

A nonparametric approach to modeling dependence among production parameters for energy cost estimation

Dependence existing among production parameters can significantly affect energy costs. For material removal processes, processing times and material amounts to be cut have positive dependence, and the dependence can affect energy costs by varying a peak electricity load. Existing methods to model the dependence of production parameters are based on parametric approaches that cannot accurately represent the dependence due to the rigid nature of parametric models. To address this issue, this study proposes a method to quantify dependence among manufacturing parameters through the application of the empirical copula to the dependence between the milling processing time and the amount of volume to be cut. The proposed method is illustrated by a case study of a manufacturing facility consisting of milling machines; a total of 27 scenarios are simulated for energy cost estimations. The case study clearly shows that the proposed method can capture the dependence between the milling parameters more accurately than a conventional dependence measure from parametric correlation models. Furthermore, the findings from this study would be useful to estimate energy costs in that the proposed method provides a better fit to real production data than conventional parametric approaches can.

42 ENGINEERING↗
DOE OSTI2026

Mechanochemical synthesis of hydraulically reactive calcium silicate minerals via thermally-assisted mechanical grinding

This study explores a thermally assisted mechanochemical approach alternative to conventional cement synthesis as a potential to produce hydraulically reactive calcium silicate phases. Ball milling of mixed CaO/SiO 2 feedstocks at temperature ranges 100-300 °C increases the formation of the Ca-O-Si bonds and precursor reactivity. Spectroscopic analyses (FTIR, MAS-NMR, UV-Vis DRS) indicate increasing amorphization with milling temperature, attributed to improved mixing and thermally assisted diffusion. Upon hydration, all treated samples exhibit exothermic heat release, with the sample prepared at 300 °C showing the most pronounced reactivity. Thermal analysis reveals weight loss consistent with C-S-H formation, confirming cement-like behavior. In summary, moderate thermal input during milling promotes structural activation and enhances downstream hydraulic reactivity, providing a proof-of-concept for energy-reduced cement precursor processing.

Alite↗
DOE OSTI2025

Investigating the impact of preparation routes on the properties of copper-decorated silicon particles as anode materials for lithium-ion batteries

In recent years, the calendar life of Si has been recognized as a significant issue that must be addressed prior to technology deployment: The carbon conductive additive is a potential source of parasitic side reactions. However, carbon remains essential due to the low electronic conductivity of Si. In this study, we investigate the use of Cu as a conductive additive and potential alternative to carbon. Some Cu-decorated silicon particles (Si Cu ) were prepared using physical vapor deposition (PVD) via sputtering and high-energy milling. Other Si Cu particles were prepared by using a solution method and examined briefly. The milling method caused Cu to appear as island-like features on the Si surface, whereas the PVD method initially produced similar island-like features that gradually developed into a continuous coating around the Si as sputtering time increased. Electrodes fabricated from Si Cu exhibited lower overall resistivity, demonstrating the beneficial effect of Cu in improving electronic percolation through the electrode. Electrochemical tests showed that the milled SiCu exhibited higher capacity retention, improved rate capability, and lower overpotential. Furthermore, Si Cu coupled with an NMC811 cathode exhibited lower leakage currents compared with the baseline silicon, indicating that incorporating Cu provided an additional advantage of minimizing parasitic currents in the cells.

25 ENERGY STORAGE↗
DOE OSTI2022

Precursor Analysis Report: Cyber Attack on Thyssenkrupp Blast Furnace 2014

The Cyber Attack on Thyssenkrupp Blast Furnace 2014 Precursor Analysis Report leverages publicly available information about the Thyssenkrupp Steel Mill cyber attack and catalogs anomalous observables for each technique employed in the attack. This analysis is based upon the methodology of the Cybersecurity for the Operational Technology Environment (CyOTE) program. In December 2014, the German Government’s Federal Office for Information Security (BSI) released a report detailing a cyber attack on a German steel mill that occurred earlier that year, though exact dates and details of the attack were not revealed. While the report did not specify the name of the company, multiple sources identified the victim as one of Europe’s largest steel manufacturers, Thyssenkrupp AG. Further, Thyssenkrupp announced on 16 May of that year that Europe’s largest blast furnace, “Schwelgern 2,” located at its facility in Duisburg, Germany, would be offline for several weeks for repairs and upgrades, suggesting Schwelgern 2 was likely the target of the attack. The attack began in early 2014, when adversaries infiltrated the victim steel mill’s Information Technology (IT) network via a spearphishing campaign, then worked their way into the Operational Technology (OT) environment, where they executed software that caused denial of service, denial of control, and eventually a loss of control. This led to the blast furnace shutting down without proper safety procedures, resulting in catastrophic physical damage. No lives were lost in the incident, but ThyssenKrupp suffered $4 million in damage to the blast furnace and an additional $6 million in lost revenue. The adversaries required specialized knowledge and expertise in steel production, which enabled them to compromise a variety of internal systems and components across both IT and OT networks. The attack also demonstrated detailed knowledge of the industrial control systems (ICS) and production processes being used. This combination resulted in one of the earliest known publicly reported cybersecurity incidents resulting in physical damage to ICS equipment. Researchers and analysts identified 19 unique techniques (used in a sequence of 20 steps) utilized during the attack with a total of 454 observables using MITRE ATT&CK® for Industrial Control Systems. The CyOTE program assesses observables accompanying techniques used prior to the triggering event to identify opportunities to detect malicious activity. If observables accompanying the attack techniques are perceived and investigated prior to the triggering event, earlier comprehension of malicious activity can take place. Fifteen of the identified techniques used during the Thyssenkrupp cyber attack were precursors to the triggering event. Analysis identified 369 observables associated with these precursor techniques, 316 of which were assessed to have an increased likelihood of being perceived in the 120 days preceding the triggering event. The response and comprehension time could have been reduced if the observables had been identified earlier. The information gathered in this report contributes to a library of observables tied to a repository of artifacts, data sources, and technique detection references for practitioners and developers to support the comprehension of indicators of attack. Asset owners and operators can use these products if they experience similar observables or to prepare for comparable scenarios.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2020

Surface-Controlled Conversion of Ammonia Borane from Boron Nitride

“One-pot regeneration”, which is simple regneneration method of ammonia borane (AB) using hydrazine and liquid ammonia, enables conversion of AB from hexagonal boron nitride (h-BN) after milling hydrogenation. Solution 11 B-NMR revealed the presence of AB after NH 3 /N 2 H 4 treatment of milled h-BN (BNH x ) although the yield of AB was less than 5%. The conversion mechanism was clarified as B-H bonds on the h-BN surface created by ball-milling under hydrogen pressure have an ability to form AB, which was confirmed by Thermogravimetry-Residual Gas Analysis (TG-RGA) and Infrared (IR) analysis. The reaction routes are also the same as regeneration route of polyborazylene because intermediates of AB such as (B(NH 2 ) 3 and hydrazine borane were found by solution 11 B-NMR after soaking BNH x in liquid NH 3 and hydrazine, respectively. Because of the fact that all reactions proceed on the h-BN surface and no reaction proceeds when neat h-BN is treated, breaking of B 3 N 3 ring structure and then creation of B-H bond is the key issue to increase conversion yield of AB.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Microstructural Transitions during Powder Metallurgical Processing of Solute Stabilized Nanostructured Tungsten Alloys

Exploiting grain boundary engineering in the design of alloys for extreme environments provides a promising pathway for enhancing performance relative to coarse-grained counterparts. Due to its attractive properties as a plasma facing material for fusion devices, tungsten presents an opportunity to exploit this approach in addressing the significant materials challenges imposed by the fusion environment. Here, we employ a ternary alloy design approach for stabilizing W against recrystallization and grain growth while simultaneously enhancing its manufacturability through powder metallurgical processing. Mechanical alloying and grain refinement in W-10 at.% Ti-(10,20) at.% Cr alloys are accomplished through high-energy ball milling with transitions in the microstructure mapped as a function of milling time. We demonstrate the multi-modal nature of the resulting nanocrystalline grain structure and its stability up to 1300 °C with the coarser grain size population correlated to transitions in crystallographic texture that result from the preferred slip systems in BCC W. Field-assisted sintering is employed to consolidate the alloy powders into bulk samples, which, due to the deliberately designed compositional features, are shown to retain ultrafine grain structures despite the presence of minor carbides formed during sintering due to carbon impurities in the ball-milled powders.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Modified instanton sum in QCD and higher-groups

We consider the SU(N) Yang-Mills theory, whose topological sectors are restricted to the instanton number with integer multiples of p. We can formulate such a quantum field theory maintaining locality and unitarity, and the model contains both 2π-periodic scalar and 3-form gauge fields. This can be interpreted as coupling a topological theory to Yang-Mills theory, so the local dynamics becomes identical with that of pure Yang-Mills theory. The theory has not only $\mathbb{Z}$ N 1-form symmetry but also $\mathbb{Z}$ p 3-form symmetry, and we study the global nature of this theory from the recent ’t Hooft anomaly matching. The computation of ’t Hooft anomaly incorporates an intriguing higher-group structure. We also carefully examine that how such kinematical constraint is realized in the dynamics by using the large-N and also the reliable semiclassics on $\mathbb{R}$ 3 × S 1 , and we find that the topological susceptibility plays a role of the order parameter for the $\mathbb{Z}$ p 3-form symmetry. Introducing a fermion in the fundamental or adjoint representation, we find that the chiral symmetry becomes larger than the usual case by $\mathbb{Z}$ p , and it leads to the extra p vacua by discrete chiral symmetry breaking. No dynamical domain wall can interpolate those extra vacua since such objects must be charged under the 3-form symmetry in order to match the ’t Hooft anomaly.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

The metamorphosis of semi-classical mechanisms of confinement: from monopoles on ℝ 3 × S 1 to center-vortices on ℝ 2 × T 2

There are two distinct regimes of Yang-Mills theory where we can demonstrate confinement, the existence of a mass gap, and the multi-branch structure of the effective potential as a function of the theta angle using a reliable semi-classical calculation. The two regimes are deformed Yang-Mills theory on ℝ 3 × S 1 , and Yang-Mills theory on ℝ 2 × T 2 where the torus is threaded by a ’t Hooft flux. The weak coupling regime is ensured by the small size of the circle or torus. In the first case the confinement mechanism is related to self-dual monopoles, whereas in the second case self-dual center-vortices play a crucial role. These two topological objects are distinct. In particular, they have different mutual statistics with Wilson loops. On the other hand, they carry the same topological charge and action. We consider the theory on ℝ × T 2 × S 1 and extrapolate both the monopole and vortex regimes to a quantum mechanical domain, where a cross-over takes place. Both sides of the cross-over are described by a deformed ℤ N TQFT. On ℝ 2 × S 1 × S 1 , we derive an effective field theory (EFT) of vortices from the EFT of monopoles in the presence of a ’t Hooft flux. This construction is based on a two-stage Higgs mechanism, reducing SU(N) to U(1) N−1 in 3d first, followed by reduction to a ℤ N EFT in 2d in the second step. This result shows how monopoles transmute into center-vortices, and suggests adiabatic continuity between the two confinement mechanisms. The basic mechanism is flux fractionalization: the magnetic flux of the monopoles splits up and is collimated in such a way that 2d Wilson loops detect it as a center vortex.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Mechanisms of mechanochemical synthesis of cesium lead halides: pathways toward stabilization of α-CsPbI 3

Cesium lead iodide with cubic perovskite structure (α-CsPbI 3 ) is gaining significant interest in photovoltaic applications due to its excellent absorbance of the visible solar light and other attractive optoelectronic properties. However, the synthesis of stable α-CsPbI 3 poses a significant challenge. Mechanochemical synthesis is emerging as a suitable method for the preparation of cesium lead halides. This work investigates the ball milling-induced synthesis of cesium lead halides perovskite phase using halide mixing or doping approaches. The synthesis in the CsI + PbI 2 , CsBr + PbBr 2 , CsBr + PbI 2 , and CsI + PbI 2 + NdI 3 mixtures and halide exchange reactions in the CsPbBr 3 + 3KI and CsBr + PbBr 2 + 3KI systems are investigated to elucidate the mechanism of this process. Then, CsPb(I 1–x Br x ) 3 and CsPb( 1–y )Nd y I 3 materials with different x and y ratios are prepared, and their stability is probed in the air using light absorption spectroscopy. These results suggest that Nd doping is more efficient in the stabilization of the perovskite structure than partial replacement of iodine with bromine. Microstructure observations reveal the existence of two different product formation mechanisms depending on the mechanical properties of reactants. The results reveal that the milling temperature has a significant impact on the reaction kinetics. Here, the produced particles nucleate and grow at the reactant interface and retard the synthesis reaction by creating a diffusion barrier. Extended milling reduces the product particle size and creates fresh contact between reactants, thus facilitating reaction completion.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhancing the flowability of woody biomass slurries in wet biorefineries

Feeding wet lignocellulosic biomass (e.g., softwood and hardwood) slurries into high-pressure, high-temperature reactors at an industrially relevant scale presents significant challenges, such as process equipment plugging. Here, in this study, we investigate the possibility of improving the flowability of biomass slurries in an industrial scale wet biorefinery by tuning the physical and chemical characteristics of the biomass particles. To understand the effects of the chemical characteristics of woody biomass on flowability, cellulose pulp particles are produced from pulp sheets via knife milling, pelletizing, and crumbling. These cellulose pulp particles are processed for acid hydrolysis dehydration (AHDH) at one –tonne-per day pilot scale. The levulinic acid yield (a product of cellulose AHDH) and the flowability of the biomass particles are compared using market pulp, 1 mm crumbled pine softwood, a blend of 2 mm hammer-milled pine softwood with 10 wt.% bark, and 2 mm hammer-milled hardwood material with 10 wt.% bark (to represent forest residues). The results indicate that the presence of hemicellulose and lignin influences the flowability of lignocellulosic feedstocks. Crumbled wood particles show poor flowability at the pilot scale, while the presence of fine materials (less than 0.7 mm) and bark improves the flowability of biomass slurries without affecting the organic acid yields (based on C6 carbohydrate content).

09 - BIOMASS FUELS↗
DOE OSTI2022

Direct observation of Mn distribution/speciation within and surrounding a basidiomycete fungus in the production of Mn-oxides important in toxic element containment

Biogenic manganese (Mn) oxides occur ubiquitously in the environment including the uranium (U) mill tailings at the Ningyo-toge U mine in Okayama, Japan, being important in the sequestration of radioactive radium (Ra). To understand the nanoscale processes in Mn oxides formation at the U mill tailings site, Mn 2+ absorption by a basidiomycete fungus, Coprinopsis urticicola, isolated from Ningyo-toge mine water samples, was investigated in the laboratory under controlled conditions utilizing electron microscopy, synchrotron-based X-ray analysis, and fluorescence microscopy with molecular pH probe. The fungus’ growth was first investigated in an agar-solidified medium supplemented with 1.0 mmol/L of Mn 2+ , ± Cu 2+ (50 – 200 µM), ± Zn 2+ (50 – 200 µM), or ± diphenyleneiodonium chloride (DPI) (50 – 100 µM) at 25 °C. The results revealed that Zn 2+ has no significant effects on the Mn oxides formation, whereas Cu 2+ and DPI significantly inhibit both fungal growth and Mn oxidation, indicating superoxide-mediated Mn oxidation. During the interaction of Mn 2+ with the fungi in solution medium at the initial pH of 5.67, a small fraction of Mn 2+ infiltrated into the fungal hyphae within 8 h, forming a few tens nm-sized concentrates of soluble Mn2+ in the intracellular pH of ~6.5, which can be released back to solution within a day as shown in a subsequent releasing experiment. After 1 day of incubation, Mn oxides began to precipitate on the hyphae, which were characterized to be fibrous nanocrystals with a hexagonal birnessite-structure, these forming spherical aggregates with a diameter of ~1.5 µm. When the fungi were reacted using the Ningyo-toge mine water, the Mn concentration decreased at a rate of 1.0 mmol·day-1 per unit dry weight. The nanoscale processes associated with the fungi derived from the Ningyo-toge mine area provides additional insights into the existing mechanisms of Mn oxidation by filamentous fungi at other U mill tailings sites under circumneutral pH conditions. Such processes add to the class of reactions important to the sequestration of toxic elements.

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

Synthesis of bulk reactive Ni–Al composites using high pressure torsion

Self-propagating exothermic reactions, for instance in the nickel-aluminum (Ni-Al) system, have been widely studied to create high performance intermetallic compounds or for in-situ welding. Their easy ignition once the phase spacing is reduced below the micron scale, makes top-down methods like high-energy ball milling, ideal to fabricate such reactive nanostructures. A major drawback of ball milling is the need of a sintering step to form bulk pieces of the reactive material. However, this is not possible, as the targeted reactions would already proceed. Therefore, we investigate the ability of high pressure torsion as an alternative process, capable to produce bulk nanocomposites from powder mixtures. Severe straining of powder mixtures with a composition of 50 wt% Ni and 50 wt% Al enables fabrication of self-reactive bulk samples with microstructures similar to those obtained from ball milling or magnetron sputtering. Additionally, samples deformed at ambient temperature are highly reactive and can be ignited significantly below the Al melting point, finally predominantly consisting of Al 3 Ni 2 and Al 3 Ni, independent of the applied strain. Although the reaction proceeds first at the edge of the disk, the strain gradient present in the disks does not prevent reaction of the whole sample.

36 MATERIALS SCIENCE↗