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At least 811 records · Page 45

Canted antiferromagnetism in the quasi-one-dimensional iron chalcogenide BaFe 2 Se 4

We report the synthesis and physical properties studies of quasi-one-dimensional (quais-1D) iron chalcogenide BaFe 2 Se 4 which shares the FeSe 4 tetrahedra building motif commonly seen in the iron chalcogenide superconductors. A high-quality polycrystalline sample was achieved by solid-state reaction method and characterized by x-ray diffraction, electrical resistivity, magnetic susceptibility, and neutron diffraction measurements. BaFe 2 Se 4 is a narrow gap semiconductor that magnetically orders at ~310 K. Therefore, both neutron powder diffraction results and isothermal M-H loops suggest a canted antiferromagnetic structure where Fe sublattices are antiferromagnetically ordered along the c-axis quasi-1D chain direction, resulting in a net ferromagnetic moment in the perpendicular direction along the a axis with tilted angle of 18.7° towards the b axis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Advanced Synthesis of Na 4 Si 24

The recently discovered orthorhombic allotrope of silicon, Si 24 , is an exciting prospective material for the future of solar energy due to a quasi-direct bandgap near 1.3 eV, coupled with the abundance and environmental stability of silicon. Synthesized via precursor Na 4 Si 24 at high temperature and pressure (~850 °C, 9 GPa), typical synthesis results have yielded polycrystalline samples with crystallites on the order of 20 μm. Several approaches to increase the crystal size have yielded success, including in-situ thermal spikes and refined selection of the starting materials. Microstructural analysis suggests that coherency exists between diamond silicon (d-Si) and Na 4 Si 24 . This hypothesis has led to the successful attempts at single crystal synthesis by selecting large crystals of d-Si along with metallic Na as the precursors rather than powdered and mixed precursor material. The new synthesis approach has yielded single crystals of Na 4 Si 24 greater than 100 μm. These results represent a breakthrough in synthesis that enables further characterization and utility. The promise of Si 24 for the future of solar energy generation and efficient electronics is strengthened through these advances in synthesis.

catalysis (heterogeneous)↗

Initial Assessment of Ruthenium Removal Systems for Tritium Pretreatment Off-Gas

The processing of used nuclear fuel releases volatile and semivolatile radionuclides into the off-gas streams associated with the various processing steps. Ongoing efforts to develop methods to control the release of gaseous radionuclides to the environment have identified ruthenium (specifically 106 Ru) as one of the semivolatile nuclides requiring a high degree of abatement. The tritium pretreatment process will release a fraction of the ruthenium as volatile ruthenium tetroxide (RuO 4 ). Scoping tests were conducted to characterize the adsorption/deposition of RuO 4 from dry gas streams by two different substrates: steel wool and silica gel. A simple test system was assembled to produce RuO 4 through oxidation of powdered ruthenium metal, followed by a temperature-controlled sorption column. Tests were conducted with no sorbent present in the column to obtain baseline data on the evolution of RuO 4 and deposition of ruthenium on the internal surfaces of the column. Silica gel and steel wool were tested as adsorbent media. Gaseous effluent from the column was scrubbed with caustic solution to remove any remaining ruthenium. Ultraviolet/visible spectroscopy (UV/Vis) and inductively coupled plasma–mass spectroscopy analyses were used to measure the amount of ruthenium in the scrub solutions. The UV/Vis analysis proved to be problematic because of precipitation of ruthenates, ruthenium oxides, and hydrated ruthenium oxides that occurred over time. An effective stabilization agent that does not adversely affect the desired spectra needs to be identified if this method is to be used in the future. There were indications that oxidation of powdered ruthenium metal did not generate a stream with steady concentration of RuO 4 , so improved techniques are needed for follow-on experiments designed to infer deposition rate. Both steel wool and silica gel are able to decrease the effluent Ru concentration by a factor of 10–100 during the 5-hour tests conducted. These tests were conducted using a dilute RuO 4 -bearing dry gas stream and the short test duration did not result in sorbent saturation or in an estimation of Ru breakthrough time. RuO 4 desorbs from silica gel at room temperature. As interactions between RuO 4 and silica gel are not irreversible, it cannot function as a disposal media without pretreatment to reduce RuO 4 to a less mobile species. Silica gel may be useful as a RuO 4 sorbent or delay media in some applications. Based on visual observations, steel wool was an effective deposition substrate with no evidence of RuO 4 release. The deposition form should be identified and methods to assay the ruthenium content need to be developed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Wyoming CarbonSAFE Phase III: Site Characterization and Permitting Commercial-Scale Carbon Storage Complex Feasibility Study at Dry Fork Station, Wyoming

This report presents the findings of the technical and non-technical site characterization and permitting activities (“Phase III”) conducted under the Wyoming CarbonSAFE: Accelerating CCUS Commercialization and Deployment at Dry Fork Power Station (DFS) and the Wyoming Integrated Test Center project (“Wyoming CarbonSAFE”). Wyoming CarbonSAFE is part of the U.S. Department of Energy’s (DOE) National Energy Technology Laboratory (NETL) Carbon Storage Assurance Facility Enterprise (“CarbonSAFE”) Initiative. The results of Phase III demonstrate that the Wyoming CarbonSAFE project - referred to as the Northern Powder River Basin Carbon Sequestration Hub (NPRB-CSH) - meets the technical, regulatory, and commercial feasibility requirements necessary to advance toward commercial development and construction. The activities completed under this project Phase make the NPRB-CSH one of the region’s most commercially ready carbon storage sites. Completion of this Phase included the finalization of all site surface and subsurface characterization activities, completion and testing of two Class VI standard wells, 10 draft Class VI permits-to construct to address the future needs of a storage complex, finalized NEPA assessments, transportation and capture FEED studies, and a full commercialization strategy with economic modeling, operation and site closure strategies. The NPRB-CSH meets all requirements to progress to a CarbonSAFE Phase IV program or advance to full commercial operations under the development of a business partner.

01 COAL, LIGNITE, AND PEAT↗

Characterizing the solid hydrolysis product, UF 4 (H 2 O) 2.5 , generated from neat water reactions with UF 4 at room temperature

Uranium tetrafluoride (UF 4 ) is an important intermediate in the production of UF 6 and uranium metal. Room temperature hydrolysis of UF 4 was investigated using a combination of Fluorine-19 nuclear magnetic resonance spectroscopy ( 19 F NMR), Raman and infrared spectroscopy, powder X-ray diffraction, and microscopy measurements. UF 4 (H 2 O) 2.5 was identified as the primary solid hydrolysis product when anhydrous UF 4 was stirred in deionized water. Static NMR and 19 F magic angle spinning NMR measurements revealed that a small amount of uranyl fluoride can also form when anhydrous UF 4 is left in water, although this species comprises less than 5% of the total sample with the remaining parts being UF 4 (H 2 O) 2.5 . Since UF 4 is generally considered to be stable under ambient conditions, these findings mark the first time that a room temperature reaction between UF 4 and water has been detected and analyzed without interference from additional chemical reagents. The Raman characterization of UF 4 (H 2 O) 2.5 presented herein is the first on record. Since UF 4 is one of the most used intermediates during chemical conversion of uranium ore to uranium metal for nuclear fuel and weapons, the results presented herein are applicable to numerous nuclear science fields where solid state detection of uranium is of value, including nuclear nonproliferation, nuclear forensics, and environmental remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructure and properties of a high temperature Al–Ce–Mn alloy produced by additive manufacturing

An Al–10Ce-8Mn (wt%) alloy was designed and fabricated by laser powder bed fusion additive manufacturing (AM). The rapid cooling rates of the AM process produced a refined microstructure with a large fraction of reinforcing intermetallic phases. The tensile properties of the alloy were characterized in the as-fabricated state and following thermal exposure. The properties of the as-fabricated microstructure showed exceptional high-temperature performance and strength retention at elevated temperatures up to 400 °C relative to benchmark wrought Al and AM Al alloy properties. Characterization of the microstructure and thermodynamic modeling of the ternary Al–Ce–Mn system rationalized the solidification and solid-state phase transformations. Finally, analysis of the relevant strengthening mechanisms for both the as-fabricated and thermally exposed conditions was performed.

36 MATERIALS SCIENCE↗

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.

36 MATERIALS SCIENCE↗

Materials Characterization Techniques Lecture Series: X-Ray Diffraction, A Summary of LANL's Materials Capabilities in MPA-11 [Slides]

This presentation provides an overview on X-Ray Diffraction (XRD) to cover background, fundamentals, limitations, best practices, applications, analysis, software, and resources. To summarize: XRD is a great tool for characterizing solid crystalline samples. X-Rays are E-Mag radiation and generate diffraction profiles based on the phase of the sample. Diffraction patterns are unique to the phase of the sample. Powder diffraction gives us better diffraction profiles. We can obtain both qualitative and quantitative data. Analysis requires us to know a little about our sample and a lot about our diffractometer.

36 MATERIALS SCIENCE↗

Development of Engineered Metal-Organic Framework (MOF) materials for perfluorooctane sulfonate (PFOS) Remediation

In this project, an engineered form of a Metal-Organic Framework (MOF) based material is developed for the removal of perfluorooctane sulfonate (PFOS) for real-world applications. The powdered MOF material has been demonstrated at the Pacific Northwest National Laboratory (PNNL) to selectively capture PFOS from distilled (DI) water with a large performance advantage over granulated activated carbon (GAC). In this project, the powdered material was transformed into an engineered form (using a polymer) to demonstrate PFOS adsorption capacity in tap water. PNNL developed and processed the MOF material in the engineering form (granules). After thorough characterization and stability testing, these engineered MOF granules were provided to an industrial collaborator, AVANTech, LLC, for testing and demonstration of continuous, long-term PFOS removal from tap water. The preliminary results showed PFOS sorption capacities at parts per billion (ppb) concentrations in tap water under a flow system. Also provided insight into sorbent-based material utilization in a continuous flow system. Further studies are required to optimize and understand sorption in such industrial-scale applications.

36 MATERIALS SCIENCE↗

Microstructure of Neutron-Irradiated Al 3 Hf-Al Thermal Neutron Absorber Materials

A thermal neutron-absorbing metal matrix composite (MMC) comprised of Al 3 Hf particles in an aluminum matrix was developed to filter out thermal neutrons and create a fast flux environment for material testing in a mixed-spectrum nuclear reactor. Intermetallic Al 3 Hf particles capture thermal neutrons and are embedded in a highly conductive aluminum matrix that provides conductive cooling of the heat generated due to thermal neutron capture by the hafnium. These Al 3 Hf-Al MMCs were fabricated using powder metallurgy via hot pressing. The specimens were neutron-irradiated to between 1.12 and 5.38 dpa and temperatures ranging from 286 °C to 400 °C. The post-irradiation examination included microstructure characterization using transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy. This study reports the microstructural observations of four irradiated samples and one unirradiated control sample. All the samples showed the presence of oxide at the particle–matrix interface. The irradiated specimens revealed needle-like structures that extended from the surface of the Al 3 Hf particles into the Al matrix. An automated segmentation tool was implemented based on a YOLO11 computer vision-based approach to identify dislocation lines and loops in TEM images of the irradiated Al-Al 3 Hf MMCs. This work provides insight into the microstructural stability of Al 3 Hf-Al MMCs under irradiation, supporting their consideration as a novel neutron absorber that enables advanced spectral tailoring.

36 MATERIALS SCIENCE↗

Structural and optical analysis of Fe doped NiO nanoparticles synthesized by chemical precipitation route

Highlights: • The Fe doped NiO nanoparticles were synthesized by chemical precipitation route. • XRD analysis reveals cubic rock-salt fcc structure of the synthesized nanoparticles. • The Ni-O and Fe-O bonding were confirmed through FTIR spectroscopy. • Existence of nickel or interstitial oxygen vacancies indicates p-type nature of nanoparticles. - Abstract: The Ni{sub 1-x}Fe{sub x}O (x = 0.00, 0.02, 0.04 and 0.06) nanoparticles are synthesized by chemical precipitation route using polyvinyl-pyrrolidone (PVP) and nitrate metal salts. The results of thermogravimetric analysis (TGA) of the synthesized dried hydroxide powders showed that thermal decomposition occurs up to 500 °C so as to form pure Ni{sub 1-x}Fe{sub x}O. Therefore, all synthesized samples were calcined at 500 °C for 4 h and then used for further characterization. Energy dispersive X-ray spectroscopy (EDS) of all the samples showed the presence of Ni, O and Fe without any other impurities. From X-ray diffraction (XRD) and transmission electron microscopy (TEM) we could prove that the samples are polycrystalline in nature and are in single phase. The different vibrational modes in Ni{sub 1-x}Fe{sub x}O (x = 0.00, 0.02, 0.04 and 0.06) nanoparticles were studied by Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). Further, we analyzed the optical response from ultraviolet-visible spectra and Photoluminescence (PL) spectra.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

SR19016 - Characterization of AM Materials for SRTE Service

This project addresses several issues and challenges for the use of AM produced components in the tritium facility. It will evaluate the effect of low level hydrogen and tritium exposure on the mechanical and chemical characteristics of Arcam A2X Electron Beam Powder Bed Fusion Produced (EPBF) Ti-6AI-4V by printing tensile samples and testing them in the as printed, machined, and hydrogen exposed conditions. Hydrogen uptake will be measured using an Eltra Hydrogen-Oxygen- Nitrogen analyzer. Hydride response will be measured using a Seiffert's apparatus and determining the effects of various surface treatments on the hydriding susceptibility. Tools, fixtures, and other objects will be deigned and printed for use in the AM lab and tritum facility and for other groups that support the tiritum mission.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Phase Stability of Yttrium Titanium Oxide

This proposed study aims at elevating Idaho National Laboratory (INL)’s portfolio in nuclear material research on two major fronts: 1) expanding INL’s material characterization capabilities to provide holistic microstructural and microchemical characterization ranging from atomic scale to millimeter scale, and 2) filling the knowledge gap on the effect of microstructural evolution on material phase stability at extreme conditions resembling those inside nuclear reactors, using Yttrium-Titanium-Oxide (YTO) as a model material. Previous research indicated the kinetics of phase transition of YTO materials varies between bulk samples and powder samples, suggesting that microstructural characteristics such as defect, micro-strain, and crystallite size could play a significant role in phase transition. The effect of crystallite size on the thermodynamics of phase transition has been well documented for other ceramic materials at nanometer crystallite size, with potential impacts from surface and strain energy and defects. In this proposed study, we will perform microstructural (micro-strain, crystallite size, defects, phase) and microchemical (elemental mapping) analyses through in-situ high temperature measurements using X-ray diffraction (XRD; at millimeter scale for powder and bulk samples) and transmission electron microscopy (TEM, at nanometer scale and atomic scale for powder and thin foil samples), to provide a comprehensive view of the effect of microstructural and microchemical evolution on phase transition and phase stability of YTO materials. These findings will also establish a roadmap and provide new insights on the phase stability of other materials that are critical to nuclear energy and other renewable energy infrastructure. Besides advancing our understanding of this fundamental material science question, this project will also enable the development of state-of-the-art material characterization capabilities at INL/MFC for microstructural and microchemical analysis at high temperature conditions. The new collaboration between the High-Resolution Materials Characterization group at INL and the Electron Microscopy group at the University of Florida (UF) in this project will open the possibilities for more fruitful and synergetic cutting-edge nuclear material research in the future.

36 MATERIALS SCIENCE↗

Microstructural diversity and digestion yields of select bituminous and subbituminous coals as raw material candidates for carbon fiber precursor production

Here, this work investigates the use of coals as raw materials for carbon fiber precursor production as a new alternative to coal utilization. Coal being a highly complex and heterogeneous material with different macerals and minerals complicates this task. Extensive microstructural characterization as well as preliminary digestion studies are performed on three bituminous coals (Herrin and Springfield from the Illinois Basin and the Blue Gem from the Central Appalachians) and one subbituminous coal from the Powder River Basin (Monarch), as raw material candidates. The subbituminous coal was richer in oxygen, lower in sulfur, and had a higher volatile matter yield. Microstructural investigations were performed using X-ray diffraction, X-ray/neutron computed tomography, scanning electron microscopy with energy dispersive spectroscopy, and petrology. Mild solvent extraction studies were conducted using creosote and decant oil as solvents in microreactors. The extraction yield was sensitive to temperature and time (350 to 450 °C between 30 and 120 mins.) for both creosote and decant oil digestions. While the Blue Gem coal had more desirable microstructural properties with less mineral content and cleaner macerals, it had the lowest coal conversion to quinoline soluble ‘liquid’ (of the bituminous coals). The lower coal conversion yield was hypothesized to be connected to the lack of FeS2 which could act as a catalyst when Fe is liberated from the structure under solvent extraction conditions. The Herrin and Springfield coals revealed similar microstructures and coal conversion efficiencies (higher than Blue Gem). These coals were the most promising candidates for further examination from this first approximations study. The subbituminous Monarch coal, however, was deemed less suitable due to poor coal conversion and less desirable microstructures. Additionally, the presented results with combined microstructural data from multiple length scales established a framework necessary for a first approximations study in this new coal utilization approach.

01 COAL, LIGNITE, AND PEAT↗

Adsorption of Iodine on Metal Coupons in Humid and Dry Environments

In this study, five different metal coupons were evaluated for gaseous iodine [I2(g)] adsorption including two stainless steels (i.e., SS304 and SS316), two Inconel® alloys (i.e., 625 and 718) and pure Ni (i.e., Ni-200) within a dynamic flow-through system where temperature, iodine concentration, flow rate, atmosphere, and relative humidity were controlled. Humidity was shown to be critical to iodine adsorption on SS304 and SS316 and Ni-200 at ambient temperatures. The results presented herein suggest that a moisture mediated reaction is occurring. However, higher humidity levels decrease the adsorption, suggesting an ideal range of humidity for highest corrosion. A comparison of the five metal substrates showed the highest I2(g) adsorption in the following descending order Ni-200 > SS304 > SS316 >718>625.The 625 and 718 Inconel alloys were fairly inert to iodine adsorption under the conditions tested. Characterization by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction of the Ni-200 coupon indicates that NiI2 is formed and flakes off the surface as a black powder. The SS304 and SS316 coupons showed evidence of extensive reactions with I2(g) and formed a much more deliquescent corrosion product, which reacted with air when removed from the flow-through system for weighing on the analytical balance. These findings assist in predicting iodine adsorption behavior on a variety of metal surfaces under various conditions.

Beck, Chelsie L.↗

Microstructural evolution, defect mitigation, and precipitation behavior in AA6061 via laser powder bed fusion with high-temperature substrate heating

Defects, particularly solidification cracking, remain persistent challenges in the laser powder bed fusion (LPBF) processing of AA6061 aluminum alloy. This study systematically investigates defect mitigation, microstructural evolution, and mechanical properties associated with high-temperature substrate preheating at 500 °C. Comprehensive microstructural analyses, including characterization of defects, grain structures, and precipitation behavior, were performed on samples in both as-built and T6 heat-treated states. Elevated preheating substantially reduced solidification cracking across a wide processing window, while demonstrating decreased crack sensitivity to laser parameters. Columnar cracks along the build direction were observed despite substrate preheating. Lack-of-fusion and keyhole porosity were effectively eliminated, though gas-induced microporosity persisted at higher powers. In-depth characterization of two distinct laser power and speed conditions confirmed the formation of micron-sized, non-coherent Mg 2 Si precipitates under heated substrate conditions, alongside α-AlFeCrMnSi intermetallic phases indicative of in-situ thermal effects during fabrication. Subsequent T6 heat treatment revealed the formation of fine, coherent needle-shaped β″ strengthening precipitates. Despite substantial differences in processing parameters, comparable mechanical properties were measured in the as-built samples (∼52 MPa yield strength, ∼130 MPa tensile strength), primarily due to reduced strain hardening effects and consistent precipitation characteristics. Meanwhile, the T6 heat treatment led to significant improvement in properties, enhancing yield strength by over 400%, aligning closely with the performance of conventional wrought AA6061-T6. These findings underscore that high-temperature substrate preheating offers an effective means to suppress cracks, control precipitation, and enhance mechanical performance in LPBF-processed AA6061.

36 MATERIALS SCIENCE↗

Structural Insights into the Vapochromic Behavior of Pt- and Pd-Based Compounds

Anionic complexes having vapochromic behavior are investigated: [K(H 2 O)][M(ppy)(CN) 2 ], [K(H 2 O)][M(bzq)(CN) 2 ], and [Li(H 2 O) n ][Pt(bzq)(CN) 2 ], where ppy = 2-phenylpyridinate, bzq = 7,8-benzoquinolate, and M = Pt(II) or Pd(II). These hydrated potassium/lithium salts exhibit a change in color upon being heated to 380 K, and they transform back into the original color upon absorption of water molecules from the environment. The challenging characterization of their structure in the vapochromic transition has been carried out by combining several experimental techniques, despite the availability of partially ordered and/or impure crystalline material. Room-temperature single-crystal and powder X-ray diffraction investigation revealed that [K(H 2 O)][Pt(ppy)(CN) 2 ] crystallizes in the Pbca space group and is isostructural to [K(H 2 O)][Pd(ppy)(CN) 2 ]. Variable-temperature powder X-ray diffraction allowed the color transition to be related to changes in the diffraction pattern and the decrease in sample crystallinity. Water loss, monitored by thermogravimetric analysis, occurs in two stages, well separated for potassium Pt compounds and strongly overlapped for potassium Pd compounds. Furthermore, the local structure of potassium compounds was monitored by in situ pair distribution function (PDF) measurements, which highlighted changes in the intermolecular distances due to a rearrangement of the crystal packing upon vapochromic transition.

36 MATERIALS SCIENCE↗