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Solid State Quantum Refrigeration Superconducting, Absorption and Measurement Based (Final Technical Report)

During this DOE grant, DE-SC0017890, in place for the past six years, all proposed research was carried out and published in peer-reviewed papers, as well as other projects that emerged during the research. In that effort the research team accomplished all proposed research, as well as many closely related research projects discovered and conceived of during the grant. These works included “Efficient Quantum Measurement Engines”, a work published in Physical Review Letters, giving a theory of quantum measurement-based engines, which uses quantum measurement as a resource. These engines are designed to efficiently convert energy from the stochastic quantum measurement process into useful work. Further publications include “Experimental Realization of a Quantum Dot Energy Harvester”, a joint theory and experimental work in collaboration with the group of Charles Smith in Cambridge, UK, as well as long time theoretical collaborators, Rafael Sánchez and Björn Sothmann. This work, featured as an Editor’s Suggestion in Physical Review Letters, realized an earlier theoretical proposal of ours, whereby two resonant tunneling quantum dots are connected to a central electronic cavity that is heated by a hot energy source. We also published “Superconducting Quantum Refrigerator: Breaking and Rejoining Cooper Pairs with Magnetic Field Cycles” a work done in collaboration with experimentalist Francesco Giazotto from ENS Pisa, Italy, which also resulted in a patent. This paper, published in Phys. Rev. Applied, advanced the concept of a cyclic fridge based on the normal/superconducting phase transition together with layered materials separated by tunnel junctions. We also completed the proposed research on a heat transistor, publishing “Thermal transistor and thermometer based on Coulomb-coupled conductors”, carried out as a collaboration between my group and theorists Splettstoesser (Lund U., Sweden), Sothmann (U. Duisburg-Essen, Germany), and Sánchez (U. Autónoma de Madrid, Spain). We carried out an analysis of a quantum coupled to a quantum point contact as a sensitive thermometer and heat transistor. We found the optimal statistical estimator for the temperature and compared it with experiments on the same type of devices. We also investigated autonomous quantum absorption refrigerators using quantum dots to cool by using a very hot thermal reservoir to drive heat between two other reservoirs. In the article “Quantifying the quantum heat contribution from a driven superconducting circuit”, we demonstrated that for a driven superconducting circuit, we showed heat flow provided by a hot source to the qubit can be switched on and off by varying external parameters, the frequency and the intensity of the driving. In the work “Stochastic thermodynamic cycles of a mesoscopic thermoelectric engine”, we reconsidered the autonomous thermoelectric heat engine in terms of underlying cycles. Rather than periodic behavior, the cycles were stochastic in nature. Nevertheless, by undertaking a graph theoretical analysis of the elementary transport processed, great quantitative and qualitative insight could be found. We also considered the quantum measurement process and showed that a quantum version of Maxwell’s demon could be related to the work extraction of a quantum system, closely related to arrow-of-time measures for quantum measurement, as described in our article “Thermodynamics of quantum measurement and Maxwell's demon's arrow of time”. This work was selected in Phys. Rev. A as an Editor’s Suggestion. A recent preprint titled “Cyclic Superconducting Quantum Refrigerators Using Guided Fluxon Propagation” accomplished an important piece of this grant: to propose a new kind of quantum refrigerator using the dynamics of fluxons in a type II superconductor. This invention envisioned a race-track type geometry where fluxons are confined. By applying a gradient of magnetic field together with electric current in a Corbino geometry, the circulating fluxons can actively cool a cold reservoir, realizing a new type of cyclic superconducting refrigerator. We also investigated the possibility of thermal control from different points of view. The application of quantum measurement to the system gives a new kind of control on the system of interest – we have pioneered this approach and shown that measurement can boost the thermal power of quantum engines as described in “Continuous measurement boosted adiabatic quantum thermal machines”. The ability to have heat flows on demand is an outstanding challenge, and we have provided new solutions to this problem in Thermal control across a chain of electronic nanocavities” for a chain of electron cavities using gating voltage control. The control methods using qubit/qubit coupling to create absorption fridges at their most fundamental level have also been developed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Targeted Rare Earth Element Extraction from Mine Drainage Treatment Solids Informed by Advanced Characterization

In support of a clean energy transition in the U.S., National Energy Technology Laboratory (NETL) has collaborated with staff at Hedin Environmental and students at the University of Pittsburgh to characterize critical mineral content and recovery potential from acid mine drainage treatment solids (AMD solids). AMD solids in Appalachia are an unconventional feedstock of rare earth elements (REEs), with potential of suppling 1,102 tons REE/year. To inform recovery efforts, select AMD solids were examined using synchrotron microprobe analysis in conjunction with USGS-developed geochemical modeling to indicate likely phases hosting critical minerals (REE, Co, Ni, etc.) and associated metals . More than 100 AMD solids were collected from 94 passive AMD treatment systems in Pennsylvania, where limestone aggregates are used for acidity neutralization. As pH increases, dissolved metals and critical minerals in AMD are attenuated as surface coatings on limestone. The collected AMD solids contained up to 2000 mg/kg REE, up to 13,000 mg/kg transition metals (Co, Ni, Zn) and up to 440 mg/kg Li. Regardless of the diverse chemical compositions from AMD solids (Al-rich, Mn-rich, or Al,Fe,Mn-rich), REEs were mostly associated with Al and Mn (hydr)oxides, while select heavy REEs (e.g., Gd, Dy) were co-localized with Fe (hydr)oxides. Co and Ni have different distribution zones, while both co-localized with Mn (hydr)oxides. Based on this characterization, NETL developed a patent-pending innovative step-leaching protocol, “Targeted Rare Earth Extraction (TREE)” to effectively recover up to 90% REE and 60% Co in separate steps. In addition, select post-TREE solid residuals (purified Al oxides, or Mn oxides) can be further developed into functional materials (e.g., lithium and CO2 sorbents) needed for green energy transition and carbon management. This characterization-informed approach as well as TREE processing from AMD solids can be used for other legacy wastes (e.g., coal ash, oil and gas drill cutting, mine tailings), and offers an opportunity to transform waste streams into environmental and economic assets that meet U.S. Department of Energy and U.S. Environmental Protection Agency goals.

characterization and extraction of rare earth elem↗

A tutorial on high-order harmonic generation in atoms, molecules, and condensed matter

This tutorial introduces strong-field-driven high-order harmonics, their experimental generation and characterization techniques, and their main applications including attosecond pulse generation and ultrafast spectroscopy of the target material. We begin from the use of atomic targets, where the first high-order harmonic generation (HHG) experiments were realized in the late 1980s. Then, we briefly discuss the basics of the microscopic generation mechanism and how various steps of the mechanism were exploited in applications such as generating isolated attosecond pulses and probing molecular orbitals. We introduce and describe the standard experimental approaches for condensed phase HHG, where we discuss unique technical challenges of the use of solid-state materials, such as the mitigation of plasma formation and laser damage. We cover the fundamentals of high-harmonic spectroscopy in condensed matter systems, such as wide bandgap dielectrics, semiconductors, liquid media, and 2D-crystals. We provide some examples of rapidly emerging spectroscopic capabilities, such as for probing crystal symmetries, Berry phases, and associated non-trivial topological properties of the source material. Finally, we provide an overview of the research field, including some of the challenges, opportunities, and open questions.

Attosecond pulses↗

Fluidized Bed Gasification For Conversion of Biomass and Waste Materials to Renewable Hydrogen

This project was undertaken in order to study the potential for hydrogen production, at low cost, from mixtures of biomass and municipal solid waste (MSW). This approach allows for the production of hydrogen with a very low fossil carbon burden, while taking advantage of tipping fees (associated with MSW) to improved process economics. The team sourced three primary feedstocks (wood, MSW, and waste plastics) and characterized them comprehensively using established techniques with a long track record in the field of gasification. All three primary feedstocks were highly reactive and lost most of their mass during initial devolatilization. The production of tars, including heavy tars, was quite high, and was most problematic in the case of the MSW and Waste Plastics feedstocks. Little practical difference was identified between the MSW and Waste Plastics materials, and the addition of bed-forming materials (dolomite and brown alumina) to the feedstocks was found to reduce production of tars during devolatilization under thermogravimetric analysis and/or Fischer Assay conditions. A series of four tests in a lab-scale bubbling-fluidized-bed gasifier, at 50 psig of pressure and about 825 C, confirmed these findings. Pellet feedstocks, broken into fragments, were used for these tests, and pellets comprised of 50% MSW and 50% biomass were found to be the best option in terms of fossil carbon burden, economic potential, and gasification characteristics. Tests were then undertaken in a pilot-scale gasifier facility based on the GTI U-Gas fluidized-bed gasification technology. The feedstock handling train of the 20 TPD U-Gas pilot-scale gasifier located in Des Plaines, IL, was operated under simulated gasification conditions, and the 50/50 pellets were found to be very robust and unproblematic. An improved design for the forward end of the feedstock injection screw of the gasifier was developed and installed. The design approach was based on improved passive cooling of the front-most shroud at the end of the screw, since this approach was found in comprehensive modeling studies to be more than sufficient to accomplish the project objectives associated with this phase of the work, while also avoiding thermal gradients that could have caused heat-stress-induced damage to the refractory around the feedstock inlet if an active cooling approach had been applied. Careful technoeconomic analysis (TEA) of two possible 1000 TPD facilities was carried out. The TEA of conversion of MSW with corn stover in one case, and MSW with woody feedstock in the other case, showed that both had the potential to provide hydrogen at about $1/kg (minimum selling price, 2018 dollar basis). Of the two TEA cases, the one that was based on the conversion of wood in the southeastern USA was found to have slightly better economic potential. The other TEA case was based on a real location in Nebraska and called for corn stover feedstock conversion along with MSW. An underserved communities outreach program plan was developed in cooperation with personnel from the Nebraska Public Power District.

08 HYDROGEN↗

Single Crystalline Na 0.67 Ni 0.33 Mn 0.67 O 2 Positive Electrode Material via Molten Salt Synthesis for Sodium Ion Batteries

P2-layered Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) has emerged as a promising positive electrode material for sodium ion batteries due to its appealing electrochemical properties. Synthesis of polycrystalline NNMO (PC-NNMO) materials through conventional calcination of solid precursors remains the prevailing method, where heating occurs in a dry environment with air or O 2 . On the other hand, the molten salt method, where precursors are submerged in molten salt medium during calcination, emerged in recent years to be a scalable technique for more controlled crystal growth and uniform morphology in a variety of materials. Here, we utilize the molten salt method to synthesize single crystalline NNMO (SC-NNMO) materials with enhanced electrochemical properties. The SC-NNMO material exhibits an initial specific discharge capacity of 95 mAh g –1 at a 0.1C rate, retaining approximately 88.5% of its capacity after 100 cycles over a wide voltage range of 2.0–4.2 V. Furthermore, SC-NNMO maintains a capacity retention of 83.9% after 300 cycles at a 1C rate compared to 66.6% for PC-NNMO, indicating excellent long-term cycling stability. This stability is further confirmed by the performance of an SC-NNMO//hard carbon full cell, which retains 90.3% of its capacity after 200 cycles at 1C within a voltage window of 1.9–4.1 V. The enhancement in stability of the SC-NNMO sample is attributed to the single crystalline structure suppressing the undesired P2–O2 phase transition at high voltage. This study also presents an easy, efficient, and straightforward molten salt process for SC-NNMO material synthesis, offering valuable insights into the potential application of such methodology for the large-scale, cost-effective production of various sodium-layered transition metal oxide positive electrode materials for SIBs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Implementation and evaluation of multi-dual mode counter-current chromatography in the CUP Modeler software

Counter-current chromatography (CCC) is a separation technique that utilizes immiscible solvent pairs as stationary and mobile phases, which imparts numerous benefits compared to solid-liquid chromatography including the ability to treat either the more-dense or less-dense solvent layer as the mobile phase. Multi-dual mode (MDM) is a CCC elution mode capable of improving the separation of closely eluting compounds by alternating upper- and lower-layer solvent flows in opposing directions within the same separation. While some effort has been made to model MDM, implementation of these models in experimental design has yet to be widely adopted. Accordingly, we further developed our previously published cell utilized partitioning (CUP) model to include MDM predictions with CCC and packaged the full suite of CUP modeling capabilities into a user-friendly, open-source tool called the CUP Modeler. The mathematical model for MDM CCC was derived and validated with experimental separation of ethyl guaiacol (EG) and ethyl phenol (EP), two compounds that co-elute in our previously demonstrated reductive catalytic fractionation (RCF) lignin monomer isolation method. The developed MDM model provided insights into the effect of multiple operating parameters - including stationary phase retention, flow rate, column efficiency, feed concentration ratio, selectivity factor, and solute distribution ratios - on the separation yields, productivity, and purities. Our model agreed with prevailing understanding of MDM but also revealed new insights including that the ideal distribution ratios for co-eluting solutes to be separated by MDM is between 1.1 and 1.5, with the lower value ideally close to 1.25. Overall, this work provides fundamental insights for MDM process design and enables broader adoption of general liquid-liquid chromatography with a new, open-source user-friendly interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Full Scale HEPA Filter Encapsulation in Ultra-High-Performance Grout - Proof of Concept

The Hanford Tank Waste Treatment and Immobilization Plant (WTP) currently being constructed to treat radioactive waste, includes vitrification facilities for both the high-level waste (HLW) and low activity waste (LAW) fractions. Operation of the WTP will produce contaminated high-efficiency particulate air filters (HEPA), as part of the solid secondary waste (SSW) stream. The HEPA filters receive off-gas from the vessel vent header and primary off-gas treatment system in LAW Facility and remove particulate contaminants including 99 Tc and 129 I salts. The current disposal method for HEPA filters is encapsulation in metal containers using cementitious material (CM) and disposal in the Integrated Disposal Facility (IDF). Results from the 2017 IDF Performance Assessment (PA) WRPS (2018) demonstrated that while compliance is maintained for the 1000 year compliance period mandated by DOE O 435.1 and its accompanying manual, release of constituents from the HEPA filters result in exceedance of the performance objective imposed as the groundwater regulatory limit at later times. For example, at about 1500 years post-closure, solid secondary waste (SSW), including HEPA filters is predicted to become a dominant contributor to 99 Tc release and over the 10,000-year sensitivity analysis period, SSW is the dominant contributor of 129 I release to the groundwater. The estimated release could potentially be reduced if the HEPA filters are not compacted and waste containers could be distributed throughout a large space, thereby diluting the contaminant release. Additionally, a better cementitious material could be used to encapsulate the HEPA filters. One alternative method for disposal of contaminated HEPA filters is encapsulation of the filters in ultra high-performance grout (UHPG). UHPG is a variation of ultra-high-performance concrete (UHPC) is commonly used in the prestressed concrete industry for large structural members. Recent studies of UHPG show it has excellent properties for containing radionuclides such as 99 Tc and 129 I Nichols and Kaplan (2021). This report presents the results of the first attempt to encapsulate a clean, full-size HEPA filter in UHPG and evaluate the effectiveness of the immobilization process and final waste form. A full-scale proof-of-concept simulated waste form was prepared by encapsulating a HEPA filter in a 110-gallon stainless steel (SS) drum using UHPG. A change from Type I/II PC to Type 1L PLC was made after American Rock Products informed the team that they would no longer be using Type I/II by the end of 2024 and the northwest was phasing out Type I/II PC overall. Type I/II PC used in previous studies of UHPG for encapsulation (Nichols and Kaplan 2021). After the UHPG was cured both the scaled mockup and the full-scale simulated waste forms were sectioned for visual examination. UHPG completely encapsulated the filters and bonded to the external surfaces of materials comprising the filters. No cracks were observed in the sectioned waste forms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Surface Wettability Analysis from Adsorption Energy and Surface Electrical Charge

Surface wettability is determined by the attraction of a liquid phase to a solid surface. It is typically quantified by using contact angle measurements at mineral surfaces in the case of the flotation of mineral particles. Contact angle research to describe wettability has been investigated at different scales by sessile drop measurements, molecular dynamic simulation, and atomic force microscopy. In this study, the density functional theory (DFT) was employed for predicting the surface free energy and contact angles of a well-known hydrophobic phyllosilicate mineral talc and a well-known hydrophilic phyllosilicate mineral muscovite based on the calculated interfacial energy and surface charge. The results revealed that the predicted contact angle at the atomic scale was larger than the experimental value, and identified two interactions: electrostatic interaction and hydrogen bonding, between the hydrophilic muscovite surface and the water layer, while a water-exclusion zone of 3.346 Å was found between the hydrophobic talc surface and the first water layer. This investigation gives a new perspective for wettability determination at the atomic scale.

Geochemistry & Geophysics↗

Self-Assembly Driven Microlithography via Near-Infrared Light Activation

Current vat photopolymerization (VP) relies on UV or visible light to start the rapid crosslinking of liquid photocurable resins into 3D-printed structures. Here, we develop a self-assembly-driven photopatterning approach to photothermally generate polymeric solids by combining thermoplasmonic nanoparticles and thermoresponsive polymers, in which near-infrared (NIR) light activates thermoplasmonic heating of nanoparticles, triggering the irreversible self-assembly of thermoresponsive polymers into insoluble mesoglobules. A small amount of thermal initiator and crosslinker leads to irreversible self-assembly of polymer nanocomposites. NIR light offers deeper penetration and reduced scattering compared to UV, enabling more uniform curing of thicker or filled materials and expanded process control for composites or opaque systems. Thermoplasmonic heat generation is achieved using surface-modified gold nanorods (AuNRs) with a longitudinal localized surface plasmon resonance peak in the NIR region. Key variables such as polymer composition, molecular weight, physical interactions at the nanoparticle–polymer interface, which can be tuned by surface functionalization, AuNR concentration, and pH can be used to tailor the assembly behavior of these systems, including photothermal effect, flocculation, and cloud point temperature, and the mechanical properties of the final structures. Collectively, these results highlight a platform for photothermally-driven microlithography of polymer solids with diverse, tunable macroscopic properties, enabled by low-energy NIR light-activated self-assembly.

36 MATERIALS SCIENCE↗

Solventless, Ambient-Pressure Production of Bio-Based Lactones Over Earth-Abundant, Mixed Metal Oxide Catalysts for Circular Polyesters

Transitioning to a circular plastics economy will require use of renewable feedstocks, energy-efficient processes, and closed-loop recyclable polymers, such as polyesters. A key challenge lies in sustainably sourcing monomers used to make recyclable polyesters. This work presents a catalytic platform utilizing earth-abundant Cu(x)Ca(1-x)O mixed metal oxides for the oxidative dehydrocyclization of bio-based diols to lactones, which are advantaged for energy-efficient ring-opening polymerization. Operating below 200 degrees C, at ambient pressure, and without solvent, the process uses air as the sole oxidant, achieving high yields of lactones across a broad substrate scope of C4-8 diols in the liquid phase. The oxidative dehydrocyclization reaction is thermodynamically downhill due to water formation and energy-efficient compared to incumbent, non-redox pathways utilized in fossil carbon-based industrial processes for lactone production. Mechanistic studies reveal facile redox cycling of Cu2+-O(Ca2+)-Cu2+ interfacial sites unique to the developed catalyst. Techno-economic analysis and life cycle assessment estimate 40% lower energy demand and 15% lower GHG intensity per mass of butyrolactone produced compared to the fossil carbon-based route. Liquid-phase oxidative dehydrocyclization offers a promising approach for scalable lactone production from renewable, bio-based diols to enable circular polyesters.

36 MATERIALS SCIENCE↗

Plant Characteristics, Porewater, Gas Flux, and Soil Biogeochemistry at Council Road Site Mile Marker 71, Seward Peninsula, Alaska, 2023

Data collected at Council, AK (64°51’35.0”N 163°41’59.1”W) during a summer campaign in 2023. Water data consists of soil porewater collected by centrifuging soil cores and also by field collection with porewater samplers (rhizons). Gas data consists of CO2, CH4 and N2O surface soil fluxes measured with a portable FTIR analyzer. Plant and root data consists of biomass, root length, diameter and mass. Soil data consists of total C and N. Air, water and soil samples span two main locations: a thermokarst wetland and an upland tussock. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).This dataset was generated to broadly address the following research question: how will climate change (i.e., thawing permafrost, landscape change) alter the ecosystem flux (sink versus source) of important greenhouse gases such as CO2, CH4 and N2O?Description of the contents of this data package: This dataset contains 5 different individual .csv files containing plant, soil, water and gas data. No software is needed to utilize them. PFTCover: Plant functional type ground cover in 1x1 meter plots. SoilCores: Solidphase and porewater phase soil biogeochemical variablesPlantData: Above and belowground plant traits. GasFlux: Surface plant-soil gas measurementsFieldPorewater: Field collected porewater biogeochemical variables

54 ENVIRONMENTAL SCIENCES↗

Evaluation of New Additions to OLI Software in Predicting Mercuric and Mercurous Species in Liquid Waste Operations

Speciation of mercury during the pretreatment steps of tank waste processing is critical to successful mercury removal prior to vitrification during Liquid Waste Operations (LWO) at SRS. OLI software has been used to predict mercury speciation and activity throughout LWO. The OLI software operates based on a thermodynamic framework called the Mixed Solvent Electrolyte (MSE) framework. The MSE framework allows prediction in theoretically infinitely dilute to concentrated mixtures (e.g., purely solute solutions). Before modification to the MSE framework databanks, certain critical mercury species were missing in the MSE databank, and some thermodynamic data needed to be updated for the OLI software to accurately predict mercury chemical species in SRS waste tanks. To better reflect streams across LWO, new mercury species were integrated into the MSE database. To evaluate the changes to the OLI MSE framework per the Technical Task Request (TTR) and the Task Technical and Quality Assurance Plan (TTQAP), waste stream compositions from Tanks 38, 43, and Tank 50 decontaminated salt solution (DSS) were used as model inputs. Models were developed and executed using both the old and new databases. Compositional analyses from caustic Tank 50 DSS and caustic Tanks 38 and 43 were used as the input streams. These streams represent the most comprehensive chemical data sets where both mercury and tank constituents were measured together. Results for Tank 50 DSS predict HgO as the predominant species in both databases. Both methyl and dimethyl Hg species are present when the new database is ‘on’ and are not predicted with the new database turned ‘off’. The new database predicts a greater amount of HgO and a greater fraction of it in the solid phase. Pourbaix diagrams (potential vs. pH) generated for each Tank 50 DSS were identical regardless of which database was used. Elemental Hg and HgO were predicted in the water stable region under basic conditions. Tanks 38 and 43 follow similar trends as the Tank 50 DSS models. Unlike Tanks 38 and 50 DSS, the Tank 43 Pourbaix plot shows a region of stability for an aqueous HgOHCO3 - species between approximately pH 7-11. In all streams, when MeHg+ is included in the inputs, the new database predicts aqueous MeHgOH as the dominant species. If elemental or dimethyl mercury is in the waste stream, the new database model predicts they are unchanged and remain in those states and quantities. Additionally, the total mercury values are reported for both the measured input data and the OLI output data for all considered tanks. The summary indicates that the percentage error between the measured and calculated values is less than 1% in all cases The reconciliations and generation of the Pourbaix diagrams for Tank 50 DSS took approximately ten times longer with the new database ‘on’. In addition, over the course of that time, models with the new database ‘on’ were more likely to crash or display an error. Some modest performance improvements were noted when modeling with an i7 processor versus an i5. An example error is found in Appendix A. Furthermore, Appendix B provides V&V for two chemical systems analyzed with the OLI software, results were satisfactory. It is recommended to utilize the new databases (i.e., HCO.ddb and SR-Hg.ddb) in future Savannah River Mission Completion applications of OLI to represent pseudo steady-state. Furthermore, the integration and utilization of the new databases (i.e., HCO.ddb and SR-Hg.ddb) in modeling applications (e.g., Aspen) is also recommended.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Experimental and Theoretical Thermokinetic Analysis of the Na 3 VO 4 –CO 2 Reaction System under Different Physicochemical Conditions

Sodium vanadate (Na 3 VO 4 ) was synthesized, structural and microstructurally characterized as well as tested as possible carbon dioxide (CO 2 ) captor through thermodynamic calculations in addition to thermogravimetric dynamic and isothermal analyses. Ceramic structural characterization evidenced the formation of the Na 3 VO 4 crystal phase, while microstructural features evidenced dense agglomerates with a poor specific surface area, although synthesis temperature (600 °C) was not as high as that for other sodium ceramics. Na 3 VO 4 was investigated for the CO 2 capture process through dynamic and isothermal experiments, in the presence or absence of oxygen. All these experiments showed that Na 3 VO 4 possesses interesting CO 2 capture properties in a specific temperature range (520 and 600 °C). Isothermal products characterization allowed to elucidate the reaction pathway, implying the Na 4 V 2 O 7 formation, as possible reactive intermediate. In fact, reaction path evolution was supported with theoretical thermodynamic data. Moreover, the kinetic analysis, performed using the Avrami-Erofeev mathematical model and subsequent thermodynamic data obtention, probed the positive influence of the temperature, in both CO 2 superficial and bulk chemical sorption processes, while oxygen addition did not enhance the superficial process. Additionally, as it would be expected, kinetics were enhanced as a function of the CO 2 concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactive flash sintering and characterization of bulk high entropy nitrides

Over the past decade, numerous high-entropy ceramics have been synthesized, often displaying attractive properties. However, the study on facile preparation of bulk high entropy nitrides (HEN) are limited, despite its broad potential applications. This research demonstrates for the first time rapid fabrication (within ∼6 min) of bulk high-entropy nitrides, especially (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N, from binary nitride powder mixtures using a highly efficient reactive flash sintering (RFS) technique. X-ray diffraction (XRD) shows the HENs from RFS are near single-phase solid solutions with a rock salt crystal structure, while in situ synchrotron study carried out during RFS captured in real time the formation of HEN, which was preserved upon cooling, suggesting thermodynamic stability of the HEN phase, even up to extreme pressure (∼35.6 GPa). Microscopic analyses using SEM, STEM, and EDS reveal decent uniformity for HEN with no obvious segregation of elements, even to submicron scale. Some properties of the obtained bulk HENs are consistent with expectations. For example, their hardness and bulk modulus are close to estimates based on rule-of-mixture (ROM) values from the constituent binary nitrides. Meanwhile, some other measured properties seem to show surprises. For example, the fracture toughness for the HENs (e.g., 7.81 ± 1.40 MPa•m 1/2 or higher) turns out to be more than double of the expected ROM estimates. The significantly improved fracture toughness is attributed to the observed nano-layered structure of the HENs, despite the HEN’s cubic crystal structure and high hardness. In addition, the oxidation resistance shows improvement up till ∼800°C, possibly due to Ta doping that suppress oxygen vacancy formation in the oxide shell, while the 5-metal HEN of (Al 0.17 Nb 0.17 Ta 0.17 Ti 0.32 Zr 0.17 )N displays superconductivity (T c of ∼5–7 K from magnetism and resistivity measurements, slightly lower than ROM estimate), despite insulating property of starting AlN. Furthermore, future study combining experimental investigation using larger samples to confirm the observed increase in fracture toughness and oxidation resistance, theoretical modeling at different length scale, and more detailed structural/chemical characterization, especially at the atomic scale, are all needed to fully understand the inter-relationships between composition, processing, structure, and novel properties for these HENs and the development of related new materials for different applications.

Flash sintering↗

Probing intrinsic magnetization dynamics of the Y 3⁢ Fe 5 ⁢O 12 /Bi 2 ⁢Te 3 interface at low temperature

Topological insulator–magnetic insulator (TI–MI) heterostructures hold significant promise in the field of spintronics, offering the potential for manipulating magnetization through topological surface state–enabled spin-orbit torque. However, many TI–MI interfaces are plagued by issues such as contamination within the magnetic insulator layer and the presence of a low-density transitional region of the topological insulator. These interfacial challenges often obscure the intrinsic behavior of the TI–MI system. In this study, we addressed these challenges by depositing sputtered Bi 2 ⁢Te 3 on liquid phase epitaxy grown Y 3 ⁢Fe 5 ⁢O 12 /Gd 3 ⁢Ga 5 ⁢O 12 . The liquid phase epitaxy grown Y 3 ⁢Fe 5 ⁢O 12 has been previously shown to have exceptional interface quality, without an extended transient layer derived from interdiffusion processes of the substrate or impurity ions, thereby eliminating rare-earth impurity-related losses in the MI at low temperatures. At the TI–MI interface, high-resolution depth-sensitive polarized neutron reflectometry confirmed the absence of a low-density transitional growth region of the TI. By overcoming these undesirable interfacial effects, we isolate and probe the intrinsic low-temperature magnetization dynamics and transport properties of the TI–MI interface. In conclusion, our findings revealed strong spin pumping at low temperatures, accompanied by an additional in-plane anisotropy. The enhanced spin pumping at low temperatures is correlated with the observed suppression of bulk conduction and the weak antilocalization in the TI film, highlighting the interplay between the transport and spin pumping behavior in the TI–MI system.

36 MATERIALS SCIENCE↗

Efficient machine learning interatomic potentials robust for liquid and multiple solid polymorphs of NaF and KF

Achieving atomic-level understanding of crystallization of molten salts is of importance to a wide range of technological applications. Recent work [Fan et al., Proc. Natl. Acad. Sci. USA 122, e2425702122 (2025)] revealed that crystal nucleation in molten LiF salt is a multistage process according to the molecular-dynamics (MD) simulations based on an atomic cluster expansion (ACE) machine-learning interatomic potential (MLIP). In order to understand the influence of increasing cation size on nucleation pathways and nucleation rates of molten fluoride salts, here we develop two new ACE MLIPs for NaF and KF. The two ACE MLIPs feature DFT-SCAN-level accuracy for liquid and multiple solid polymorphs over a wide temperature (0–2000 K) and pressure (0–100 GPa) range, and also reproduce well a number of experimental data for solid and liquid equilibrium properties. The efficiency of the two ACE MLIPs enable million-atom-scale or microsecond-scale MD simulations. The two general-purpose ACE MLIPs are expected to be useful for atomistic simulations for different purposes, in addition to studying crystallization of molten NaF and KF salts.

Crystal melting↗

Suppressing Ordering in Equiatomic Fe-Co via Laser Powder Bed Fusion

Neutron and electron diffraction was employed to evaluate the effectiveness of thermal management strategies in suppressing the formation of the equilibrium-ordered B2 (CsCl) phase in equiatomic binary Fe-Co specimens fabricated by laser powder bed fusion additive manufacturing. Specimens with a tensile dogbone geometry were fabricated using various combinations of process parameters (laser power and raster speed) and thermal management strategies (no support struts, struts only in the top gauge section, and struts throughout the gauge section). Diffraction results demonstrate that the rapid solidification during PBF-L effectively minimized B2 formation, with laser power and effective scan velocity having no significant impact on the degree of ordering. Furthermore, the inclusion of support struts in the top grip region had no perceivable impact on ordering, whereas specimens with support struts in the gauge region exhibited no detectable ordering. Results are discussed in the context of thermal finite element analysis predictions.

Laser Material Processing↗

Filtration of Hanford Tank 241-AW-105 Supernatant at 16 °C

Approximately 9 L of supernatant from Hanford waste tank 241-AW-105 was delivered by Hanford Tank Waste Operations and Closure (H2C) to the Radiochemical Processing Laboratory (RPL) at Pacific Northwest National Laboratory (PNNL). The thirty-six 241-AW-105 sample bottles consisted of four sets of nine samples, with each set pulled from a unique tank sampling level. Prior to testing, samples from each level were composited and diluted to 5.5 M Na to provide nominally level-independent feed for dead-end filtration and ion exchange testing. The composited 241-AW-105 supernatant was chilled to 16 °C for 1 week prior to testing. Filtration testing was then conducted using a backpulse dead-end filter (BDEF) system equipped with a feed vessel and a Mott inline filter (Model 6610, Media Grade 5) in the hot cells of the RPL. The purpose of this testing was to (a) demonstrate dead-end filtration (DEF) of 241-AW-105 feed at reduced temperature to obtain prototypic Tank Side Cesium Removal (TSCR) flux rates and identify issues that may impact filtration after dilution to 5.5 M Na, and (b) provide feed for follow-on ion exchange unit operation. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft2. For most of the filtration campaign, the differential pressure required to effect filtration at 0.065 gpm/ft2 was slow to increase. After all the feed bottles had been pumped into the slurry reservoir, the bottoms of the bottles were added to the reservoir and transmembrane pressure (TMP) reached 2.0 psid (the TSCR action limit). A backpulse was performed after >50 hours of filtration to remove fouled solids and reduce the TMP. The filter was cleaned after completing filtration of the 241-AW-105 feed, and clean water flux tests showed filter performance was effectively restored. Solids concentrated from the backpulse solutions were composed of steel-like particles, uranium-bearing phases, Mn-Fe phases, a Ce-bearing phase, Zr phases, and some smaller Ca-bearing particles. The Ca-bearing and U bearing phases were identified as calcite and clarkeite, respectively.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗