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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Benchmarking the AirSquared All-Metal Scroll Pump Against the Normetex 15 - Preliminary report

Tritium operations require specialized equipment for material compatibility, safety, and waste considerations. Non-metallic pump materials (polymer, oil, or grease) on a tritium-wetted surface can absorb tritium and/or undergo isotope exchange between tritium and more common protium, creating tritiated compounds that can result in material property modification via beta-radiolysis, inventory loss, reduced performance and special waste considerations, all of which increase the operating cost for a facility. Vacuum pumps move gas via a pressure differential between volumes of an operation. Several types of all-metal vacuum pumps exist for this application including metal bellows, diaphragm and scroll pumps. A metal bellows pump incorporates only metal components at the wetted surfaces. The common metal bellows pump employed in tritium facilities, the MB601 (Senior Metal Bellows, Sharon, PA, USA) creates a gas-motive force with a vacuum pressure between 30-40 torr. These pumps can efficiently move gas from one process step to another, as long as sub-30 torr pressures are not required. However, for higher vacuum demand, an all-metal scroll pump can be used with the bellows pump serving as a “backing” pump. This configuration typically provides an achievable vacuum of less than 20 mTorr. All-metal scroll pumps are a technology uniquely applicable to tritium gas handling. The industry standard all-metal scroll pump for glovebox-scale tritium operations is the Normetex 15 m 3 /hr, typically referred to as the Normetex 15 (Normetex Pompes, Pont Audemer, France). However, the final Normetex pumps were manufactured in 2012, rendering them no longer available. Eumeca SaRL (formerly Normetex) has developed and is marketing a scroll pump based on the design of the Normetex 15. A US company, AirSquared (Broomfield, Colorado), has developed and is marketing a potential alternative to the Normetex 15. The Gas Transfer Systems group (Q-7) of the Los Alamos National Laboratory (LANL) procured serial number 0001 of the AirSquared All Metal Vacuum Scroll pump model number V16H034A-C01 in 2019. The LANL Hydrogen Processing Laboratory (HPL) has been evaluating the performance of the pump compared to a Normetex pump as a potential replacement in tritium and fusion facilities requiring this type of pump.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Surface heat flux and its association with the MJO in the tropical western Pacific using ARM observations

The Madden-Julian oscillation (MJO) is a major atmospheric phenomenon in the tropics that moves eastward every 20 to 100 days. It brings heavy rain and strong winds, influencing extreme weather events far beyond the tropics – including flooding, hurricanes, tornadoes and heavy snow in the United States. Therefore, an improved understanding of the MJO is critical for enhancing weather forecasts and supporting better decision-making for communities, emergency managers, and the private sector. Past studies, based on short-term observations or long-term model data, have emphasized the dominant role of atmospheric humidity in driving the MJO. Our research, using long-term observations (2000-2014) from three U.S. Department of Energy’s Atmospheric Radiation Measurement (ARM) sites in the tropical western Pacific (Manus, Nauru, and Darwin) confirms those past findings. However, we also show that atmospheric temperature, especially in the mid and upper troposphere, also plays a key role in the MJO’s evolution from its quiet (suppressed) to convective (active) phase. These findings provide valuable insights into how the MJO evolves and may help evaluate and improve weather and climate models. Our study also examined how the exchange of heat between the Earth's surface and the atmosphere, called surface heat flux, interacts with the MJO. This flux includes components such as latent heat (related to evaporation), sensible heat (related to temperature difference between surface and atmosphere), and radiation. We found that modulation in MJO convection is well connected to surface heat flux over the tropical western Pacific. One surface heat flux component often overlooked is the sensible heat flux due to precipitation (Q P ). Since falling raindrops are typically cooler than the land or ocean surface, they can cool the surface and affect local weather. To test the impact of Q P on convection during MJO, we incorporated it into a weather model, and ran simulations for two periods: April 2009 (when the MJO was active) and June 2006 (when it was not). Including Q P reduced errors in simulating the daily peak of rainfall—by 83% during the strong MJO and 23% during the inactive phase. It also improved the timing of peak daily rainfall and reduced the overall precipitation error by about 10%. These improvements were especially noticeable during periods of heavy rainfall. Our results suggest that even small heat exchanges from rainfall can play a significant role in shaping local weather. Accounting for these effects, particularly in regions like the tropical islands, can lead to more accurate simulations of the MJO-associated precipitation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Uniaxial Spin Texture in a Superconducting Electron Gas Revealed by Exchange Interactions

Two-dimensional (2D) superconductors with spin-textured Fermi surfaces can be a platform for realizing unconventional pairing states and are of substantial interest in the context of quantum information science and superconducting spintronics/orbitronics. We observed an unusual in-plane uniaxial anisotropy in the superconducting 2D electron gas (2DEG) formed at EuOx/KTaO3 (110) interfaces. This anisotropy is not evident in AlOx/KTaO3 (110) where the overlayer is nonmagnetic. Our results are consistent with a highly anisotropic “half-Rashba” spin-textured Fermi surface in 2DEGs formed at the KTaO3 (110) interface that is hidden from external magnetic fields due to a near cancellation between orbital and spin moments but revealed by exchange interactions of the electrons in the 2DEG with Eu moments near the EuOx/KTaO3 (110) interface. The interactions between the uniaxial spin texture and the magnetic overlayer offer previously unexplored ways to explore the interplay between magnetism and 2D superconductivity.

Yang, Junyi↗
DOE OSTI2022

Domain state exchange bias in a single layer FeRh thin film formed via low energy ion implantation

Modern spintronics relies heavily on the exchange bias effect to pin the orientation of ferromagnetic layers in magnetic tunnel junctions. The current implementations of exchange bias in magnetic tunnel junctions employ pristine interfaces between antiferromagnetic and ferromagnetic layers. Here we reveal an interfacial exchange bias introduced by a single-step, low-energy ion implantation process in a single layer FeRh thin film. Both 1 keV He + ions and 5 keV Fe + were investigated, their energy selected to ensure the ions would stop within the FeRh film. The ions reduce the metamagnetic transition temperature through defect generation to form a surface layer with ferromagnetic ordering. Temperature dependent magnetism measurements reveal a room temperature exchange bias between the ferromagnetic surface and the antiferromagnetic bulk of ~41 Oe in 5 keV Fe + implanted samples and ~36 Oe for 1 keV He + implanted samples. We directly scrutinize this exchange bias effect in magnetic depth profiles obtained by polarized neutron reflectometry which clearly show a pinned ferromagnetic layer adjacent to the disordered layer created by low energy Fe + ion implantation. These results reveal a novel method to implement exchange bias in an antiferromagnetic layer that can have direct application in the field of spintronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Isotope ratio-based quantification of carbon assimilation highlights the role of plastidial isoprenoid precursor availability in photosynthesis

Abstract Background We report a method to estimate carbon assimilation based on isotope ratio-mass spectrometry (IRMS) of 13 CO 2 labeled plant tissue. Photosynthetic carbon assimilation is the principal experimental observable which integrates important aspects of primary plant metabolism. It is traditionally measured through gas exchange. Despite its centrality in plant research, gas exchange performs poorly with rosette growth habits typical of Arabidopsis thaliana , mutant lines with limited biomass, and accounts poorly for leaf shading. Results IRMS-based carbon assimilation values from plants labeled at different light intensities were compared to those obtained by gas exchange, and the two methods yielded similar values. Using this method, we observed a strong correlation between 13 C content and labeling time (R 2 = 0.999) for 158 wild-type plants labeled for 6 to 42 min. Plants cultivated under different light regimes showed a linear response with respect to carbon assimilation, varying from 7.38 nmol 13 C mg −1 leaf tissue min −1 at 80 PAR to 19.27 nmol 13 C mg −1 leaf tissue min −1 at 500 PAR. We applied this method to examine the link between inhibition of the 2 C -methyl- d -erythritol-4-phosphate (MEP) pathway and suppression of photosynthesis. A significant decrease in carbon assimilation was observed when metabolic activity in the MEP pathway was compromised by mutation or herbicides targeting the MEP pathway. Mutants affected in MEP pathway genes 1-DEOXY- d -XYLULOSE 5-PHOSPHATE SYNTHASE (DXS) or 1-HYDROXY-2-METHYL-2-(E)-BUTENYL 4-DIPHOSPHATE SYNTHASE (HDS) showed assimilation rates 36% and 61% lower than wild type. Similarly, wild type plants treated with the MEP pathway inhibitors clomazone or fosmidomycin showed reductions of 52% and 43%, respectively, while inhibition of the analogous mevalonic acid pathway, which supplies the same isoprenoid intermediates in the cytosol, did not, suggesting inhibition of photosynthesis was specific to disruption of the MEP pathway. Conclusions This method provides an alternative to gas exchange that offers several advantages: resilience to differences in leaf overlap, measurements based on tissue mass rather than leaf surface area, and compatibility with mutant Arabidopsis lines which are not amenable to gas exchange measurements due to low biomass and limited leaf surface area. It is suitable for screening large numbers of replicates simultaneously as well as post-hoc analysis of previously labeled plant tissue and is complementary to downstream detection of isotopic label in targeted metabolite pools.

2C‑methyl‑d‑erythritol 4‑phosphate pathway↗
DOE OSTI2025

Nickel hydroxide–nickel carbonate competitive growth on carbonate surfaces

The thermodynamic and kinetic factors controlling the competitive heterogeneous nucleation and growth of ubiquitous metal carbonate and hydroxide phases are poorly understood. In this work, calcite (CaCO 3 ) and magnesite (MgCO 3 ) powders were reacted with NiCl 2 (0–600 μM) for 7 days at 22 °C and 5 °C. The reacted powders were analyzed with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and energy-dispersive X-ray spectroscopy to characterize the Ni surface precipitates formed. Evidence from these techniques pointed to the formation of mixed Ni carbonate-Ni hydroxide amorphous surface precipitates. On calcite, XPS detected primarily Ni(OH) 2 despite the initial solutions being more supersaturated with respect to gaspéite (NiCO 3 ) than to theophrastite (Ni(OH) 2 ) by a factor of 17–18. In contrast, NiCO 3 was the dominant component detected by XPS on magnesite in the same conditions. Decreasing the temperature had the effect of increasing the proportion of NiCO 3 to the detriment of Ni(OH) 2 . The experimental observations were consistent with low lattice/cation size mismatch favoring NiCO 3 nucleation and temperature most influencing Ni(OH) 2 nucleation. Comparison to previous work on Co-reacted powders indicated the differences in lattice/cation size mismatch and/or water exchange rate impacted the composition of the surface precipitates more than the relative thermodynamic stabilities of the competing minerals. This work explored the heterogeneous growth regime of Ni carbonate and hydroxide phases on carbonate surfaces and shed light on the factors that control the competition between surface precipitates when mineral surfaces are in contact with aqueous solutions supersaturated with respect to multiple mineral phases. In conclusion, these results contribute to geochemists’ efforts toward interpreting data from geochemical systems with elevated Ni concentrations, improving Ni environmental remediation and recovery strategies, and predicting the fate and transport of Ni in geochemical systems.

Heterogeneous nucleation↗
DOE OSTI2024

Unraveling the Luminescence Quenching Mechanism in Strong and Weak Quantum-Confined CsPbBr 3 Triggered by Triarylamine-Based Hole Transport Layers

Luminescence quenching by hole transport layers (HTLs) is one of the major issues in developing efficient perovskite light-emitting diodes (PeLEDs), particularly prominent in blue-emitting devices. While a variety of material systems have been used as interfacial layers, the origin of such quenching and the type of interactions between perovskites and HTLs are still ambiguous. Here, we present a systematic investigation of the luminescence quenching of CsPbBr 3 by a commonly employed hole transport polymer, Poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (TFB) in LEDs. Strong and weakly quantum-confined CsPbBr 3 (nanoplatelets (NPLs)/nanocrystals (NCs)) are rationally selected to study the quenching mechanism by considering the differences in their morphology, energy level alignments, and quantum confinement. The steady-state and time-resolved Stern-Volmer plots unravel the dominance of dynamic and static quenching at lower and higher concentrations of TFB, respectively, with maximum quenching efficiency of 98%. The quenching rate in NCs is faster than in NPLs owing to their longer PL lifetimes and weak quantum confinement. The ultrafast transient absorption results support these dynamics and rule out the involvement of Forster or Dexter energy transfer. Finally, the 1D 1 H and 2D NOESY NMR study confirms the exchange of native ligands at the NCs surface with TFB, leading to dark CsPbBr 3 -TFB ensemble formation accountable for luminescence quenching. This highlights the critical role of the triarylamine functional group on TFB (also the backbone of many HTLs) in the quenching process. These results shed light on the underlying reasons for the luminescence quenching in PeLEDs and will help to choose the interfacial layers rationally for developing efficient LEDs.

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

A multirate mass transfer model to represent the interaction of multicomponent biogeochemical processes between surface water and hyporheic zones (SWAT-MRMT-R 1.0)

Abstract. Surface water quality along river corridors can be modulated by hyporheic zones (HZs) that are ubiquitous and biogeochemically active. Watershed management practices often ignore the potentially important role of HZs as a natural reactor. To investigate the effect of hydrological exchange and biogeochemical processes on the fate of nutrients in surface water and HZs, a novel model, SWAT-MRMT-R, was developed coupling the Soil and Water Assessment Tool (SWAT) watershed model and the reaction module from a flow and reactive transport code (PFLOTRAN). SWAT-MRMT-R simulates concurrent nonlinear multicomponent biogeochemical reactions in both the channel water and its surrounding HZs, connecting the channel water and HZs through hyporheic exchanges using multirate mass transfer (MRMT) representation. Within the model, HZs are conceptualized as transient storage zones with distinguished exchange rates and residence times. The biogeochemical processes within HZs are different from those in the channel water. Hyporheic exchanges are modeled as multiple first-order mass transfers between the channel water and HZs. As a numerical example, SWAT-MRMT-R is applied to the Hanford Reach of the Columbia River, a large river in the United States, focusing on nitrate dynamics in the channel water. Major nitrate contaminants entering the Hanford Reach include those from the legacy waste, irrigation return flows (irrigation water that is not consumed by crops and runs off as point sources to the stream), and groundwater seepage resulting from irrigated agriculture. A two-step reaction sequence for denitrification and an aerobic respiration reaction is assumed to represent the biogeochemical transformations taking place within the HZs. The spatially variable hyporheic exchange rates and residence times in this example are estimated with the basin-scale Networks with EXchange and Subsurface Storage (NEXSS) model. Our simulation results show that (1), given a residence time distribution, how the exchange fluxes to HZs are approximated when using MRMT can significantly change the amount of nitrate consumption in HZs through denitrification and (2) source locations of nitrate have a different impact on surface water quality due to the spatially variable hyporheic exchanges.

58 GEOSCIENCES↗
DOE OSTI2022

Binder jet additive manufacturing of ceramic heat exchangers for concentrating solar power applications with thermal energy storage in molten chlorides

Triply periodic minimal surface (TPMS) geometries can only be fabricated by additive manufacturing methods and are of interest for heat exchangers. Ceramic TPMS heat exchangers can operate at higher temperatures and pressures with superior performance and increased operating efficiencies compared to metal heat exchangers. The properties of ultra-high temperature ceramic (UHTC) materials are also favorable for heat exchangers and potentially suited to concentrated solar power (CSP) systems, such as those based on a molten chloride salt thermal energy storage (TES) medium used to heat CO 2 in a closed-loop Brayton power cycle. We intended to demonstrate binder jet additive manufacturing feasibility of a UHTC-TPMS structure by printing and sintering a null candidate. We aimed to achieve parts with a relative density ≥ 92 % of theoretical and to provide a TPMS part demonstration. The target density indicates the transition from intermediate to final stage sintering, a requirement to inhibit gas permeability and for sintering complex near net shapes to full density with sinter-HIP technology. The goal of the TPMS part demonstration was to determine if printing and sintering parameters developed from test coupons apply to the complex geometries that will eventually be used in a heat exchanger design. Our objective was to print cubic TPMS parts with a 9 cm 3 volume and sinter it without distorting and cracking. We report we were able to sinter ZrB 2 -MoSi 2 composite parts based on the Schwarz-D TPMS and achieve isotropic shrinkage up to 60 % by volume, resulting in densities ranging from 92 % to 96 % of theoretical.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Organic matter transformations are disconnected between surface water and the hyporheic zone

Abstract. Biochemical transformations of organic matter (OM) are a primary driver of river corridor biogeochemistry, thereby modulating ecosystem processes at local to global scales. OM transformations are driven by diverse biotic and abiotic processes, but we lack knowledge of how the diversity of those processes varies across river corridors and across surface and subsurface components of river corridors. To fill this gap we quantified the number of putative biotic and abiotic transformations of organic molecules across diverse river corridors using ultra-high-resolution mass spectrometry. The number of unique transformations is used here as a proxy for the diversity of biochemical processes underlying observed profiles of organic molecules. For this, we use public data spanning the contiguous United States (ConUS) from the Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems (WHONDRS) consortium. Our results show that surface water OM had more biotic and abiotic transformations than OM from shallow hyporheic zone sediments (1–3 cm depth). We observed substantially more biotic than abiotic transformations, and the numbers of biotic and abiotic transformations were highly correlated with each other. We found no relationship between the number of transformations in surface water and sediments and no meaningful relationships with latitude, longitude, or climate. We also found that the composition of transformations in sediments was not linked with transformation composition in adjacent surface waters. We infer that OM transformations represented in surface water are an integrated signal of diverse processes occurring throughout the upstream catchment. In contrast, OM transformations in sediments likely reflect a narrower range of processes within the sampled volume. This indicates decoupling between the processes influencing surface water and sediment OM, despite the potential for hydrologic exchange to homogenize OM. We infer that the processes influencing OM transformations and the scales at which they operate diverge between surface water and sediments.

58 GEOSCIENCES↗
DOE OSTI2021

High flux boiling heat transfer enhancement using triangle shaped vertical walls in two-phase microchannel heat exchangers

Two-phase heat exchangers allow heat loads to be dissipated with lower fluid flow rates without inducing thermal gradients, and high surface area microchannels further reduce the thermal resistance of these heat exchangers. However, there are many practical limits that prevent widespread use of two-phase microchannel heat exchangers. Many authors have looked to address these practical limits by treating the channel floors or creating artificial nucleation sites. Few works look to enhance heat transfer in the walls of channels with hydraulic diameters below 200 μm. This work is aimed at increasing the efficacy of high aspect ratio silicon microchannels that use R134a as the working fluid. The 125 parallel channels are 40 μm wide, 200 μm deep, and 2 mm long and contain a 15 μm wide, 150 μm long restriction at each inlet. The thermal resistance and dryout characteristics of traditional, plain-walled channels are compared to channels with 2 area enhancement patterns each of which increases the area available for heat transfer by 41%. Furthermore, a resistance to dryout is seen in both area-enhanced test sections, and a 15.5% reduction in thermal resistance is shown for the area-enhanced part with a 6 μm triangular pitch. Only a 7.8% performance increase is seen in the test section with a 3 μm pitch. Both area enhancement patterns induce an average 27% increase in pressure drop for all tests. Heat transfer characteristics are solved for using a finite element analysis (FEA) model. By examining heat transfer coefficients and local heat fluxes, it is postulated that the area enhancement reduces heat transfer coefficients and the performance increase is caused by increasing the number of active nucleation sites.

42 ENGINEERING↗
DOE OSTI2024

Reducing Ohmic Resistances in Membrane Capacitive Deionization Using Micropatterned Ion-Exchange Membranes, Ionomer Infiltrated Electrodes, and Ionomer-Coated Nylon Meshes

Membrane capacitive deionization (MCDI) is an emerging water desalination platform that is compact, electrified, and does not require high-pressure piping. Herein, highly conductive poly(phenylene alkylene) ion-exchange membranes (IEMs) are micropatterned with different surface geometries for MCDI. The micropatterned membranes increase the interfacial area with the liquid stream leading to a 700 mV reduction in cell voltage when operating at constant current (2 mA cm -2 ; 2000 ppm NaCl feed) while improving the energy normalized adsorbed salt (ENAS) value by 1.4 times. Combining the micropatterned poly(phenylene alkylene) IEMs with poly(phenylene alkylene) ionomer-filled electrodes reduces the cell voltage by 1000 mV and improves the ENAS values by 2.3 times relative to the base case. This reduction in cell voltage allows for higher current density operation (i.e., 3–4 mA cm -2 ) . The reduction in cell voltage is ascribed to the ameliorating ohmic resistances related to ion transport at the membrane-process stream interface and in the carbon cloth electrode. Finally, porous ionic conductors are implemented into the spacer channel with flat and micropatterned IEM configurations and ionomer infiltrated electrodes. For the configuration with flat IEMs, the porous ionic conductor improves ENAS values across the current density regime (2–4 mA cm -2 ), while for micropatterned IEMs it gets improved only at 4 mA cm -2 .

42 ENGINEERING↗
DOE OSTI2025

Over three decades, and counting, of near-surface turbulent flux measurements from the Atmospheric Radiation Measurement (ARM) user facility

Processes mediating the coupling of terrestrial, aquatic, biospheric, and atmospheric systems influence weather, climate, and ecosystem dynamics via transfer of energy, momentum, water, and carbon (or other species). These exchange processes are quantified by measurements of near-surface turbulent fluxes. Understanding processes at these interfaces provides insight toward understanding and predicting current and future states within the Earth system. The Atmospheric Radiation Measurement (ARM) user facility has been conducting measurements of near-surface turbulent fluxes since the early 1990s at long-term fixed locations and shorter-term mobile deployments across the Earth. ARM has utilized two established methods for conducting these measurements: energy balance Bowen ratio (EBBR) and eddy covariance (EC). Primary measurements from the former include sensible and latent heat flux, while the latter also measures fluxes of momentum and carbon (primarily carbon dioxide, with methane fluxes measured at two locations to date). The EBBR systems have been deployed at 22 locations, and, to date, the EC systems have been deployed at over 50 sites, with plans for additional novel site locations in the future. Herein, the history, evolution, and key aspects of these instrument systems are documented, along with information on data quality assurance and post-processing, as well as best use practices. Additionally, three data validation experiments were recently conducted, and their key findings are summarized. Finally, ancillary datasets acquired by ARM, which can contextualize and aid interpretation of the near-surface turbulent flux measurements, are discussed. The datasets described herein include the eddy correlation flux measurement system: 30ECOR (https://doi.org/10.5439/1879993, Sullivan et al., 1997), 30QCECOR (https://doi.org/10.5439/1097546, Gaustad, 2003), ECORSF (https://doi.org/10.5439/1494128, Sullivan et al., 2019a), and associated AmeriFlux and Methane Value-Added Product, AMCMETHANE (https://doi.org/10.5439/1508268, Billesbach, 2011); the energy balance Bowen ratio system: 30EBBR (https://doi.org/10.5439/1023895, Sullivan et al., 1993) and 30BAEBBR (https://doi.org/10.5439/1027268, Gaustad and Xie, 1993); and the carbon dioxide flux measurement system: CO2FLX (https://doi.org/10.5439/1287574, https://doi.org/10.5439/1287575, https://doi.org/10.5439/1287576, Koontz et al., 2015a, b, c; https://doi.org/10.5439/1989774, https://doi.org/10.5439/1989776, https://doi.org/10.5439/1992202, Biraud and Chan, 2002a, b, c). These data can be found by searching the above data stream names at https://adc.arm.gov/discovery/#/results/ (last access: 8 September 2025).

Sullivan, Ryan C. [Argonne National Laboratory (AN↗
DOE OSTI2020

Competing ferro- and antiferromagnetic exchange drives shape-selective $\mathrm{Co_3O_4}$ nanomagnetism

We have synthesized three different shapes of Co 3 O 4 nanoparticles to investigate the relationships between the surface Co 2+ and Co 3+ bonding quantified by exploiting the known exposed surface planes, terminations, and coordiations of Co 3 O 4 nanoparticle spheres, cubes and plates. Subsequently this information is related to the unusual behaviour observed in the magnetism. The competition of exchange interactions at the surface provides the mechanism for different behaviours in the shapes. The cubes display weakened antiferromagnetic interactions in the form of a spin-flop that occurs at the surface, while the plates show distinct ferromagnetic behaviour due to the strong competition between the interactions. We elucidate the spin properties which are highly sensitive to bonding and crystal field environments. This work provides a new window into the mechanisms behind surface magnetism.

36 MATERIALS SCIENCE↗
DOE OSTI2022

MECHANICAL PERFORMANCE EVALUATION OF THE PRINTED CIRCUIT HEAT EXCHANGER CORE EXPERIMENTS UNDER TENSION AND PRESSURE LOADING

The printed circuit heat exchanger (PCHE) has small channels with high surface area, making them an efficient solution for next-generation nuclear plants (NGNPs). These PCHEs are fabricated through a diffusion bonding process. This fabrication step changes the microstructure of wrought metal plates. The current ASME design code does not support the PCHE design for NGNPs due to a lack of test data. Hence, there has been initiative towards elevated temperature mechanical property characterization of the diffusion bonded material. One of the most common channel shapes is a semicircular channel with sharp corners. These corners act as a stress riser at the diffusion bonding interface. Evaluating elevated temperature mechanical performance of diffusion bonded material in the presence of stress risers is an essential step towards the ASME code development of PCHE design. This study selected two specimen geometries: the first is a PCHE bar specimen for tensile loading with three rows and three columns of channels, and the second is a lab-scaled PCHE with six rows and eight columns of channels. A set of elevated temperature monotonic and cyclic tests were conducted on the PCHE bar specimen to evaluate the mechanical performance under axial tensile loadings to study the failure mechanism. The lab-scaled PCHE specimens were tested under overpressure loads at room temperature, and pressure creep and pressure creep-fatigue loadings to mimic the realistic loading conditions observed in typical NGNPs. The X-ray scans of channeled specimens show interesting observations. The test results and observations are presented in the paper.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Uncovering the predictive pathways of lithium and sodium interchange in layered oxides

Ion exchange is a powerful method to access metastable materials with advanced functionalities for energy storage applications. However, high concentrations and unfavourably large excesses of lithium are always used for synthesizing lithium cathodes from parent sodium material, and the reaction pathways remain elusive. Here, using layered oxides as model materials, we demonstrate that vacancy level and its corresponding lithium preference are critical in determining the accessible and inaccessible ion exchange pathways. Taking advantage of the strong lithium preference at the right vacancy level, we establish predictive compositional and structural evolution at extremely dilute and low excess lithium based on the phase equilibrium between Li 0.94 CoO 2 and Na 0.48 CoO 2 . Such phase separation behaviour is general in both surface reaction-limited and diffusion-limited exchange conditions and is accomplished with the charge redistribution on transition metals. Guided by this understanding, we demonstrate the synthesis of Na y CoO 2 from the parent Li x CoO 2 and the synthesis of Li 0.94 CoO 2 from Na y CoO 2 at 1-1,000 Li/Na (molar ratio) with an electrochemical assisted ion exchange method by mitigating the kinetic barriers. Our study opens new opportunities for ion exchange in predictive synthesis and separation applications. Ion exchange is a powerful method to access metastable materials for energy storage, but identifying lithium and sodium interchange in layered oxides remains challenging. Using such model materials, vacancy level and corresponding lithium preference are shown to be crucial for ion exchange pathway accessibility.

25 ENERGY STORAGE↗
DOE OSTI2022

Simulations of x-ray absorption spectra for CO desorbing from Ru(0001) with transition-potential and time-dependent density functional theory approaches

The desorption of a carbon monoxide molecule from a Ru(0001) surface was studied by means of X-ray Absorption Spectra (XAS) computed with Transition Potential (TP-DFT) and Time Dependent (TD-DFT) DFT methods. By unraveling the evolution of the CO electronic structure upon desorption, we observed that at 2.3 Å from the surface, the CO molecule has already predominantly gas-phase character. While C 1s XAS is quite insensitive to changes in the C–O bond length, the O 1s excitation is very sensitive with the π* coming down in energy upon CO bond stretching, which competes with the increase in orbital energy due to the repulsive interaction with the metallic surface. We show in a systematic way that the TP-DFT method can describe the XAS rather well at the endpoints (chemisorbed and gas phase) but is affected by artificial charge transfer and/or incorrect spin treatment in the transition region in cases like CO, where there are low-lying π* orbitals and large exchange interactions between the core 1s and valence-acceptor π* orbitals. As an alternative, we demonstrate by comparing with experimental data that a linear response approach using TD-DFT employing common exchange-correlation functionals and finite-size clusters can yield a good description of the spectral evolution of the 1s → π* transition with correct spin and gas-to-chemisorbed chemical shifts in good agreement with experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Temperature effects on adsorption and capillarity water retention mechanisms in constrained unsaturated soils

Abstract This paper focuses on the impact of elevated temperatures on the adsorptive and capillarity water retention mechanisms of unsaturated soils under constrained (constant volume) conditions. This topic is critical for simulating the thermo-hydraulic behavior of soils in hydrogeological or geotechnical applications, including climate change effects on near surface soils, energy piles or soil borehole thermal energy storage systems in unsaturated soil layers, and buffers for geological nuclear waste repositories. A nonisothermal soil water retention curve (SWRC) that separately considers the temperature-dependency of the key parameters governing adsorptive and capillarity water retention mechanisms and soil physical parameters (e.g., surface tension, contact angle, adsorption capacity, cation exchange capacity, mean cavitation suction, air entry value and equilibrium film thickness) was developed to provide insights into the impact of temperature on water retention over the full suction range. The nonisothermal SWRC was validated using experimental data on high plasticity clays, with a good prediction of temperature effects on adsorption and capillarity water retention mechanisms in constrained unsaturated soils.

Lu, Yu↗