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At least 1,063 records · Page 59

Symmetry Breaking and Ascending in the Magnetic Kagome Metal FeGe

Spontaneous symmetry breaking—the phenomenon in which an infinitesimal perturbation can cause the system to break the underlying symmetry—is a cornerstone concept in the understanding of interacting solid-state systems. In a typical series of temperature-driven phase transitions, higher-temperature phases are more symmetric due to the stabilizing effect of entropy that becomes dominant as the temperature is increased. However, the opposite is rare but possible when there are multiple degrees of freedom in the system. Here, we present such an example of a symmetry-ascending phenomenon upon cooling in a magnetic kagome metal FeGe by utilizing neutron Larmor diffraction and Raman spectroscopy. FeGe has a kagome lattice structure with simple A-type antiferromagnetic order below Néel temperature T N ≈ 400 K and a charge density wave (CDW) transition at T CDW ≈ 110 K , followed by a spin-canting transition at around 60 K. In the paramagnetic state at 460 K, we confirm that the crystal structure is indeed a hexagonal kagome lattice. On cooling to around T N , the crystal structure changes from hexagonal to monoclinic with in-plane lattice distortions on the order of 10 − 4 and the associated splitting of the double-degenerate phonon mode of the pristine kagome lattice. Upon further cooling to T CDW , the kagome lattice shows a small negative thermal expansion, and the crystal structure gradually becomes more symmetric upon further cooling. A tendency of increasing the crystalline symmetry upon cooling is unusual; it originates from an extremely weak structural instability that coexists and competes with the CDW and magnetic orders. These observations are against the expectations for a simple model with a single order parameter and hence can only be explained by a Landau free energy expansion that takes into account multiple lattice, charge, and spin degrees of freedom. Thus, the determination of the crystalline lattice symmetry as well as the unusual spin-lattice coupling is a first step towards understanding the rich electronic and magnetic properties of the system, and it sheds new light on intertwined orders where the lattice degree of freedom is no longer dominant. Published by the American Physical Society 2024

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Design of the Electromagnetic Particle Injector (EPI) for Tokamak Deployment

Both predicting and controlling disruptions are critical and urgent issues for ITER as some disruptions with a short warning time may be unavoidable. For these cases, a rapid response disruption mitigation system (DMS) referred to as the electromagnetic particle injector (EPI) is being developed. The primary advantages of the EPI are its fast response time and high velocity, which have been demonstrated in offline experiments (Raman et al., 2021). The EPI is capable of accelerating a metallic sabot electromagnetically using a rail gun to the required velocities ( > 2 km/s) within 2 ms. Two high-field racetrack magnets able to generate fields over 2 T are positioned above and below the rails to permit high velocity at low rail currents, a requirement to minimize electrode erosion. At the end of the acceleration phase, a sabot capture mechanism retains the spent sabot inside the vacuum chamber that houses the EPI. At this point, it releases well-defined microspheres, or a shell pellet, of a radiative payload into the disrupting plasma. A remotely operated sabot loading system positioned behind the injector contains several pre-equipped sabots that can be loaded by an operator from the tokamak control room. The injector is interfaced to the tokamak through a guide tube attached to the front of the EPI vacuum chamber. Finally, the advantages of the EPI system over other DMSs under consideration are described in conjunction with the details of an EPI system designed for near-term test on an existing large tokamak.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Experimental observations of amorphization in multiple generations of boron carbide

Boron carbide is an excellent armor material due to its light weight and ultrahigh hardness. However, high-rate mechanical behavior can be degraded by stress-induced amorphization. In this paper, we review the progressive advances in the understanding of amorphization in three successive generations of boron carbide: stoichiometric (undoped), B-rich, and B/Si codoped boron carbides. For each generation of boron carbide, the crystal structure and microstructure are first discussed. Then, we outline the experimental observations of amorphization made by Raman spectroscopy and transmission electron microscopy. The susceptibility of amorphization in each generation of boron carbide will be compared and the fundamental mechanisms that explain the reduction in amorphization for B-rich and B/Si codoped boron carbides elucidated. Furthermore, comments on future research directions to further broaden and deepen the understanding of stress-induced amorphization of boron carbide are also provided.

36 MATERIALS SCIENCE↗

Deposition and characterization of α-Fe 2 O 3 /Pd thin films for neutron reflectometry studies

Here, we report deposition of hematite/Pd thin films on silicon wafers via radio frequency (RF) magnetron sputtering and subsequent characterization for future in situ neutron reflectometry studies. Following deposition, the hematite/Pd thin films were characterized as prepared and after annealing in air for 2h at 400, 500, and 600 °C, respectively. Raman spectroscopy, grazing incidence x-ray diffraction, and neutron reflectometry (NR) were used to characterize the structure and chemical compositions of the thin films. The results indicate that pure α-Fe 2 O 3 (hematite) films were produced, free from other iron oxide phases and impurities. NR data reveal that one intermediate layer between the Pd layer and the hematite layer was formed during sputtering deposition processes. The fitted scattering length density (SLD) of the as-deposited hematite layer is 70% of the theoretical SLD value, indicating that the grains are loosely packed in the RF-deposited hematite films. After annealing at elevated temperatures, the hematite films show increased SLD values but remain comparable to that of preannealed.

36 MATERIALS SCIENCE↗

Molecular beam epitaxy growth and characterization of GePb alloys

Pb based group-IV alloys such as GePb have been gaining interest as a potential alternative for infrared detectors, quantum materials, and high-speed electronic devices. Challenges remain in their growth due to the extremely low solid solubility of Pb in the Ge–Pb system. This paper reports molecular beam epitaxy growth of GePb alloy thin films on Ge(100) substrates. Effusion cells of Ge and Pb are used to control the flux ratio independently. The optimal substrate temperature is found to be near the thermocouple temperature of 300 °C based on the characterization of the grown films using high-resolution x-ray diffraction. A large change in the Ge:Pb beam equivalent pressure ratio from 10:1 to 1:1 results in only a minimal increase of the Pb composition from 0.74% to 2.84% as estimated from Raman spectroscopy and Rutherford backscattering spectrometry. Furthermore, scanning electron microscopy images show a large volume of Pb islands on the surface that form into either long trapezoidal rods or uniform droplets, with increasing Pb flux and growth time the density of Pb islands increased.

36 MATERIALS SCIENCE↗

Comprehensive Characterization of Multi-Phase Sulfurized Polyacrylonitrile Cathodes for Lithium-Sulfur Batteries

Sulfurized polyacrylonitrile (SPAN) is considered one of the most promising cathode materials to overcome the operational challenges that plague lithium-sulfur (Li-S) batteries. However, material properties and electrochemical performance implications of SPAN prepared under different synthesis conditions are not yet fully investigated. In this study, we show the impacts of different synthesis conditions on the formation of sulfur to PAN bonds and redox reaction mechanisms of multi-phase SPAN via comprehensive material and electrochemical characterizations. In-situ Raman analysis was first applied to study the multi-phase SPAN-based Li-S cells. We found that both elemental sulfur and chemically bonded sulfur are present under the synthesis condition of 300 degree C/3 h along with unreacted PAN. The incompletely sulfurized, multi-phase SPAN exhibited an unusually rapid capacity degradation in the resultant Li-S cells, which is attributed to polysulfide formation and continuously growing interfacial impedance in the Li-S cells. On the other hand, SPAN samples prepared under the synthesis condition of 350 degree C/3 h are found completely sulfurized with chemically bonded sulfur to the PAN backbone without the presence of free elemental sulfur. Complete sulfurization of SPAN led to exceptionally stable cycle performance due to excellent reversible redox processes of chemically bonded sulfur with Li+ in the Li-S cells.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗

Laser-Induced Plasmas of Plutonium Dioxide in a Double-Walled Cell

Plutonium research has been stifled by the significant number of administrative controls and safety procedures, space and instrumentation limitations in radiological gloveboxes, and the potential for personnel and equipment contamination. To address the limited number of spectroscopic studies in Pu-bearing compounds in the current scientific literature, this work presents the use of double-walled cells (DWCs) in “clean” buildings/laboratories as an alternative to research in radiological gloveboxes. This study reports the first laser-induced breakdown spectroscopy (LIBS) experiments of a PuO 2 pellet contained within a DWC, where the formation of elemental (atomic and ionic) species as well as the evolution from elemental to molecular products (Pu x O y ) was measured. Raman spectroscopy was also used to characterize the surface of the ablated pellet and the particulates deposited on the window of the inner cell. The full width half-maximum of the T 2g band enabled us to obtain an estimate of the temperature at the pellet surface after the ablation pulse and the particulates based on the crystal lattice disorder. Particulates deposited on the window of the DWC during laser ablation were characterized using scanning electron microscopy, where molten irregular particulates and spheroids were observed. This exciting research conducted in a DWC describes our initial attempts to incorporate LIBS in the arsenal of spectroscopic tools for nuclear forensics applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

In situ potassium and hydrogen ion exchange into a cubic zirconium silicate microporous material

The selective separation of ions from aqueous systems, and even in the human body, is a crucial to overall environmental management and health. Nanoporous materials are widely known for their selective removal of cations from aqueous media, and therefore have been targeted for use as a pharmaceutical to treat hyperkalemia. This study investigated the detailed crystallographic molecular mechanisms that control the potassium ion selectivity in the nanoporous cubic zirconium silicate (CZS) related materials. Using time-resolved in situ Raman spectroscopy and time-resolved in situ X-ray diffraction, the selectivity mechanisms were determined to involve a synchronous cation-cation repulsion process that serves to open a favorable coordination bonding environment for potassium, not unlike the ion selectivity filter process found in potassium ion channels in proteins. Enhancement of ion exchange was observed when the CZS material was in a partial protonated state (≈3:1 Na:H), causing an expansion of the unit-cell volume, enlargement of the 7 member-ring window, and distortion of framework polyhedra, which allowed increased accessibility to the cage structures and resulted in rapid irreversible potassium ion exchange.

59 BASIC BIOLOGICAL SCIENCES↗

Identification and time evolution of thionyl chloride (SOCl 2 ) radiolysis products

In this study, innovative solutions are needed to reduce the amount of high-level waste generated by used nuclear fuel recycling strategies to support the widespread adoption of sustainable nuclear fission energy technologies. To this end, a new sulfur chloride-based process has been developed to recycle zirconium alloy-based materials, which make up a significant fraction of high-level radioactive waste. To support the continued development of this process, we present new data on the potential reaction pathways over time of the products arising from the gamma and electron beam radiolysis of neat thionyl chloride (SOCl 2 ). Interrogation of the gamma irradiated liquid by Raman spectroscopy provided more conclusive identification of the SOCl 2 degradation products, specifically sulfur dichloride (SCl 2 ), molecular chlorine (Cl 2 ), sulfur dioxide (SO 2 ), and sulfuryl chloride (SO 2 Cl 2 ). In comparison, the high dose rate (~10 7 Gy s -1 ) electron beam irradiations formed significantly more degradation products. For both cobalt-60 gamma and electron beam irradiations, the observed degradation products were found to evolve as a function of time post-irradiation via the same reaction pathways, with indication of a solvent regeneration mechanism. These findings are fortuitous for process development, as such a mechanism would be beneficial for process longevity and cost effectiveness.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

High-Spectral Resolution Lidar (HSRL) Instrument Handbook

High-spectral-resolution lidar (HSRL) systems provide vertical profiles of optical depth, backscatter cross-section, depolarization, and backscatter phase function. All HSRL measurements are calibrated by reference to molecular scattering, which is measured at each point in the lidar profile. Like the Raman lidar (RL), but unlike simple backscatter lidars such as the micropulse lidar (MPL), this enables the HSRL to measure backscatter cross-sections and optical depths without prior assumptions about the scattering properties of the atmosphere. The depolarization observations allow robust discrimination between ice and water clouds. Rigorous error estimates can be computed for all measurements. A very narrow angular field of view reduces multiple scattering contributions. The small field of view, coupled with a narrow optical bandwidth, nearly eliminates noise due to scattered sunlight. The laser transmitter is a diode-pumped, frequency-doubled Nd:YAG laser. Narrow-band, single-frequency operation is provided by injection seeding with a single-frequency, cw-diode-pumped diode laser. The main laser cavity is maintained in resonance with the seed laser by adjusting the cavity length to minimize the time between the Q-switch trigger and the emission of the laser pulse. The emission wavelength is tuned via temperature control of the seed laser crystal and is locked to line #1109 of the iodine absorption spectra. Locking is accomplished by minimizing the transmission through a 2-cm-long iodine absorption cell. Use of a high-repetition-rate laser and expansion of the transmitted beam through a 400-mm telescope reduces the transmitted energy density to eye-safe levels. It is possible to look directly into the output beam without hazard. The receiver and transmitter use the same afocal telescope, simplifying the maintenance of stable alignment of the transmitter and receiver although the angular FOV is only 100 μrad. The small FOV and the 4-kHz repetition rate also limit the near-field signal strength, making it possible to record continuous profiles that start at an altitude of ~100 m and extend to 30 km using photon counting detectors. The small FOV also suppresses multiple scattering contributions.

54 ENVIRONMENTAL SCIENCES↗

Characterizing the Turbulent Structure of the Convective Boundary Layer Using ARM/ASR Observations and LES Model Output

This project will ultimately combine observations from Raman lidar, Doppler lidar, AERI, eddy correlation measurements, and airborne and ground-based high spectral resolution lidar systems with many large eddy simulations (LES) of realistic boundary layer cases to study: The diurnal evolution of the boundary layer thermodynamic structure; The turbulent structure of the CBL and the entrainment zone; The ability of LES models to simulate the thermodynamic and turbulent structure of the CBL; How perturbations in the surface properties and CBL properties influence boundary layer clouds; The similarities and differences in the boundary layer and cloud interaction in the marine vs. continental boundary layer.

54 ENVIRONMENTAL SCIENCES↗

Impurity Characterization in Device Quality Hot Filament Chemical Vapor Deposition (HFCVD) Grown 3C Silicon Carbide (3C-SiC) (CRADA CRD-17-00684 Final Report)

BASiC-3C needs advanced characterization of material properties to continue making progress towards high quality 3C-SiC. For over 190 growth runs, BASiC 3C has relied almost exclusively on feedback from commercially available metrology such as cross-sectional FESEM, AFM, Raman, XRD and SIMS. This standard feedback loop has enabled BASiC 3C to "rough-in" growth conditions and achieve growth of epitaxial growth over a 4" wafer size, at respectable growth rates. Still, the material quality deduced from X-ray rocking FWMH and APB density must be further improved to be viable for our industry partners. Electron Spin Resonance (EPR) and time-resolved photoluminescence (TRPL) data and interpretation by an experienced scientist is identified as a critical, yet not commercially readily available feedback that would enable further material improvement.

36 MATERIALS SCIENCE↗

High-throughput chemical imaging for optimizing biofuel synthesis using synthetic biology (Final Technical Report)

Fatty acids can be produced biosynthetically in microbes and these compounds can serve as precursors to biodiesels and other high value oleochemicals. However, progress on engineering fatty acid biosynthesis, and biofuel synthesis more generally, has been hindered by current quantification methods that are either indirect or not amenable to high-throughput or single-cell resolution screening. In this project, we assembled an interdisciplinary team with complimentary expertise in synthetic biology and microscopy, metabolic engineering, and chemical imaging to address these challenges. We used chemical imaging to directly measure lipid biosynthesis in Escherichia coli engineered to produce fatty acids, obtaining detailed single-cell resolution measurements. We deployed stimulated Raman scattering (SRS) microscopy in concert with multiplexed genome engineering and gene circuit design strategies from synthetic biology to optimize production of fatty acids. These results provided novel insight into cell-to-cell heterogeneity present in biofuel production strains. In addition, we introduced new chemical imaging methods which are label-free and do not require fluorescent reporters. These efforts were complemented by other studied developing foundational tools for regulation and control, which offer excellent potential for advancing researchers’ ability to rapidly design, build, and test strains for enhanced biofuel synthesis.

09 BIOMASS FUELS↗

Novel High Resolution High Temperature In-Line Sensors for Steel Manufacturing

To support efficiency, productivity, yield improvements, and future industry 4.0 and SMART manufacturing objectives for a competitive and prosperous steel industry, this program has embarked on an effort to develop, demonstrate and deploy several novel sensing technologies based on fiber optics for use in production steel facilities. Over the duration of this program, our team has successfully demonstrated three of these technologies: (1) near continuous Rayliegh Scattering optical frequency domain reflectometry (OFDR) sensing with single mode silica fibers for temperature sensing to 700 C, (2) semi-distributed fiber Bragg grating (FBG) sensing with multimode sapphire fibers for temperature sensing to >1600 C, and (3) remote in-situ Raman analysis for slag and flux chemistry analysis at steelmaking temperatures >1550 C. Each of these sensor and interrogation systems was developed, refined, and tested in our labs at Missouri S&T and then successfully deployed at SSAB’s production facilities at two sites, one in Montpelier, IA and one in Mobile, AL.

36 MATERIALS SCIENCE↗

Evaluation of Properties for Microsample Identification

A study was conducted to determine if individual particle characteristics could be used to identify particles of interest, sub-samples, from bulk post-detonation debris. Three archived post-detonation debris samples were used for this effort. Particles from these samples were identified as active (produced fission tracks), and inactive (did not produce fission tracks), as the first defining characteristic. Morphology was the secondary characteristic to select particles for further study, i.e. spherical/non-spherical. Once particles were identified and isolated, they were characterized by optical microscopy for size in µm, number of fission tracks, morphology, transmitted light color, and reflected light color. Particles were then analyzed by scanning electron microscopy for morphology, elemental content, and compound identification. Raman spectroscopy was attempted on five particles with indeterminate results due to environmental mixing (heterogeneity) during the events of particle formation. Once all non-destructive analyses were completed all particles were analyzed by thermal ionization mass spectrometry to determine isotopic atom percents of plutonium and uranium, and an estimate of atoms of plutonium and uranium in each particle. An estimate of the ratio of uranium to plutonium was also obtained (U/Pu). Data analytics of the data from the particles showed that combining characteristics of the particles have a high probability of identifying particles of interest from bulk post-detonation debris samples. Please note that this version of the report is an abridged version of the full report (Wagnon et al. 2025) that has been edited to be appropriate for public release.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Laser Measurements and Modeling of Shock Tunnel Freestream Velocity and Multispecies Thermal Nonequilibrium

Coherent anti-Stokes Raman scattering (CARS) and nitric oxide molecular tagging velocimetry (NO-MTV) were used to characterize the freestream in Sandia’s Hypersonic Shock Tunnel (HST) using a burst-mode laser operated at 100 kHz. Experiments were performed at nominal freestream velocities of 3 and 4 km/s using both air and N 2 test gas. The CARS diagnostic provides nonequilibrium characterization of the flow by measuring vibrational and rotational temperatures of N 2 and O 2 , which are compared to NO temperatures from separate laser absorption experiments. Simultaneous, collinear freestream velocities were measured using NO MTV along with pitot pressure measurements. Furthermore, this extensive freestream dataset is compared to nonequilibrium CFD that is capable of modeling species-specific, vibrational temperatures throughout the nozzle expansion. Significant nonequilibrium between vibrational and rotational temperatures was measured at each flow condition. N 2 exhibits the most nonequilibrium, followed by O 2 and NO. The CFD model captures this trend, although it consistently overpredicts N 2 and O 2 vibrational temperatures. At 3 km/s, the modeled NO nonequilibrium is underpredicted, whereas it is overpredicted at 4 km/s. Good agreement is seen between CFD and the velocity and rotational temperature measurements. Experiments with water added to the test gas yielded no discernable difference in vibrational relaxation.

Aerodynamics↗

Chemical Preparation, Crystal Structure Reinvestigation and Vibrational Study of CoNa 3 P 3 O 10 ·12H 2 O and X-ray Characterization of the New Anhydrous Triphosphate CoNa 3 P 3 O 10

The triphosphate dodecahydrate of cobalt and sodium CoNa 3 P 3 O 10 ·12H 2 O was prepared by the ion exchange resin process. Its structure was studied by X-ray diffraction and determined in the monoclinic space group P12 1 /c1 with the unit-cell parameters a = 14.6650(5) Å, b=9.1916(3) Å, c = 15.0239(5) Å,β =90.2210(10)°, Z = 4 and V = 2025.13(12) Å 3 . The thermal dehydration of this compound was performed, leading to an anhydrous new form, CoNa 3 P 3 O 10 , which was characterized by X-ray diffraction. The obtained CoNa 3 P 3 O 10 crystallized in monoclinic space group P21/n with the unit-cell parameters a=15,3774 Å, b=7,6988 A°, c=14,2832A°, β=92,9115°. The characteristic IR wavenumbers of the P 3 O 10 5- ions observed in the vibrational spectra were calculated using isotopic substitutions, which confirms the existence of these groups in the studied compound. A comparison between the IR and Raman wavenumbers of CoNa 3 P 3 O 10 ·12H 2 O, CoNa 3 P 3 O 10 and Na 5 P 3 O 10 ·12H 2 was performed. A kinetic study was also made for CoNa 3 P 3 O 10 ·12H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗