Search NASA⌕ Search

SEARCH · Search NASA

Results for “Layered electron gas”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Residual stress and microstructure in IN718-René41 graded superalloy fabricated by laser blown directed energy deposition

Additively printed Ni-based superalloy with a compositionally graded transition from IN718 to René41 was fabricated by laser blown-powder directed energy deposition (DED/LB-M), with the goals of meeting location-specific temperature capability and reducing component cost for hot gas path turbine components. Residual stress distribution in thin wall specimens with three sets of DED build parameters in the as-built and stress-relieved states was measured by neutron diffraction. For calculating residual stress, the calculated d0 method was found to be more appropriate as stress-free reference than using the lattice spacing measured from the stress-relief heat treated specimens. Longer dwell time (lower interpass temperature), higher energy input, smaller layer thickness resulted in a higher magnitude of tensile residual stresses at edges and compressive residual stresses at center of the specimens. The residual stress results did not show a strong dependence on graded compositions, indicating that the residual stress build-up was more geometry and process dependent. Non-destructive neutron imaging based on the attenuation coefficient qualitatively visualized the compositional variation in the bulk and showed good agreement with quantitative Electron Probe Micro-Analysis (EPMA) measurement. Grain structure, texture, and residual plastic strain along the build direction were characterized by Electron Backscatter Diffraction (EBSD). Long columnar grains with (001) preferred grain orientation were dominant along the build direction. Compositional change did not show an obvious effect on the epitaxial growth of dendrites and the continuation of the columnar grains. Residual plastic strain was relatively low in the as-built specimens.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Measurements of plasma parameters in the divertor island of Wendelstein 7-X through line-ratio spectroscopy on helium

We report electron temperature T e and density n e have been measured in the divertor island of Wendelstein 7-X by means of a new thermal He-beam system utilizing line-ratio spectroscopy. This system is equipped with a poloidal arrangement of five gas valves that allows to infer 2D plasma profiles T e ( R,Z ) and n e ( R,Z ) across the magnetic island forming the island divertor. A local maximum in T e ( R,Z ) was measured along the flux surfaces located between the island center and the outer separatrix. In the island center, characterized by closed field lines, a clear local minimum in T e was measured, indicating that no direct heat deposition occurs in this region and that the perpendicular heat flux from the core plasma into this domain is small. Increasing the island size leads to a reduction of the connection length in the scrape-off layer (SOL) and to a shift of the island center towards the divertor target. In this scenario, the T e ( R,Z ) are reduced in the entire island domain. Density profiles are found flat across the divertor island for both island size scenarios. These findings are supported by similar observations made with a reciprocating probe plunging through the same SOL island at the mid-plane of W7-X representing the upstream position in this 3D divertor geometry.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Automated Segmentation of Twin Boundaries in TRISO Silicon Carbide Using Deep Neural Networks

Coated particle fuels, such as the tristructural isotropic (TRISO) fuel particle, are essential for high-temperature gas reactor (HTGR) applications due to their efficiency and stability under normal and off-normal conditions. However, widespread commercialization and deployment of this technology for next-generation nuclear applications require robust quality assurance and quality control (QA/QC) methods linking fabrication, properties, and performance. Of the many important metrics for TRISO QA/QC, quantification of the silicon carbide (SiC) microstructure is critical because it correlates with fission product retention during irradiation. Previous work has shown extensive twinning of the SiC microstructure, which strongly affects microstructural metrics; however, twin grain boundaries are not expected play a significant role in fission product diffusion. This report summarizes the initial development, training, and testing of a machine learning image processing algorithm to detect twin grain boundaries in a backscattered electron image, which can be removed so that microstructural metrics can be recalculated for legacy data. Further development and deployment of this model will provide automated, scalable improvement of potential QA/QC methods for the SiC layer of TRISO particles.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Computational Insights into Phase Equilibria Between Wide-Gap Semiconductors and Contact Materials

Novel wide-band-gap semiconductors are needed for next-generation power electronics, but there is a gap between a promising material and a functional device. Finding stable (metal) contacts is one of the major challenges that is currently dealt with mainly via trial and error. Herein, we computationally investigate the thermochemistry and phase coexistence at the junction between three wide-gap semiconductors, ..beta..-Ga2O3, GeO2, and GaN, and possible contact materials. The pool of possible contacts includes 47 elemental metals and a set of 4 common, n-type transparent conducting oxides (ZnO, TiO2, SnO2, and In2O3). We use first-principles thermodynamics to model the Gibbs free energies of chemical reactions as a function of gas pressure (pO2/pN2) and equilibrium temperature. We deduce whether a semiconductor/contact interface will be stable at relevant conditions or a chemical reaction between them is to be expected, possibly influencing the long-term reliability and performance of devices. We generally find that most elemental metals tend to oxidize or nitridize and form various interface oxide/nitride layers. Exceptions include select late- and post-transition metals and, in the case of GaN, also the alkali metals, which are predicted to exhibit stable coexistence, although in many cases at relatively low gas partial pressures. Similar is true for the transparent conducting oxides, for which, in most cases, we predict a preference toward forming ternary oxides when in contact with ..beta..-Ga2O3 and GeO2. The only exception is SnO2, which we find to form stable contacts with both oxides. Finally, we show how the same approach can be used to predict gas partial pressure vs temperature phase diagrams to help direct synthesis of ternary compounds. We believe these results provide a valuable guidance in selecting contact materials to wide-gap semiconductors and suitable growth conditions.

contact materials↗
DOE OSTI2022

Irradiation of Sintered Mo Disks with Presence of Organic Impurities in He Gas Flow

Argonne National Laboratory (Argonne) is assisting NorthStar Medical Technologies in the development of a domestic supply of 99 Mo. Specifically, the present study focuses on the production of 99 Mo-feed solution used by the RadioGenix™ 99m Tc generator. During the target-irradiation phase of production, impurities can potentially be introduced into the feed, and can lead to disturbance of ligand- 99m Tc complexation chemistry and contamination of the final radiopharmaceutical that directly interacts with the patient. To address this issue, Argonne performed irradiations and chemical processing to identify whether the potential contamination of He flow with hydrocarbon oil during irradiation affects the radiochemical purity of the final K 2 MoO 4 (K 2 TcO 4 ) in 5M KOH solution. To mimic the conditions of real irradiation at NorthStar, Argonne used its electron linear accelerator and Van de Graaff facilities, heated the target and oil source to >800°C, and controlled oxygen in the presence of He during irradiation. Following irradiation, scanning electron microscopy (SEM) and carbon analysis (CA) were used to detect carbon contamination on the solid targets. The radiochemical purity of the dissolved targets was studied via thin-layer paper chromatography (TLC). As a result of these experiments, small regions of the surface of some irradiated disks were found to be high in carbon, but the total carbon content was still negligible in comparison to the reference sample, which had experienced no irradiation or contact with oil. The summarized results from the SEM, CA, and TLC tests lead to the conclusion that even an excess of oil and heating during irradiation do not affect the radiochemical purity of the final product.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Methods development towards automated, physics-informed, quantitative quality control of TRISO-SiC

Tristructural-isotropic (TRISO) fuel particles have been developed as a high-performance fuel for use in high-temperature gas-cooled reactor (HTGR) systems due to their high efficiency and stability under both normal and off-normal conditions. Broader deployment of this technology in advanced nuclear applications may benefit from quantitative quality assurance and quality control (QA/QC) methods that directly link TRISO properties to downstream performance. A key TRISO property is the SiC layer microstructure, which influences fission product retention during irradiation. However, existing QA/QC for the TRISO-SiC microstructure comprises only a qualitative visual inspection; therefore, there is a clear opportunity for the development of quantitative methods for TRISO QA/QC. Here, to this end, previous work has demonstrated an image processing approach to grain boundary (GB) identification and subsequent extraction of microstructural metrics; however, extensive twinning within the SiC layer complicates such analyses because twin GBs significantly influence microstructural metrics but are not expected to contribute to fission product transport. This study presents the initial development, training, and testing of an ML-based image segmentation algorithm designed to identify and remove twin GBs from standard backscattered electron micrographs, providing an industrially applicable, quantitative, and physically meaningful QA/QC approach for the TRISO-SiC microstructure. Although pixel-wise performance metrics for the twin predictions are low, the change in grain area and the number of GB pixels after twin removal predicted by the ML workflow are within 1% of the true values calculated using crystallographic data. This suggests that the model is well capable of predicting overall twin boundary structures and grain morphology, and continued advancement of this approach could enable automated, scalable, and physics-informed QA/QC for TRISO-SiC microstructures, supporting the reliable qualification of coated particle fuels for next-generation reactor systems.

Computer vision↗
DOE OSTI2023

Majorana bound states in a d -wave superconductor planar Josephson junction

We study phase-controlled planar Josephson junctions comprising a two-dimensional electron gas with strong spin-orbit coupling and d-wave superconductors, which have an advantage of a high critical temperature. We show that a region between the two superconductors can be tuned into a topological state by the in-plane Zeeman field, and can host Majorana bound states. The phase diagram as a function of the Zeeman field, chemical potential, and the phase difference between superconductors exhibits the appearance of Majorana bound states for a wide range of parameters. We further investigate the behavior of the topological gap and its dependence on the type of d-wave pairing, i.e., d, d+is, or d+id', and note the difficulties that can arise due to the presence of gapless excitations in pure d-wave superconductors. On the other hand, the planar Josephson junctions based on superconductors with d+is and d+id' pairings can potentially lead to realizations of Majorana bound states. Furthermore, our proposal can be realized in cuprate superconductors, e.g., in a twisted bilayer, combined with the layered semiconductor Bi 2 O 2 Se.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Computational Fermi Level Engineering and Doping-Type Conversion of Ga2O3 Via Three-Step Processing

Ga2O3 is being actively explored for power electronics, deep-ultraviolet optoelectronics, and other applications due to its ultra-wide bandgap and low projected fabrication cost of large-size and high-quality crystals. N-type doping of Ga2O3 can be achieved and tuned, but p-type doping faces fundamental obstacles due to deep character of acceptor levels and polaron transport of resulting holes. However, successful engineering of Ga2O3 based devices requires critical control of doping density, Fermi level position, and free carrier concentration, providing opportunities for predictive process simulation. We use first-principles defect theory and defect equilibrium calculations to simulate a 3-step growth-annealing-quench protocol for hydrogen assisted Mg doping in Ga2O3, taking into account the hydrogen-oxygen-water gas phase equilibrium. We predict type conversion to a net p-type regime following O-rich annealing after growth under reducing conditions in the presence of H2. This process is similar to the Mg acceptor activation by H removal in GaN. We show that there is an optimal temperature that maximizes the net acceptor density during the equilibrium annealing step for a given Mg doping level. Quenching of non-equilibrium annealed samples then results in a Fermi level EF below mid-gap down to about EV +1.5 eV, creating a significant number of uncompensated neutral MgGa0 acceptors. The resulting free hole concentration in quenched samples is very low (109 – 1012 cm-3) due to deep energy level of these Mg acceptors, but this type converted Ga2O3 material can create a significant built-in field in a p-n junction with an adjoining n-type material. Additionally, the electron concentration is greatly suppressed in such acceptor-doped Ga2O3, which could enable the use as a current blocking layer to fabricate normally-off (enhancement-mode) vertical Ga2O3 based metal-oxide-semiconductor field effect transistors (MOSFETs), and as a guard ring for edge termination in MOSFETs and Schottky barrier diodes (SBDs) with increased breakdown voltage.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗
DOE OSTI2023

Permeability of Single–Layer–Free–Standing Meshes at Varying Capillary Pressure via a Novel Method

The permeability of mesh wicks is important for various applications, including two–phase heat transfer. However, the understanding of the permeability of single–layer, free–standing mesh wicks, with liquid–gas interfaces on both sides, is limited. A novel and simpler method is presented to determine the permeability of a free–standing wick and apply it to a representative mesh. This method involves modifying the capillary pressure via elevation and simultaneously measuring the permeability to determine the permeability–capillary pressure relationship. When applied to a copper mesh with plain weave having undergone surface cleaning, the permeability is found to decrease as capillary pressure for deionized water increases. A dimensional analysis is presented to generalize this data for other mesh sizes with similar weaves and fluids. The behavior of mesh in application is modeled, based on the integration of Darcy's law with an analytic function fit to measured data, and parametric studies are conducted to investigate the superficial velocity of liquids through the mesh under varying driving pressures, transport lengths, and liquid viscosity, based on the obtained capillary pressure–permeability relationship. This study provides valuable insights into the transport properties of mesh wicks, with potential applications in fields such as electronics cooling, electrochemical devices, and fluid purification technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Exceptional Electrical Detection of Trace NO 2 via Mixed Metal MOF-on-MOF Film-Based Sensors

The tunability of metal–organic frameworks (MOFs) makes them exceptional materials for the development of highly selective, low-power sensors for toxic gas detection. Herein, we demonstrate enhanced detection of NO 2 gas by a MOF-based electrical impedance sensor made using a unique mixed metal MOF-on-MOF synthesis. For this work, a combined experimental and computational study was performed using the exemplar Ni x Mg 1–x -MOF-74 to understand the fundamental structure–property relationships behind metal mixing and MOF film synthesis methods on sensor performance. Density functional theory results indicated that the presence of Ni in Mg-MOF-74 increased framework stability and increased the electron density of states at lower energies near the HOMO, as well as enhanced the NO 2 –Mg adsorption interaction. Impedance data of the Ni x Mg 1–x -MOF-74 films with larger Ni contents showed greater impedance change after exposure to 1 ppm of NO 2 gas. Furthermore, when synthesized through either a drop-cast or direct solvothermal film growth approach, the monometallic Ni-based sensors had the best performance. However, the mixed metal Ni x Mg 1–x -MOF-74 sensors synthesized through a MOF-on-MOF approach resulted in the highest impedance change, outperforming all monometallic Ni-based sensors. In particular, the mixed metal Ni-on-Mg-MOF-74 film was the best-performing sensor with an impedance change of 309 upon trace NO 2 exposure. Change in impedance response after NO 2 exposure was improved by 52% compared to the best monometallic Ni-on-Ni-MOF-74 sensor. Structural analysis of the Ni-on-Mg film showed that the first Mg-MOF-74 layer acts as a structural template controlling the structural features of the final film after metal exchange with Ni. This led to improved film quality, evidenced by the greater crystallinity and larger MOF grain sizes, and resulted in enhanced sensor performance which was not achievable through other metal mixing methods. Altogether, this study identifies structure–property relationships and synthetic templating methods that inform MOF-based sensor design, allowing for improved detection of toxic compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Radiolytic Gas Production from Aluminum Coupons (Alloy 1100 and 6061) in Helium Environments—Assessing the Extended Storage of Aluminum Clad Spent Nuclear Fuel

Corrosion of aluminium alloy clad nuclear fuel, during reactor operation and under subsequent wet storage conditions, promotes the formation of aluminium hydroxide and oxyhydroxide layers. These hydrated mineral phases and the chemisorbed and physisorbed waters on their surfaces are susceptible to radiation-induced processes that yield molecular hydrogen gas (H 2 ), which has the potential to complicate the long-term storage and disposal of aluminium clad nuclear fuel through flammable and explosive gas mixture formation, alloy embrittlement, and pressurization. Here, we present a systematic study of the radiolytic formation of H 2 from aluminium alloy 1100 (AA1100) and 6061 (AA6061) coupons in “dry” (~0% relative humidity) and “wet” (50% relative humidity) helium environments. Cobalt-60 gamma irradiation of both aluminium alloy types promoted the formation of H 2 , which increased linearly up to ~2 MGy, and afforded G-values of 1.1 ± 0.1 and 2.9 ± 0.1 for “dry” and “wet” AA1100, and 2.7 ± 0.1 and 1.7 ± 0.1 for “dry” and “wet” AA6061. The negative correlation of H 2 production with relative humidity for AA6061 is in stark contrast to AA1100 and is attributed to differences in the extent of corrosion and varying amounts of adsorbed water in the two alloys, as characterized using optical profilometry, scanning electron microscopy, Raman spectroscopy, and X-ray diffraction techniques.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Hyperstoichiometric Uranium Dioxides: Rapid Synthesis and Irradiation-Induced Structural Changes

Uranium dioxide (UO 2 ), the primary fuel for commercial nuclear reactors, incorporates excess oxygen forming a series of hyperstoichiometric oxides. Thin layers of these oxides, such as UO 2.12 , form readily on the fuel surface and influence its properties, performance, and potentially geologic disposal. This work reports a rapid and straightforward combustion process in uranyl nitrate–glycine–water solutions to prepare UO 2.12 nanomaterials and thin films. We also report on the investigation of the structural changes induced in the material by irradiation. Despite the simple processing aspects, the combustion synthesis of UO 2.12 has a sophisticated chemical mechanism involving several exothermic steps. Raman spectroscopy and single-crystal X-ray diffraction (XRD) measurements reveal the formation of a complex compound containing the uranyl moiety, glycine, H 2 O, and NO 3 – groups in reactive solutions and dried combustion precursors. Combustion diagnostic methods, gas-phase mass spectroscopy, differential scanning calorimetry (DSC), and extracted activation energies from DSC measurements show that the rate-limiting step of the process is the reaction of ammonia with nitrogen oxides formed from the decomposition of glycine and uranyl nitrate, respectively. However, the exothermic decomposition of the complex compound determines the maximum temperature of the process. In situ transmission electron microscopy (TEM) imaging and electron diffraction measurements show that the decomposition of the complex compound directly produces UO 2 . The incorporation of oxygen at the cooling stage of the combustion process is responsible for the formation of UO 2.12 . Spin coating of the solutions and brief annealing at 670 K allow the deposition of uniform films of UO 2.12 with thicknesses up to 300 nm on an aluminum substrate. Irradiation of films with Ar 2+ ions (1.7 MeV energy, a fluence of up to 1 × 10 17 ions/cm 2 ) shows unusual defect-simulated grain growth and enhanced chemical mixing of UO 2.12 with the substrate due to the high uranium ion diffusion in films. As a result, the method described in this work allows the preparation of actinide oxide targets for fundamental nuclear science research and studies associated with stockpile stewardship.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Overview of the recent experimental research on the J-TEXT tokamak

The J-TEXT capability is enhanced compared to two years ago with several upgrades of its diagnostics and the increase of electron cyclotron resonance heating (ECRH) power to 1 MW. With the application of electron cyclotron wave (ECW), the ECW assisted plasma startup is achieved; the tearing mode is suppressed; the toroidal injection of 300 kW ECW drives around 24 kA current; fast electrons are generated with toroidal injected ECW and the runaway current conversion efficiency increases with ECRH power. The mode coupling between 2/1 and 3/1 modes are extensively studied. The coupled 2/1 and 3/1 modes usually lead to major disruption. Their coupling can be either suppressed or avoided by external resonant magnetic perturbation fields and hence avoids the major disruption. It is also found that the 2/1 threshold of external field is significantly reduced by a pre-excited 3/1 mode, which can be either a locked island or an external kink mode. The disruption control is studied by developing prediction methods capable of cross tokamak application and by new mitigation methods, such as the biased electrode or electromagnetic pellet injector. The high-density operation and related disruptions are studied from various aspects. Approaching the density limit, the collapse of the edge shear layer is observed and such collapse can be prevented by applying edge biasing, leading to an increased density limit. The density limit is also observed to increase, if the plasma is operated in the poloidal divertor configuration or the plasma purity is increased by increasing the pre-filled gas pressure or ECRH power during the start-up phase.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Pt 8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization

Alumina supported Pt nano clusters under hydrogen environment play a crucial role for many heterogeneous catalysis applications. As such, we conducted grand canonical genetic algorithm (GCGA) simulations for supported Pt 8 clusters in hydrogen gas environment to study the intra-cluster, cluster-support, and cluster-adsorbate interactions. Two alumina surfaces, α-Al 2 O 3 (0001) and $γ$-Al 2 O 3 (100), and two conditions T=600°C, p H2 = 0.1bar and T=25°C, p H2 = 1.0 bar were considered corresponding to low and high hydrogen chemical potential $μ$ H , respectively. The low free energy ensemble of Pt 8 is decorated by a medium (2–12 H), resp. high (20–30 H), number of hydrogen atoms under equilibrium at low $μ$ H , respectively, high $μ$ H , and undergoes different morphology transformations on the two surfaces. On α-Al2O3(0001), Pt8 is mostly 3D but very fluxional in structure at low μH and converts to open one-layer 2D structures with minimal fluxionality at high μH, whereas on $γ$-Al 2 O 3 (100), the exact opposite occurs, and Pt 8 clusters present one-layer 2D shapes at low $μ$ H and switch into compact 3D shapes under high $μ$ H , during which the Pt 8 cluster preserves moderate fluxionality. Further analysis reveals similar Pt–Pt bond length increase when switching from low $μ$ H to high $μ$ H on both surfaces, though morphology transformations are different. Electronic structure analysis shows the existence of bonding interactions between Pt and Lewis acidic Al 3+ sites along with the Pt – O interaction, which implies the necessity to include Al neighbors to discuss the electronic structure of small Pt clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Milestone 1.2.15: Feasibility of In Situ Accelerated Aluminum Coupon Radiolysis by Synchrotron X-Rays

Extended dry storage of aluminum-clad spent nuclear fuel (ASNF) requires an assessment of the radiolytic generation of molecular hydrogen gas (H2) from the ASNF’s corrosion layers. H2 accumulation can potentially lead to storage canister embrittlement/rupture and the accumulation of flammable gas mixtures in accident scenarios. To date, computational models have been developed for the prediction of radiolytic H2 generation from samples exposed to lower absorbed dose regimes (up to ~3 MGy). However, greater accuracy is needed for higher absorbed doses (> 25 MGy) where the concentration of H2 ultimately reaches a steady-state. Data in this area is limited due to the amount of time taken (months) to accumulate such high gamma doses. Furthermore, a recent study observed radiation-induced damage to the surface of pre-corroded aluminum alloy coupons at high absorbed gamma doses. Despite this observation and its implications, there is currently no computational connection between the radiolytic formation of H2 and changes in the composition and morphology of the cladding’s corrosion layers with absorbed dose. To develop a better understanding of the processes and effects described above, the present study aimed to evaluate the feasibility of leveraging synchrotron x-ray capabilities for coupled accelerated irradiation and in situ surface characterization of ASNF alloys. To that end, National Synchrotron Light Source II (NSLS-II) beamtime was secured and a series of aluminum alloy 1100 (AA1100) wires, prepared under a variety of conditions, were interrogated using ex situ x-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques at Idaho National Laboratory (INL) and ex situ and in situ XRD capabilities at the NSLS-II x-ray powder diffraction (XPD) beamline. Results indicated that performing synchrotron XRD using the available XPD beamline configuration can provide sufficient radiation dose but cannot discern changes in the composition and morphology of sample corrosion layers. Additionally, ex situ XRD and SEM data from Idaho National Laboratory (INL) indicated that the pre-corrosion of AA1100 wires did not generate an appreciably thick corrosion layer, as compared with previous aluminum coupon studies. These thinner surface corrosion layers were not sufficient for detection by both ex situ and in situ synchrotron XRD, specifically under consideration of the NSLS-II XPD beamline’s configuration primarily capturing information from the sample’s bulk material, i.e., aluminum metal. In summary, the use of the NSLS-II XPD beamline for promoting accelerated radiolysis and in situ surface characterization is not appropriate for this program’s goals.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2019

Carbene-based Difluoromethylation of Bisphenols: Application to the Instantaneous Tagging of Bisphenol A in Spiked Soil for Its Detection and Identification by Electron Ionization Gas Chromatography-Mass Spectrometry

The rapid and efficient difluoromethylation of a panel of eleven bisphenols (BPs) for their enhanced detection and identification by Electron-Ionization Gas Chromatography-Mass Spectrometry (EI-GC-MS) is presented. The derivatization employs the inexpensive, environmentally benign agent diethyl (bromodifluoromethyl) phosphonate (DBDFP) as a difluorocarbene-generating species that converts the BPs into bis-difluoromethylated ethers that can be detected and identified by GC-MS means. Key attributes of the protocol include its extreme rapidity (30 seconds) at ambient temperature, high specificity for BPs amidst other alcohol-containing analytes, and its biphasic nature that allows for its convenient adaptation to the analysis of BPs in organic as well as aqueous matrices. The protocol furnishes stable, novel BP ethers armed with a total of four fluorine atoms for their subsequent analysis by EI-GC-MS. Furthermore, each derivatized bisphenol exhibits unique retention times vastly different from their native counterparts leading to their unequivocal identification. The effectiveness and robustness of the developed methodology was applied to the tagging of the most famous member of this family of compounds, bisphenol-A (BPA), when spiked (at 1 μg.g –1 concentration) in the physically and compositionally complex Nebraska EPA standard soil. The method detection limit (MDL) for the bis-difluoromethylated BPA was determined to be 0.01 μg.mL –1 . The bis-difluoromethylated BPA was conveniently detected on the organic layers from the biphasic, derivatized mixtures, highlighting the protocol’s practicality and utility in the rapid, qualitative detection of this endocrine disruptor during environmental analysis.

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

Two-dimensional electron systems in perovskite oxide heterostructures: Role of the polarity-induced substitutional defects

The discovery of a two-dimensional electron system (2DES) at the interfaces of perovskite oxides such as LaAlO 3 and SrTiO 3 has motivated enormous efforts in engineering interfacial functionalities with this type of oxide heterostructures. However, the fundamental origins of the 2DES are still not understood, e.g., the microscopic mechanisms of coexisting interface conductivity and magnetism. In this paper, we report a comprehensive spectroscopic investigation on the depth profile of 2DES-relevant Ti 3d interface carriers using depth- and element-specific techniques like standing-wave excited photoemission and resonant inelastic scattering. We found that one type of Ti 3d interface carriers, which give rise to the 2DES are located within three unit cells from the n-type interface in the SrTiO 3 layer. Unexpectedly, another type of interface carriers, which are polarity-induced Ti-on-Al antisite defects, reside in the first three unit cells of the opposing LaAlO3 layer (~10 Å). Our findings provide a microscopic picture of how the localized and mobile Ti 3d interface carriers distribute across the interface and suggest that the 2DES and 2D magnetism at the LaAlO 3 /SrTiO 3 interface have disparate explanations as originating from different types of interface carriers.

36 MATERIALS SCIENCE↗