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DOE OSTI2014

Synchrotron and inverse-Compton emissions from pairs formed in GRB afterglows (analytical treatment)

We calculate the synchrotron and inverse-Compton emissions from pairs formed in gamma-ray burst (GRB) afterglows from high-energy photons (above 100 MeV), assuming a power-law photon spectrum C {sub ν}∝ν{sup –2} and considering only the pairs generated from primary high-energy photons. The essential properties of these pairs (number, minimal energy, cooling energy, distribution with energy) and of their emission (peak flux, spectral breaks, spectral slope) are set by the observables GeV fluence Φ(t) = Ft and spectrum, and by the Lorentz factor, Γ, and magnetic field, B, of the source of high-energy photons, at observer time, t. Optical and X-ray pseudo light curves, F {sub ν}(Γ), are calculated for the given B; proper synchrotron self-Compton light curves are calculated by setting the dynamics Γ(t) of the high-energy photon source to be that of a decelerating, relativistic shock. It is found that the emission from pairs can accommodate the flux and decays of the optical flashes measured during the prompt (GRB) phase, but it decays faster than the X-ray plateaus observed during the delayed (afterglow) phase. The brightest pair optical emission is obtained for 100 < Γ < 500, and depends mostly on the GeV fluence, being independent of the source redshift. Emission from pairs formed during the GRB phase offers an alternate explanation to reverse-shock optical flashes. These two models may be distinguished based on their corresponding flux decay index-spectral slope relations, different correlations with the Large Area Telescope fluence, or through modeling of the afterglow multiwavelength data.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

Tabulated data for Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. We demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents. This is the tabulated data for the paper

biorefining↗

DOE OSTI2026

Calculation of monomer yields, verification of PG concentration approximation, catalyst comparison for neat aromatic RCF, SEM micrographs for postreaction pulps, yields of aqueous-phase sugar derivatives after PG-H2O RCF, reactor pressure transients, GPC comparing pre- and postreaction organic solvent composition, PG-H2O miscibility testing, GPC probing dimer/oligomer fractionation in PG-H2O mixtures for

biorefining↗

DOE OSTI2026

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

biorefining↗

NASA NTRS1998

Emissions Measurements from a Lobed Fuel Injector/Burner

The present experimental study examines NO(x) and CO emissions associated with alternative fuel injector geometries. These injectors mix fuel and air to differing extents and thus create different local equivalence ratios upstream of flame ignition and stabilization. Two of the devices studied are lobed fuel injectors, in which mixing of reactants is associated with stream wise vorticity generation and straining of fuel-air interfaces, while the third is a non-lobed fuel injector which creates relatively little fuel-air mixing prior to ignition.Results show that one lobed injector geometry appears to produce locally lean premixed flame structures, resulting in low NO. emissions when compared with non-lobed injector emissions. The other lobed injector geometry appears to produce a local fuel-air mixture which is closer to stoichiometric conditions, with NO(x) emissions that are actually higher than for the non-lobed injector. For both lobed injector geometries examined here, CO emissions become high for over-all lean operating conditions, consistent with premixed combustion behavior. The present study demonstrates the importance of control of the local equivalence ratio in minimizing burner emissions.

Mitchell, M. G.↗

DOE OSTI2025

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. Here, we demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

09 BIOMASS FUELS↗

DOE OSTI2021

Pendent Relay Enhances H 2 O 2 Selectivity during Dioxygen Reduction Mediated by Bipyridine-Based Co–N 2 O 2 Complexes

Generally, cobalt–N 2 O 2 complexes show selectivity for hydrogen peroxide during electrochemical dioxygen (O 2 ) reduction. We recently reported a Co(III)–N 2 O 2 complex with a 2,2'-bipyridine-based ligand backbone which showed alternative selectivity: H 2 O was observed as the primary reduction product from O 2 (71 ± 5%) with decamethylferrocene as a chemical reductant and acetic acid as a proton donor in methanol solution. We hypothesized that the key selectivity difference in this case arises in part from increased favorability of protonation at the distal O position of the key intermediate Co(III)–hydroperoxide species. To interrogate this hypothesis, in this study we have prepared a new Co(III) compound that contains pendent –OMe groups poised to direct protonation toward the proximal O atom of this hydroperoxo intermediate. Mechanistic studies in acetonitrile (MeCN) solution reveal two regimes are possible in the catalytic response, dependent on added acid strength and the presence of the pendent proton donor relay. In the presence of stronger acids, the activity of the complex containing pendent relays becomes O 2 dependent, implying a shift to Co(III)–superoxide protonation as the rate-determining step. Interestingly, the inclusion of the relay results in primarily H 2 O 2 production in MeCN, despite minimal difference between the standard reduction potentials of the three complexes tested. EPR spectroscopic studies indicate the formation of Co(III)–superoxide species in the presence of exogenous base, with greater O 2 reactivity observed in the presence of the pendent –OMe groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

High Temperature Chemistry of Aromatic Hydrocarbons. Final Technical Report

The primary goal of this research was to uncover the principal reaction channels available to polycyclic aromatic hydrocarbons (PAHs) at high temperatures in the gas phase and to establish the factors that determine which channels will be followed in varying circumstances. New structure-property relationships for PAHs were also studied. The efficient production of clean energy from fossil fuels will remain a major component of the DOE mission until alternative sources of energy eventually displace coal and petroleum. Hydrocarbons constitute the most basic class of compounds in all of organic chemistry, and as the dominant species in fossil fuels, they figure prominently into the programs of the DOE. Much is already known about the normal chemistry of hydrocarbons under ambient conditions, but far less is known about their intrinsic chemistry at temperatures close to those reached during combustion. An understanding of the fundamental molecular transformations, rearrangements, and interconversions of PAHs at high temperatures in the gas phase, as revealed by careful studies on small, well-designed, molecular systems, provides insights into the underlying chemistry of many important processes that are more complex, such as the generation of energy by the combustion of fossil fuels, the uncatalyzed gasification and liquefaction of coal, the production of fullerenes in fuel-rich flames, and the formation of soot and carcinogenic pollutants in smoke (e.g., benzo[a]pyrene). The rational control of any of these processes, whether it be the optimization of a desirable process or the minimization of an undesirable one, requires a clear knowledge of the basic chemistry that governs the fate of the species involved. Advances in chemistry at the most fundamental level come about primarily from the discovery of new reactions and from new insights into how reactions occur. Harnessing that knowledge is the key to new technologies. The recent commercialization of a combustion synthesis of C 60 and other fullerenes depended critically on a knowledge of hydrocarbon reactions at high temperatures in the gas phase, and the research supported by this project enabled further advances in the realm of carbon-rich materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

Financial and economic determinants of collective action: The case of wastewater management

Where public environmental funds support development of wastewater infrastructure, funding institutions ensure the economic use of funds, while the beneficiaries minimize their own costs. In rural areas, there is often a choice between decentralized or centralized (multi-village) systems: if the centralized system is most economic, then only this system is eligible for public funding. However, its implementation requires a voluntary cooperation of the concerned communities, who need to organize themselves to develop and run the infrastructure. The paper analyzes the social determinants of collaboration in a generic case study, using the following variables: method of (economic) assessment, modeled by the social discount rate, funding policy, modeled by the funding rate, and users' self-organization, modeled by cost sharing. In a borderline situation, where the centralized system turns out to be most economic, but this assessment is contingent on the assessment method, collective action may fail: the advantages of collective action from funding are too small to outweigh organizational deficiencies. Considering in this situation sanitation as a human right, authors recommend using innovative forms of organization and, if these fail, reassessing either the amount of funding or the eligibility for funding of more acceptable alternatives. - Highlights: Black-Right-Pointing-Pointer A generic case study models collective action and funding in wastewater management. Black-Right-Pointing-Pointer Determinants of success: economic assessment, funding policy and self-organization. Black-Right-Pointing-Pointer Success indicators: conflict rate, funds needed to make cost shares fair. Black-Right-Pointing-Pointer Method for analyzing centralized vs. decentralized disputes. Black-Right-Pointing-Pointer If collective action has less benefits, innovative cost sharing may ensure success.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Spatial and temporal modeling of sub- and supercritical thermal energy storage

This paper describes a thermodynamic model that simulates the discharge cycle of a single-tank thermal energy storage (TES) system that can operate from the two-phase (liquid-vapor) to supercritical regimes for storage fluid temperatures typical of concentrating solar power plants. State-of-the-art TES design utilizes a two-tank system with molten nitrate salts; one major problem is the high capital cost of the salts (International Renewable Energy Agency, 2012). The alternate approach explored here opens up the use of low-cost fluids by considering operation at higher pressures associated with the two-phase and supercritical regimes. The main challenge to such a system is its high pressures and temperatures which necessitate a relatively high-cost containment vessel that represents a large fraction of the system capital cost. To mitigate this cost, the proposed design utilizes a single-tank TES system, effectively halving the required wall material. A single-tank approach also significantly reduces the complexity of the system in comparison to the two-tank systems, which require expensive pumps and external heat exchangers. A thermodynamic model is used to evaluate system performance; in particular it predicts the volume of tank wall material needed to encapsulate the storage fluid. The transient temperature of the tank is observed to remain hottest at the storage tank exit, which is beneficial to system operation. It is also shown that there is an optimum storage fluid loading that generates a given turbine energy output while minimizing the required tank wall material. Overall, this study explores opportunities to further improve current solar thermal technologies. The proposed single-tank system shows promise for decreasing the cost of thermal energy storage. (C) 2014 Elsevier Ltd. All rights reserved.

Tse, LA↗

DOE OSTI2019

NEK5000 Assessment Milestone Report: Single-Phase Natural Circulation using Direct Numerical Simulation (DNS) & Large Eddy Simulation (LES) Methods

This study evaluates the capabilities of the NEK5000 open-source code as an alternative to the commercially available software that is currently heavily relied upon. The first three case studies initiated the author with (1) the syntax and flow of the program, (2) varying initial and boundary conditions and (3) geometries of greater complexity & dimension. Case 1 studies transient conjugate heat transfer in the entry region of a pipe. Cases 2 & 3 simulate the natural convection flow in an enclosed differentially heated cavity (DHC) of two and three dimensions, respectively. The final case study, Case 4, produces three-dimensional single-phase natural convective flow using the Boussinesq approximation within a simplified representation of an aqueous homogeneous reactor system. The Boussinesq flow in Case 4 clearly depicts both Rayleigh-Taylor and Kelvin-Helmholtz instabilities qualitatively during post-processing analysis. Further analysis of Case 4, up to the point of a quasi-steady state (i.e. thermal-equilibrium condition), is done using the LES solver method in NEK5000. The volume-averaged solution temperatures, when compared between solvers, showed no significant difference. Due to its minimal compromise in fidelity of solution resolution and inexpensive computing cost, compared to the DNS solver, the LES solver is recommended for the current application. Methodology development for the four case studies are reported and a preliminary optimization study with different polynomial resolutions for Case 4 is addressed as a resource when performing future simulations using NEK5000. Hence, this report can be used as a reference starting point to the end user of NEK5000 for natural circulation phenomena in nuclear reactor safety applications.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

NASA NTRS2017

A PCR Based Microbial Monitoring Alternative Method of Detection and Identification of Microbes Aboard ISS

Previous research has shown that microorganisms and potential human pathogens have been detected on the International Space Station (ISS) with additional introduction of new microflora occurring with every exchange of crew or addition of equipment and supplies. These microbes are readily transferred between crew and subsystems (i.e. ECLSS, environmental control and life support systems). As this can be detrimental to astronaut health and optimal performance of ISS systems, monitoring of systems such as ECLSS to include identification of microbial contaminants could prevent adverse effects on human health and life support systems. Current monitoring on ISS is laborious and utilizes culture based methods followed by sample return to Earth for complete analysis. Future, long-distance spaceflight missions will require real-time monitoring capabilities that enable efficient and rapid assessments of the microbial environment allowing for expedited decisions and more targeted response to cope with anomalies. Polymerase chain reaction (PCR), a molecular microbial monitoring method was chosen and numerous PCR instruments investigated for their potential to perform in microgravity conditions. Using ISS as a test bed for PCR verification in microgravity will enable NASA to assess whether molecular based microbiological sensors may be components of reliable, closed-loop life support and habitation systems in spacecraft, enhancing infrastructure capabilities through increased efficiency, reliability, and time savings by enabling sample analysis on orbit. NASA selected the Water Monitoring Suite as one of the rapid spaceflight hardware demonstration activities utilizing a streamlined process to minimize the time required to fly experimental flight hardware. The RAZOR EX (BioFire Defense, Salt Lake City, UT) system was part of the water monitoring suite and is a commercial off-the-shelf (COTS) real-time PCR instrument designed for field work. The RAZOR EX was originally designed for Department of Defense (DoD) under a small business innovative research (SBIR) grant and is ruggedized, compact and provides a rapid, sample to answer in less than an hour. PCR assays using a fluorescent probe were optimized and spiked with known concentrations of DNA (Pseudomonas aeruginosa) ranging from 0.002 to 20 ng. PCR reagents were lyophilized and configured in customized pouches and tested for flight readiness. Three types of water were used to rehydrate the reagents and demonstrate the fidelity of the PCR reaction in microgravity. Molecular grade deionized water served as a control while filtered and unfiltered ISS potable water served to test for chemical or biological inhibitors. All three types were compared to parallel ground test results. Nine tests were run on ISS (3 of each water type) and the critical threshold cycle (Ct) was compared to parallel ground tests completed at Kennedy Space Center, FL and Johnson Space Center, TX. All concentrations of Pseudomonas aeruginosa DNA were detected. A comparison of the Ct produced in real time PCR indicated similarity between flight and ground samples. There appeared to be no significant difference between flight or ground PCR reactions or between any of the three water types. This testing demonstrated the ability to perform molecular testing during spaceflight operations with similar sensitivity. It will allow for future ground development of molecular protocols and minimize the need for spaceflight testing. Future testing will include development of additional targets including environmental and health related organisms.

Christina Khodadad↗

DOE OSTI2020

Highly Reversible Sodium Ion Batteries Enabled by Stable Electrolyte-Electrode Interphases

Sodium (Na) ion battery is a very promising technology for the alternative energy storage systems because of the abundance and low cost of Na element in the Earth’s crust. However, the limited cycle life and safety concerns still hinder its large-scale applications. Here, we report a nonflammable localized high concentration electrolyte (sodium bis(fluorosulfonyl)imide - triethyl phosphate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (1:1.5:2 in molar ratio)), which enables a very high initial Coulombic efficiency (CE) of 97.8% for Na||Na-CNFM (O3-NaCu1/9Ni2/9Fe1/3Mn1/3O2) cells and stable cycling of Na||hard carbon (HC) cells with a capacity retention of 95.4% after 500 cycles. The HC||Na-CNFM full cells using this electrolyte retain 82.5% capacity after 200 cycles with a CE of ~99.9% compared to 48.4% capacity retention in the carbonate electrolyte (1 M NaPF6/EC+DMC (1:1 in weight)). The extremely high CE and stability of HC||Na-CNFM cells in this electrolyte can be attributed to the stable interphase layers formed on both HC anode and Na-CNFM cathode. These layers minimize undesirable reaction between HC and electrolyte, and block the dissolution of transition metal from cathode. The insight obtained in this work can be used to further improve cycling stability and safety of rechargeable batteries.

Jin, Yan↗

DOE OSTI2015

SU-E-J-187: Management of Optic Organ Motion in Fractionated Stereotactic Radiotherapy

Purpose: Fractionated stereotactic radiotherapy (FSRT) for optic nerve tumors can potentially use planning target volume (PTV) expansions as small as 1–5 mm. However, the motion of the intraorbital segment of the optic nerve has not been studied. Methods: A subject with a right optic nerve sheath meningioma underwent CT simulation in three fixed gaze positions: right, left, and fixed forward at a marker. The gross tumor volume (GTV) and the organs-at-risk (OAR) were contoured on all three scans. An IMRT plan using 10 static non-coplanar fields to 50.4 Gy in 28 fractions was designed to treat the fixed-forward gazing GTV with a 1 mm PTV, then resulting coverage was evaluated for the GTV in the three positions. As an alternative, the composite structures were computed to generate the internal target volume (ITV), 1 mm expansion free-gazing PTV, and planning organat-risk volumes (PRVs) for free-gazing treatment. A comparable IMRT plan was created for the free-gazing PTV. Results: If the patient were treated using the fixed forward gaze plan looking straight, right, and left, the V100% for the GTV was 100.0%, 33.1%, and 0.1%, respectively. The volumes of the PTVs for fixed gaze and free-gazing plans were 0.79 and 2.21 cc, respectively, increasing the PTV by a factor of 2.6. The V100% for the fixed gaze and free-gazing plans were 0.85 cc and 2.8 cc, respectively increasing the treated volume by a factor of 3.3. Conclusion: Fixed gaze treatment appears to provide greater organ sparing than free-gazing. However unanticipated intrafraction right or left gaze can produce a geometric miss. Further study of optic nerve motion appears to be warranted in areas such as intrafraction optical confirmation of fixed gaze and optimized gaze directions to minimize lens and other normal organ dose in cranial radiotherapy.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2013

Coherent Elastic Neutrino Nucleus Scattering

Coherent Elastic Neutrino Nucleus Scattering (CENNS) has yet to be observed since its first prediction in 1974. The CENNS cross-section is precisely known in the Standard Model (SM). It is considerably larger than the other neutrino interaction channels at MeV energies. If measured at its predicted value, CENNS can be a very powerful tool for future neutrino oscillation experiments. Alternatively, any deviation from the very robust SM prediction could be a window to beyond-SM physics. The discovery of CENNS requires an intense source of low energy neutrinos, and a large-scale low energy threshold detector, both of which complement and build on existing programs at Fermilab. The Booster Neutrino Beamline (BNB) at Fermilab is a surprisingly powerful source of pion decay-at-rest ($\pi$DAR) neutrinos. The energy spectrum and flux of neutrinos in the backward direction (far-off-axis) of the BNB is excellent for a CENNS discovery measurement. At the closest practical location, the $\pi$DAR neutrino flux at BNB would be about a fifth of the neutrino flux of Spallation Neutron Source (SNS at Oak Ridge). The BNB site is preferable in almost every other aspect, however. First, the beam duty factor of BNB (2.5x10 -5 ) is about a factor of four better, which will help to reduce ambient backgrounds. Second, the potential experiment site, close to the BNB target, allows optimal placement of the detectors, with minimal sitting issues. The CENNS experiment would be completely parasitic to any running of the BNB. It would require no changes to the beamline, and place no additional requirements on the running mode or times. The $\pi$DAR neutrinos from the BNB are a by-product of running the beamline for MicroBooNE, and will be available for the foreseeable future. The CENNS detector would be a ton-scale single-phase Liquid Argon (LAr) detector, placed inside a water shield with an active cosmic ray veto. The low energy threshold and low background detector technology is already well developed thanks to work over the last decade in Dark Matter detector physics. Moreover, Fermilab is equipped with very strong technical and engineering resources in liquid argon detector development. One issue that must be addressed prior to the development of a full CENNS proposal is the question of whether the beam-related fast neutron background is low enough that it can be practically shielded.

Brice, S. J.↗

DOE OSTI2018

Development of LWR fuels with enhanced accident tolerance. Final report

After a tsunami triggered plant black out at the Fukushima Daiichi site, followed by hydrogen explosions, the US Department of Energy partnered with fuel vendors to study safer alternatives to the current UO2 – zirconium alloy fuel system. This accident tolerant fuel (ATF) alternative should better tolerate a loss of cooling in the core for a considerably longer time while maintaining or improving the fuel performance during normal operation conditions. General Electric, Oak Ridge National Laboratory, and their partners are proposing to replace zirconium alloy cladding in current commercial light water power reactors with an iron-chromium-aluminum (FeCrAl) cladding such as APMT, C26M or FeCrAl ODS, which has been named IronClad by GE. Extensive testing and evaluation has been conducted to determine the suitability of FeCrAl for the entire fuel cycle from rod fabrication to used fuel disposition. Most of the environmental characterization was conducted to evaluate the behavior of IronClad under normal operation conditions and under severe accident conditions. Results show that FeCrAl has excellent corrosion resistance under normal operation conditions and FeCrAl is several orders of magnitude more resistant than zirconium alloys to degradation by superheated steam under accident conditions, generating less heat of oxidation and lower amount of combustible hydrogen gas. Higher parasitic neutron absorption and potential tritium release into the coolant effects can be minimized by design and operational measures. IronClad material can be manufactured using traditional melting and forging (C26M) or powder metallurgy processes (APMT & FeCrAl ODS). Tubes can be made to full length of 5 m with a wall thickness of 0.4 mm by pilgering or drawing. The fuel rods can be readily hermetically sealed in an industrial production setting by welding end caps to the thin wall tubing using either TIG or resistance welding. The implementation of FeCrAl IronClad cladding is a near term solution to enhance the safety of the current fleet of commercial light water power reactors.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Luminescent Materials for the Detection of Economically Critical Metals in Harsh Environments

Renewable energy technologies used for electric vehicles and wind turbines are heavily reliant upon metals, such as rare earth elements, cobalt, lithium, and nickel. Indeed, there are 50 minerals that are currently considered “economically critical” by the 2022 United States Geological Survey. With anticipated global adoption of renewable energy technologies, producing sufficient metals to meet this demand presents a significant challenge, particularly due to the current monopolistic market for many of these metals. The production of metals from unconventional sources, such as coal utilization byproducts, is one of many promising strategies to boost domestic supply. However, sensitive, rapid, and inexpensive characterization technologies are needed to minimize production costs associated with metals prospecting and processing. Photoluminescence-based sensing techniques are particularly intriguing due to their potential for low cost and portability, coupled with high sensitivity and selectivity. This presentation focuses on the development of high-performance sensing materials for a range of critical metals, including metal-organic frameworks capable of sensitizing detection of parts-per-billion concentrations of six different rare earth elements, nanoparticles that can detect down to 600 parts-per-billion levels of cobalt, and thin films that sense aluminum down to 120 parts-per-billion. These materials are highly selective, capable of withstanding low pH conditions, and provide a response within minutes. Importantly, each sensing material is integrated with a custom-built, fully portable fiber-optic spectrometer for potential field deployment, providing significant cost savings over commercial instruments, along with potential advantages such as material regeneration for use across multiple sensing cycles and solvent removal for enhanced emission signal. These results highlight the exciting potential of luminescence platforms as cost-effective alternatives for metals characterization.

Crawford, Scott↗

DOE OSTI2018

Alternative model of space-charge-limited thermionic current flow through a plasma

It is widely assumed that thermionic current flow through a plasma is limited by a “space-charge-limited” (SCL) cathode sheath that consumes the hot cathode's negative bias and accelerates upstream ions into the cathode. In this paper, we formulate a fundamentally different current-limited mode. In the “inverse” mode, the potentials of both electrodes are above the plasma potential, so that the plasma ions are confined. The bias is consumed by the anode sheath. There is no potential gradient in the neutral plasma region from resistivity or presheath. The inverse cathode sheath pulls some thermoelectrons back to the cathode, thereby limiting the circuit current. Thermoelectrons entering the zero-field plasma region that undergo collisions may also be sent back to the cathode, further attenuating the circuit current. In planar geometry, the plasma density is shown to vary linearly across the electrode gap. A continuum kinetic planar plasma diode simulation model is set up to compare the properties of current modes with classical, conventional SCL, and inverse cathode sheaths. SCL modes can exist only if charge-exchange collisions are turned off in the potential well of the virtual cathode to prevent ion trapping. With the collisions, the current-limited equilibrium must be inverse. Inverse operating modes should therefore be present or possible in many plasma devices that rely on hot cathodes. Evidence from past experiments is discussed. Finally, the inverse mode may offer opportunities to minimize sputtering and power consumption that were not previously explored due to the common assumption of SCL sheaths.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗