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At least 1,621 records · Page 90

Historic and modern nuclear graphite impurities: Pathways to improved waste strategies

Graphite has been used in large volumes as a structural material and neutron moderator since the earliest days of nuclear fission. However, no international consensus exists on the disposal of irradiated graphite, leaving much of the historic radioactive graphite inventory in interim vault or silo storage. With several new graphite-moderated reactors planned or under construction, the issue of graphite waste management is becoming increasingly urgent. This paper reviews and quantifies impurities in both historic and modern nuclear graphite, with emphasis on nitrogen—responsible for much of the 14 C inventory—and chlorine, which plays a critical role in repository performance and design. Modern graphites, benefitting from stringent quality-control measures developed for non-nuclear industries, meet or exceed the ASTM Ultra-High Purity nuclear standards, even without halide purification. Both chlorine and nitrogen concentrations have declined over time. For chlorine, identified as a key impurity influencing U.S. waste repository design, we propose a target of 0.1 appm in as-fabricated billets as a reasonable benchmark. Nitrogen sources are traced throughout the graphite production process, with surface and bulk concentrations characterized for all materials studied. Modern graphites commonly exhibit nitrogen levels below 5 appm, with values approaching 1 appm achievable. Using such reduced-nitrogen grades is critical to keeping graphite-induced radioactivity below the greater-than-Class-C waste threshold, thereby avoiding disposal cost penalties of nearly an order of magnitude.

Chlorine↗

Assessing epitaxial regrowth material quality on a micro-transfer printed GaAs substrate

Micro-transfer printing has demonstrated value for device- and array-level heterogeneous integration in a variety of applications. In this report it is used instead to assemble unique substrates with the potential to enable III–V growth templates that are both low-cost and specified at any desired lattice parameter within the range of III–V materials. Critical to this, epitaxial growth crystal quality must be established as comparable to that produced on conventional epi-ready substrates. We demonstrate epitaxial regrowth on gallium arsenide membranes that were transfer printed from their source substrate and onto a target handle. Both morphology and luminescence properties were characterized. Comparing the transfer printed membrane epitaxy with epitaxy on a conventional substrate, we found recombination rates and spatial uniformity from power-dependent photoluminescence and cathodoluminescence, respectively, to yield similar results, suggesting material quality was not adversely limited by the engineered substrate.

36 MATERIALS SCIENCE↗

Comparing Sensor Fusion and Multimodal Chemometric Models for Monitoring U(VI) in Complex Environments Representative of Irradiated Nuclear Fuel

Optical sensors and chemometric models were leveraged for the quantification of uranium(VI) (0–100 μg mL –1 ), europium (0–150 μg mL –1 ), samarium (0–250 μg mL –1 ), praseodymium (0–350 μg mL –1 ), neodymium (0–1000 μg mL –1 ), and HNO 3 (2–4 M) with varying corrosion product (iron, nickel, and chromium) levels using laser fluorescence, Raman scattering, and ultraviolet–visible–near-infrared absorption spectra. In this paper, an efficient approach to developing and evaluating tens of thousands of partial least-squares regression (PLSR) models, built from fused optical spectra or multimodal acquisitions, is discussed. Each PLSR model was optimized with unique preprocessing combinations, and features were selected using genetic algorithm filters. The 7-factor D-optimal design training set contained just 55 samples to minimize the number of samples. The performance of PLSR models was evaluated by using an automated latent variable selection script. PLS1 regression models tailored to each species outperformed a global PLS2 model. PLS1 models built using fused spectra data and a multimodal (i.e., analyzed separately) approach yielded similar information, resulting in percent root-mean-square error of prediction values of 0.9–5.7% for the seven factors. Further, the optical techniques and data processing strategies established in this study allow for the direct analysis of numerous species without measuring luminescence lifetimes or relying on a standard addition approach, making it optimal for near-real-time, in situ measurements. Nuclear reactor modeling helped bound training set conditions and identified elemental ratios of lanthanide fission products to characterize the burnup of irradiated nuclear fuel. Leveraging fluorescence, spectrophotometry, experimental design, and chemometrics can enable the remote quantification and characterization of complex systems with numerous species, monitor system performance, help identify the source of materials, and enable rapid high-throughput experiments in a variety of industrial processes and fundamental studies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Sensitivity of Simulated Aerosol Properties Over Eastern North America to WRF-Chem Parameterizations

Aerosol properties and their climatic feedbacks are characterized by high uncertainty in both global and regional model simulations. We explore sources of uncertainty in the representation of aerosol properties using an ensemble of simulations performed at 24 km resolution with WRF-Chem over eastern North America. The sensitivity of aerosol optical depth (AOD) and near-surface fine particle concentrations (PM 2.5 ) to planetary boundary layer (PBL) and aerosol schemes (modal with secondary organic aerosol (SOA) versus sectional but excluding SOA), as well as different emission inventories (National Emission Inventory (NEI) 2005 versus 2011) is examined. Here, we quantify the spread among ensemble members with respect to the model setup and compute statistical metrics to identify the run configuration that exhibits greatest fidelity relative to observations of aerosol and meteorological properties. Use of the Modal Aerosol Dynamics Model for Europe/Secondary Organic Aerosol Model scheme leads to highest agreement with MODIS clear-sky AOD observations particularly when the 2005 NEI is used (with either PBL scheme). These members exhibit small negative mean fractional bias over the simulation domain (<2%), and relatively high spatial correlation in summertime mean monthly AOD (>0.5). The aerosol scheme and NEI dominate the ensemble spread in AOD. Near-surface PM 2.5 is also dependent on PBL scheme and is best reproduced in runs adopting a sectional approach and emissions for 2011. Thus, WRF-Chem configuration associated with highest agreement with AOD observations is not the same as for PM 2.5 , possibly reflecting the importance of columnar water vapor in dictating AOD.

54 ENVIRONMENTAL SCIENCES↗

A new family of cation-disordered Zn(Cu)–Si–P compounds as high-performance anodes for next-generation Li-ion batteries

The development of low-cost, high-performance anode materials for Li-ion batteries (LIBs) is imperative to meet the ever-increasing demands for advanced power sources. In this paper we report our findings on the design, synthesis, and characterization of a new cation-disordered ZnSiP 2 anode. When tested in LIBs, the disordered phase of ZnSiP 2 demonstrates faster reaction kinetics and higher energy efficiency than the cation-ordered phase of ZnSiP 2 . The superior performance is attributed to the greater electronic and ionic conductivity and better tolerance against volume variation during cycling, as confirmed by theoretical calculations and experimental measurements. Moreover, the cation-disordered ZnSiP 2 /C composite exhibits excellent cycle stability and superior rate capability. The performance surpasses all reported multi-phase anodes studied. Further, a number of the cation-disordered phases in the Zn(Cu)–Si–P family with a wide range of cation ratios show similar performance, achieving large specific capacities and high first-cycle coulombic efficiency while maintaining desirable working potentials for enhanced safety.

25 ENERGY STORAGE↗

Development of Neutron Energy Spectral Signatures for Passive Monitoring of Spent Nuclear Fuels in Dry Cask Storage

Demand for spent nuclear fuel dry casks as an interim storage solution has increased globally and the IAEA has expressed a need for robust safeguards and verification technologies for ensuring the continuity of knowledge and the integrity of radioactive materials inside spent fuel casks. Existing research has been focusing on “fingerprinting” casks based on count rate statistics to represent radiation emission signatures. The current research aims to expand to include neutron energy spectral information as part of the fuel characteristics. First, spent fuel composition data are taken from the Next Generation Safeguards Initiative Spent Fuel Libraries, representative for Westinghouse 17 x 17 PWR assemblies. The ORIGEN-S code then calculates the spontaneous fission and (α,n) emissions for individual fuel rods, followed by detailed MCNP simulations of neutrons transported through the fuel assemblies. A comprehensive database of neutron energy spectral profiles is to be constructed, with different enrichment, burn-up, and cooling time conditions. The end goal is to utilize the computational spent fuel library, predictive algorithm, and a pressurized 4 He scintillator to verify the spent fuel assemblies inside a cask. This work identifies neutron spectral signatures that correlate with the cooling time of spent fuel. Both the total and relative contributions from spontaneous fission and (α,n) change noticeably with respect to cooling time, due to the relatively short half-life (18 years) of the major neutron source 244 Cm. Identification of this and other neutron spectral signatures allows the characterization of spent nuclear fuels in dry cask storage.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development and characterization of liquid argon and methane microjets for high-rep-rate laser-plasma experiments

A cryogenic microjet system has been used here for delivering micron-scale continuous liquid hydrogen targets for laser-plasma experiments. This technique has been extended to higher-Z, higher boiling-point gases, including argon and methane. High-resolution shadowgraphy has been used to characterize the jet’s morphology and pointing stability. A split and delay illumination source has also been developed for direct measurement of jet speeds without relying on assumptions of fluid flow conditions. Under typical conditions, the argon jets freeze solid due to evaporative cooling, but the methane jets remain liquid and break up to a droplet stream. A piezo driver is used to ensure the droplets are of uniform size. This jet has enabled the investigation of methane in planetary core conditions with high-rep-rate laser heating and x-ray laser probing.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The neutron camera upgrade for MAST Upgrade

The Neutron Camera Upgrade (NCU) is a neutron flux monitor consisting of six lines of sight (LoSs) under installation on Mega Ampere Spherical Tokamak (MAST) Upgrade. The NCU is expected to contribute to the study of the confinement of fast ions and on the efficiency of non-inductive current drive in the presence of on-axis and off-axis neutral beam injection by measuring the neutron emissivity profile along the equatorial plane. This paper discusses the NCU main design criteria, the engineering and interfacing issues, and the solutions adopted. In addition, the results from the characterization and performance studies of the neutron detectors using standard γ-rays sources and a 252 Cf source are discussed. The proposed design has a time resolution of 1 ms with a statistical uncertainty of less than 10% for all MAST Upgrade scenarios with a spatial resolution of 10 cm: higher spatial resolution is possible by moving the LoSs in-between plasma discharges. Finally, the energy resolution of the neutron detector is better than 10% for a light output of 0.8 MeVee, and the measured pulse shape discrimination is satisfactory.

47 OTHER INSTRUMENTATION↗

A setup for extreme-ultraviolet ultrafast angle-resolved photoelectron spectroscopy at 50-kHz repetition rate

Time- and angle-resolved photoelectron spectroscopy (trARPES) is a powerful method to track the ultrafast dynamics of quasiparticles and electronic bands in energy and momentum space. We present a setup for trARPES with 22.3 eV extreme-ultraviolet (XUV) femtosecond pulses at 50-kHz repetition rate, which enables fast data acquisition and access to dynamics across momentum space with high sensitivity. The design and operation of the XUV beamline, pump-probe setup, and ultra-high vacuum endstation are described in detail. By characterizing the effect of space-charge broadening, we determine an ultimate source-limited energy resolution of 60 meV, with typically 80-100 meV obtained at 1-2 × 10 10 photons/s probe flux on the sample. The instrument capabilities are demonstrated via both equilibrium and time-resolved ARPES studies of transition-metal dichalcogenides. The 50-kHz repetition rate enables sensitive measurements of quasiparticles at low excitation fluences in semiconducting MoSe 2 , with an instrumental time resolution of 65 fs. Moreover, photo-induced phase transitions can be driven with the available pump fluence, as shown by charge density wave melting in 1T-TiSe 2 . The high repetition-rate setup thus provides a versatile platform for sensitive XUV trARPES, from quenching of electronic phases down to the perturbative limit.

47 OTHER INSTRUMENTATION↗

Lightwave-driven electron emission for polarity-sensitive terahertz beam profiling

The full exploitation of advanced light sources in the terahertz (THz) frequency range requires versatile experimental tools to fully characterize the spatial, temporal, and spectral shapes of the THz electric field. Several techniques for passive THz beam profiling exist that offer information about the temporally integrated intensity. Thus, any information about the electric field itself is lost. Here, we show that a UV–visible light emission produced via a lightwave-driven field emission from single-layer metasurfaces can be used to visualize the peak electric field distribution of THz beams in real time. Our technique is scalable up to frequencies approaching the plasma frequency of the metal used for the metasurface. Uniquely, our device is sensitive to the absolute polarity of the THz lightwave. These findings demonstrate a general pathway to designing metamaterial-based field-sensitive optical detectors suitable for the entire THz and IR spectral region.

42 ENGINEERING↗

Comprehensive model for evaluating voltage losses and performance improvements in thin-film photovoltaic devices

Progress of state-of-the-art and next-generation thin-film photovoltaic devices is often stymied by open-circuit voltage (𝑉 oc ) that is significantly lower than theoretical and practical limits. Yet, effectively diagnosing the primary sources of voltage loss remains challenging. Herein, a sequence of device-level characterization techniques and simulations are employed to identify and rank loss mechanisms. For the research-based Cd⁡(Se,Te) device under study, most of the loss was at the front semiconductor heterointerface due to a clifflike conduction-band offset that lowered the recombination activation energy. Additional losses due to band tails were quantified by photoluminescence analysis. The latter provided the absorption coefficient and activation energy reduction associated with band tails as inputs to device models. Simulations showed that alleviating front-interface issues would improve 𝑉 oc , but it would then be limited by bulk recombination. Further improvement of the bulk would then lead to back-contact limitations. Reducing band tails is beneficial in any circumstance. In conclusion, this analysis provides guidance for reaching toward the radiative 𝑉 oc limit.

14 SOLAR ENERGY↗

Atomic pair distribution function at the Brazilian Synchrotron Light Laboratory: application to the Pb 1– x La x Zr 0.40 Ti 0.60 O 3 ferroelectric system

This work reports the setting up of the X-ray diffraction and spectroscopy beamline at the Brazilian Synchrotron Light Laboratory for performing total scattering experiments to be analyzed by atomic pair distribution function (PDF) studies. The results of a PDF refinement for Al 2 O 3 standard are presented and compared with data acquired at a beamline of the Advanced Photon Source, where it is common to perform this type of experiment. A preliminary characterization of the Pb 1– x La x Zr 0.40 Ti 0.60 O 3 ferroelectric system, with x = 0.11, 0.12 and 0.15, is also shown.

Saleta, M. E.↗

Spatiotemporal Metrology of Broadband Optical Pulses

Accurately characterizing the field of broadband optical pulses is required for developing new optical sources, performing successful experiments, and interpreting experimental results. Temporal diagnostics for short optical pulses are now well established. The most recent developments in ultrafast metrology focus on determining the field as a function of time (conversely frequency) and space, potentially revealing the field’s nonhomogeneity and coupling between these variables. After a review of common situations where a nonhomogeneous spatiotemporal field is used as a tool or is the outcome of nonideal conditions, historical and state-of-the-art techniques for spatiotemporal ultrafast metrology are described. Lastly, the different classes of techniques demonstrate the richness of the fundamental and technical developments in this domain.

42 ENGINEERING↗

Characterization of Noise in CMOS Ring Oscillators at Cryogenic Temperatures

Allan deviation provides a means to characterize the time-dependence of noise in oscillators and potentially identify the source characteristics. Measurements on a 130 nm, 7-stage ring oscillator show that the Allan deviation declines from 300 K to 150 K as expected, but surprisingly increases from 150 K to 11 K. At low temperatures, the measured Allan deviation can be well fit using a few random telegraph noise (RTN) sources over the range of a few kilohertz to a few gigahertz. Further, the RTN characteristics evolve to reveal an enhanced role in low-frequency noise at lower temperatures.

47 OTHER INSTRUMENTATION↗

Hydrologic Impacts of a Strike-Slip Fault Zone: Insights from Joint 3D Body-Wave Tomography of Rock Valley

The Rock Valley fault zone (RVFZ), an intraplate strike-slip fault zone in the southern Nevada National Security Site (NNSS), hosted a series of very shallow (<3 km) earthquakes in 1993. The RVFZ may also have hydrological significance within the NNSS, potentially playing a role in regional groundwater flow, but there is a lack of local hydrological data. In the Spring of 2021, we collected active-source accelerated weight drop seismic data over part of the RVFZ to better characterize the shallow subsurface. Here, we manually picked ~17,000 P-wave travel times and over 14,000 S-wave travel times, which were inverted for P-wave velocity (V P ), S-wave velocity (V S ), and V P /V S ratio in a 3D joint tomographic inversion scheme. Seismic velocities are imaged as deep as ~700 m in areas and generally align with geologic and structural expectations. V P and V S are relatively reduced near mapped and inferred faults, with the most prominent lower V P and V S zone around the densest collection of faults. We image V P /V S ratios ranging from ~1.5 to ~2.4, the extremes of which occur at a depth of ~100 m and are juxtaposed across a fault. One possible interpretation of the imaged seismic velocities is enhanced fault damage near the densest collection of faults with relatively higher porosity and/or crack density at ~100 m depth, with patches of semiperched groundwater present in the sedimentary rock in higher V P /V S areas and drier rock in lower V P /V S areas. A relatively higher V P /V S area beneath the densest faults persists at depth, which suggests percolation of groundwater via the fault damage zone to the regionally connected lower carbonate aquifer. Potentially, the presence and movement of groundwater may have played a role in the 1993 earthquake aftershocks.

58 GEOSCIENCES↗

Evaluation of Radiation Proofing Polyethylene: Use of Oxygen Scavenging Additives

The degradation of polyethylene (PE) from radiation sources with both thermal and nuclear interactions show sensitivities towards oxygen and air. Characterization of the sensitivities in both inert and oxygenated atmospheres can be characterized by thermogravimetric analysis (TGA). Under argon, the thermal degradation of PE follows a random scission pathway that has activation energy of ~229 kJ mol -1 . The activation energy of PE is reduced by ~30% when 1% air is added to the inert argon atmosphere, illustrating the impact of oxygen on the degradation of PE. This effort seeks to diminish degradation of PE waste containment bags and extend their lifetime, thereby, reducing the cost and worker exposure risk. The project evaluated the use of oxygen scavenger nanoparticles to mitigate the deteriorating effects of oxygen on polymer physical properties and reduce polymer degradation. The thermal degradation of PE composites with various additives were tested and two additives showed promising results approaching the activation energy of pristine PE in an inert atmosphere. This activity was sponsored by the EM Office of Technology Development through SRNL’s Technical Task Plan SR091701.

36 MATERIALS SCIENCE↗

Investigation of Ga 2 O 3 as a new transparent conductive oxide for photovoltaics applications

This small innovation project intended to leverage recent activity and advances in ultrawide-bandgap oxide power electronics toward the investigation of Ga 2 O 3 as a transparent conductive oxide (TCO) for use in photovoltaics (PV). Ga 2 O 3 ’s theoretical advantage over incumbent TCOs is its very large bandgap of 4.8 eV, ensuring optical transparency of photons with λ ≥ 260 nm, effectively the full terrestrial solar spectrum. At the time of proposal writing, literature on Ga 2 O 3 as a TCO/optical material was relatively sparse — what little existed was focused on for UV sensors and/or emitters, with none related to PV. As such, this project was intended to help determine the potential of Ga 2 O 3 as a PV-oriented TCO by investigating its deposition using tools common to the PV and electronics industries — atomic layer deposition (ALD) and RF sputtering (RS), both of which are already used in PV manufacturing — and its resultant optical and electronic properties. Final project goals were to test its application to Si and III-V solar cells. Controllable film thickness and excellent uniformity was established for both methods deposition methods, with ALD providing higher precision for thinner films and RS more effective for growing thicker films. The as-deposited films were found to be amorphous in nature. Spectroscopic ellipsometry (SE) confirmed bandgaps of at least 4.8 eV and non-parasitic absorption across both AM0 and AM1.5G spectra; a refractive index approaching the expected value of 1.8 was also observed, with some degree of tunability based on process parameters. Using this initial optical data, a transfer matrix model, which interfaces with in-house EQE and LIV models, was developed to simulate Ga 2 O 3 optical effects on various solar cells, included potential in antireflection coatings (ARCs). Despite promising optical properties, the resultant resistivity / conductivity metrics did not meet expectations, regardless of deposition process. Although thick RS-deposited films, using both undoped and 1 at% Ge (n-type) doped sintered targets — demonstrated high net carrier concentrations (via C-V), and low specific resistance Ohmic contacts were demonstrated, transmission line measurements (TLM) showed very high resistivity. Further analysis indicated high vertical film conductivity, but very low lateral conductivity. Deeper characterization revealed a relatively high density of nano/microcrystalline inclusions that were ostensibly the source of the vertical conductivity, with the amorphous matrix serving as an effective insulator (likely due to high concentrations of electronic trap states). Despite extensive work to increase film polycrystallinity — demonstrated via high temperature annealing — sufficient lateral conductivity for TCO use was not achieved. The final phase of the project shifted focus toward investigation of ALD-deposited Ga 2 O 3 ’s potential as a passivant and/or passivating contact for both Si and III-V solar cells, with expectation of performance similar to Al 2 O 3 . However, initial rounds of testing using our baseline ALD process yielded minimal (but not quite zero) passivation of both GaInP and Si surfaces. Dielectric passivation is well-known to be highly process sensitive; given the unoptimized nature of the process used, this work was deemed inconclusive. The final outlook with respect to feasibility of Ga 2 O 3 as a PV-oriented TCO is, ultimately, still uncertain. The work performed in this project confirmed the optical properties and deposition methods, but the achieved electrical properties do not meet technological needs; literature reports in recent years are somewhat inconsistent and potentially untrustworthy, but generally appear to be in line with our results. At the very least it is clear that, should Ga 2 O 3 still be under consideration for PV TCO and/or selective contact applications, a significant amount of optimization and study is still needed.

14 SOLAR ENERGY↗

Instrument Control Software for Spectrophotometers

SRNL has developed instrument control software for diode array spectrophotometers that can be used for real time monitoring of dynamic systems. This software has evolved through several iterations as instruments have been developed for use in processing facilities at Savannah River Site. There are several noteworthy features of the software. The wavelength calibration is checked and updated in real time against reference emission lines that are designed into the instrument light source. Nonlinearities and offsets associated with the intensity response of the instruments are characterized, and absorbance spectra are appropriately corrected. These actions are necessary for accurate calculation of an absorbance spectrum from the intensity responses of two individual diode array detectors. The corrections also result in the spectra obtained for a particular sample by two (or more) different diode array detector pairs being nearly identical. This property assures consistent measurements at multiple locations with different instruments. It also permits the use of a single analyte calibration across many instruments without modification and without loss of accuracy

47 OTHER INSTRUMENTATION↗