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Methods of Fabricating Scintillators with Radioisotopes for Beta Battery Applications

Technology has been developed for a class of self-contained, long-duration power sources called beta batteries, which harvest the energy contained in the radioactive emissions from beta decay isotopes. The new battery is a significant improvement over the conventional phosphor/solar cell concept for converting this energy in three ways. First, the thin phosphor is replaced with a thick scintillator that is transparent to its own emissions. By using a scintillator sufficiently thick to completely stop all the beta particles, efficiency is greatly improved. Second, since the energy of the beta particles is absorbed in the scintillator, the semiconductor photodetector is shielded from radiation damage that presently limits the performance and lifetime of traditional phosphor converters. Finally, instead of a thin film of beta-emitting material, the isotopes are incorporated into the entire volume of the thick scintillator crystal allowing more activity to be included in the converter without self-absorption. There is no chemical difference between radioactive and stable strontium beta emitters such as Sr-90, so the beta emitter can be uniformly distributed throughout a strontium based scintillator crystal. When beta emitter material is applied as a foil or thin film to the surface of a solar cell or even to the surface of a scintillator, much of the radiation escapes due to the geometry, and some is absorbed within the layer itself, leading to inefficient harvesting of the energy. In contrast, if the emitting atoms are incorporated within the scintillator, the geometry allows for the capture and efficient conversion of the energy of particles emitted in any direction. Any gamma rays associated with secondary decays or Bremsstrahlung photons may also be absorbed within the scintillator, and converted to lower energy photons, which will in turn be captured by the photocell or photodiode. Some energy will be lost in this two-stage conversion process (high-energy particle to low-energy photons to electric current). The geometric advantage partially offsets this as well, since the absorption depth of high-energy beta radiation is much larger than the depth of a p-n junction. Thus, in a p-n junction device, much of the radiation is absorbed far away from the junction, and the electron- hole pairs are not all effectively collected. In contrast, with a transparent scintillator the radiation can be converted to light in a larger volume, and all of the light can be collected in the active region of the photodiode. Finally, the new device is more practical because it can be used at much higher power levels without unduly shortening its lifetime. While the crystal structure of scintillators is also subject to radiation damage, their performance is far more tolerant of defects than that of semiconductor junctions. This allows the scintillator- based approach to use both higher energy isotopes and larger quantities of the isotopes. It is projected that this technology has the potential to produce a radioisotope battery with up to twice the efficiency of presently used systems.

Rensing, Noa M.↗

Metallic Powder Core Tubular Wire (PCTW) Development for Additive Manufacturing

NASA Langley Research Center (LaRC) in Hampton, VA, and the Center for Welding, Joining, and Coating Research (CWJCR) in the Department of Metallurgical and Materials Engineering at the Colorado School of Mines (CSM) in Golden, CO, have collaborated for nearly fifteen years to develop metallic powder core tubular wire (PCTW) feedstock for additive manufacturing (AM) using electron beam deposition. The motivation for this development was to offset dealloying observed during deposition of titanium and aluminum alloy solid wire feedstock in the LaRC electron beam freeform fabrication (EBF3) system and to explore novel alloy compositions by tailoring the powder fill. EBF3 is a fusion-based AM process that is performed under vacuum and is consequently prone to vaporization loss of low vapor pressure alloying elements. Research spanning four graduate student research projects succeeded in developing the basic methodology to fabricate PCTW, the mass balance equations used to define the powder fill, microstructure control through particulate inoculation, and the feasibility of producing metal matrix composite materials. Metallic PCTW is comprised of a thin foil sheath wrapped around a powder blend. Fabrication of PCTW at CSM was accomplished using a tubular wire mill system to first bend a flat strip into a u-shaped cross section, deposit a powder fill, create a lap joint to seal the wire, and draw to final diameter. Powder management systems were developed to ensure uniform mixing of powder constituents and identify feed rates for optimum fill ratios. Processing parameters were successfully developed for titanium and aluminum alloy sheaths to account for material work hardening during drawing. Mass balance equations were developed to account for compositional contributions of the sheath and powder fill. PCTW composition can be adjusted through selection of the sheath or powder materials. PCTWs were successfully developed to offset Al loss in deposits of Ti-6-4 and Mg loss in Al 6061, resulting in deposits that were within the composition limits for each material. Ti-6-4 deposits were fabricated using PCTW comprised of commercially pure (CP) titanium sheath and a fill of pre-alloyed Ti-6-4 powder with additions of elemental Al and V powders. Additions of both elements were required to account for the CP Ti from the sheath, and Al was further enhanced to offset documented losses in EBF3 deposits. For Al 6061 deposits, composition was modulated through the choice of sheath material. The PCTW was made using an Al 5052 sheath to supplement Mg content and a fill composition of pre-alloyed 6061 powder with additions of Si and Cu.The slower solidification rate of the EBF3 process compared with laser powder bed fusion processes can lead to coarse-grained microstructures and mechanical property anisotropy. EBF3deposits of Ti-6-4 exhibited large epitaxially grown β grains, which result in degraded mechanical properties in the deposition direction. Microstructure refinement was achieved through a combination of electron beam modulation and the use of a PCTW designed for Ti-6-4 deposits and modified by the addition of powder made from Fe and B. Resulting deposits exhibited reductions in β grain size, α phase colony intercept length and lath width, and an increased volume fraction of β phase. The mechanism of microstructure refinement was related to precipitation of boride particles. Hardness testing confirmed that mechanical property anisotropy was reduced and an overall increase in hardness was achieved.Metal matrix composite (MMC) materials offer strength and stiffness benefits over unreinforced materials. Two methods were investigated using PCTW technology for producing Al 6061 basedMMC materials; the direct addition of SiC reinforcing particles and the in-situ generation of reinforcements through reaction synthesis of precursor powders. Al 6061 based MMCs reinforced with SiC exhibited particle clustering and formation of aluminum carbides during deposition. The application of a Ni coating to the SiC particles prior to incorporation into the powder fill eliminated aluminum carbide formation and aided particle distribution during deposition. Modulation of beam focus and power further reduced aluminum carbide formation and aided particle distribution. In reaction synthesis, precursor additions undergo an exothermic reaction during deposition to form new ceramic products, generally of finer scale than the initial precursor components. The product phases provide reinforcement in the MMC and act as nucleation sites during solidification, resulting in grain refinement, improved mechanical properties, and reduced susceptibility to solidification cracking. Higher tensile strength and stiffness were demonstrated in Al 6061 based MMCs with 2 vol% reinforcement. These combined research efforts demonstrate the potential of PCTW technology for customizing of alloy composition and achieving microstructure control. A manufacturing process for titanium- and aluminum-based PCTWs was developed based on iterative design, theoretical calculations, and empirical data. PCTW technology successfully mitigated Al loss from Ti-6-4 and Mg loss in Al 6061, resulted in grain refinement in Ti-6-4, and demonstrated fabrication of Al based MMCs

Marcia S Domack↗

Recommended Practices for Managing Induced Seismicity Risk Associated with Geologic Carbon Storage

The geologic storage of carbon dioxide (CO 2 ) is one method to help reduce or eliminate atmospheric CO 2 emissions. The sequestered CO 2 is originally captured from the atmosphere or from a stationary industrial source and subsequently injected into a deep subsurface porous rock formation. To facilitate the successful deployment of field scale carbon storage projects, the U.S. Department of Energy (DOE) is developing tools and protocols for defensible, science-based frameworks to quantify and mitigate risks associated with the long-term storage of CO 2 . This protocol specifically addresses the risk of induced seismicity due to injection in a geologic carbon storage (GCS) site. This integrated and risk-based protocol is a product of the U.S. DOE Fossil Energy’s National Risk Assessment Partnership (NRAP), a multi-year collaborative research effort of Los Alamos National Laboratory (LANL), Lawrence Berkeley National Laboratory (LBNL), Lawrence Livermore National Laboratory (LLNL), National Energy Technology Laboratory (NETL), and Pacific Northwest National Laboratory (PNNL). These recommended practices describe a set of 7 steps to evaluate, manage, communicate, and mitigate the risk of induced seismicity at GCS sites. The base methodology of the recommended practices follows a framework similar to the Protocol for Addressing Induced Seismicity Associated with Enhanced Geothermal Systems (Majer et al., 2012), developed for the Geothermal Technology Office of the U.S. DOE. These recommended practices present a framework to systematically assess the induced seismicity risk and quantify the associated uncertainties. These recommendations are based on current research and are sufficiently general to allow for modification and application to a variety of different types of sites. The substance of the recommended practices contained herein includes both technical and non-technical issues, and covers all operational stages of the GCS project lifecycle. They start at the preliminary risk assessment phase, continue through site assessment and characterization, include best practice communication and seismic monitoring plan methodologies, discuss the evaluation and mitigation of seismic hazard and risk, and closes with an exploration of operational management plans, which conclude when the induced seismicity risk abates back to background level. The focus of these recommendations is on actively managing the risks associated with induced seismicity by developing an actionable risk management plan that starts at the project proposal stage and continues through site closure through an iterative assessment and improvement process. The audience of this document is expected to include all interested stakeholders (e.g., operators, project developers, regulators, and the general public) and is expressly written to be accessible to this broad range of partners. This document is intended to disseminate knowledge gained through recent advances in the science of induced seismicity hazard and risk assessments, to provide updates based on recent experience gained by similar corollary injection-induced seismicity cases, and most importantly to establish a uniform framework to carry out a successful induced seismicity risk management plan for carbon storage projects in the future. These recommendations do not directly address any domestic or international regulations or standards. A complementary NRAP report makes recommendations for the assessment and management of environmental subsurface risks associated with unwanted fluid migration at GCS sites (Thomas et al., 2021) and should be referred to in order to address those additional GCS site risks.

54 ENVIRONMENTAL SCIENCES↗

Recommended Practices for Managing Induced Seismicity Risk Associated with Geologic Carbon Storage

The geologic storage of carbon dioxide (CO 2 ) is one method to help reduce or eliminate atmospheric CO 2 emissions. The sequestered CO 2 is originally captured from the atmosphere or from a stationary industrial source and subsequently injected into a deep subsurface porous rock formation. To facilitate the successful deployment of field scale carbon storage projects, the U.S. Department of Energy (DOE) is developing tools and protocols for defensible, science-based frameworks to quantify and mitigate risks associated with the long-term storage of CO 2 . This protocol specifically addresses the risk of induced seismicity due to injection in a geologic carbon storage (GCS) site. This integrated and risk-based protocol is a product of the U.S. DOE Fossil Energy’s National Risk Assessment Partnership (NRAP), a multi-year collaborative research effort of Los Alamos National Laboratory (LANL), Lawrence Berkeley National Laboratory (LBNL), Lawrence Livermore National Laboratory (LLNL), National Energy Technology Laboratory (NETL), and Pacific Northwest National Laboratory (PNNL). These recommended practices describe a set of 7 steps to evaluate, manage, communicate, and mitigate the risk of induced seismicity at GCS sites. The base methodology of the recommended practices follows a framework similar to the $\textit{Protocol for Addressing Induced Seismicity Associated with Enhanced Geothermal Systems}$ (Majer et al., 2012), developed for the Geothermal Technology Office of the U.S. DOE. These recommended practices present a framework to systematically assess the induced seismicity risk and quantify the associated uncertainties. These recommendations are based on current research and are sufficiently general to allow for modification and application to a variety of different types of sites. The substance of the recommended practices contained herein includes both technical and non-technical issues, and covers all operational stages of the GCS project lifecycle. They start at the preliminary risk assessment phase, continue through site assessment and characterization, include best practice communication and seismic monitoring plan methodologies, discuss the evaluation and mitigation of seismic hazard and risk, and closes with an exploration of operational management plans, which conclude when the induced seismicity risk abates back to background level. The focus of these recommendations is on actively managing the risks associated with induced seismicity by developing an actionable risk management plan that starts at the project proposal stage and continues through site closure through an iterative assessment and improvement process. The audience of this document is expected to include all interested stakeholders (e.g., operators, project developers, regulators, and the general public) and is expressly written to be accessible to this broad range of partners. This document is intended to disseminate knowledge gained through recent advances in the science of induced seismicity hazard and risk assessments, to provide updates based on recent experience gained by similar corollary injection-induced seismicity cases, and most importantly to establish a uniform framework to carry out a successful induced seismicity risk management plan for carbon storage projects in the future. These recommendations do not directly address any domestic or international regulations or standards. A complementary NRAP report makes recommendations for the assessment and management of environmental subsurface risks associated with unwanted fluid migration at GCS sites (Thomas et al., 2021) and should be referred to in order to address those additional GCS site risks

58 GEOSCIENCES↗

Lateral and Vertical Heterogeneity of Thorium in the Procellarum KREEP Terrane: As Reflected in the Ejecta Deposits of Post-Imbrium Craters

The Procellarum KREEP Terrane displays the highest concentrations of Th on the Moon. However, locations of elevated Th in this region appear to be random. As observed in the 5 deg per pixel equal-area Th data, and made more evident in the preliminary 2 deg data, Th is enhanced around the craters Aristillus, Aristarchus, Kepler, Mairan, the Apennine Bench formation, and the Fra Mauro region, while noticeably and unexpectedly lower in other locations (e.g., Archimedes, Copernicus, Eratosthenes, and Plato). We have examined the composition of the materials present in these regions with the goal of understanding the patchy nature to the distribution of Th and ultimately to decipher the geologic processes that have concentrated the Th. At present time, the published resolution of the Lunar Prospector Th gamma-ray data is low (5 deg per pixel), but this will soon be superceded by significantly higher-resolution data (2 deg per pixel). Even at this improved resolution, however, it is difficult to resolve the units that are the major source of Th. In an attempt to circumvent this problem, we employ the higher-resolution Clementine multispectral data for those regions mentioned above. We use the UV-VIS-derived compositional information and the spectral properties of craters, and their ejecta as drill holes through the mare-basalt surface to investigate the thickness and composition of underlying material. With this information we attempt to piece together the stratigraphy and geologic history of the Imbrium-Procellanim region. We processed the five-band multispectral data from the Clementine Mission (415, 750,900,950, and 1000nm) using ISIS software and calibration parameters developed by the USGS, Flagstaff, Arizona. Final image mosaics are in equal-area sinusoidal projection, and have a resolution of 250 m/pixel. Using the method of we produced maps of FeO and Ti02 composition. Here we examine the Th, FeO, and Ti02 composition and spectral properties of the craters discussed above and their ejecta, with the goal of describing the materials they excavate. One interpretation for the origin of the high-Th material is that subsurface KREEPy materials have been excavated by impact craters. The material excavated may be either volcanic KREEP (e,g., Apennine Bench Formation), KREEPy impact-melt breccia formed by the Imbrium impact (e.g., Fra Mauro Formation), or other KREEP-rich crustal material. Determining which type of material is responsible for the elevated Th and its extent is important to understanding the premare and possibly the prebasin stratigraphy of the Imbrium-Procellarum Region. Merging the 5 deg. Th data with the shaded relief map, we observe that the highest Th concentrations are not related to pre-Imbrium upper crustal materials. The Apennines, Alpes, and Caucasus Mountains represent the pre-Imbrian highlands material and do not express concentrations of Th, FeO, and TiO2 as high as the most Th-fich materials exposed within the Procellarum KREEP Terrane. We observe that, in general, these massifs contain 10-14 wt% FeO and 4-7 ppm Th. Determining whether the Th signal is from KREEP basalts or KREEPy impact-melt breccias cannot be done with the Clementine data because the two rock types are compositionally and mineralogically too similar (e.g., the Th-rich, mafic impact-melt breccias in the Apollo sample collection are dominated by a KREEP-basalt like component. Mapping-the distribution and sizes of craters and whether they display elevated Th concentrations or not, should reveal the depth and thickness of the KREEP-rich materials, and whether they are ubiquitous (i.e., impact-melt breccia) or more randomly distributed; this might be taken as an indicator of localized KREEP-basalt flows. Within the southeastern region of the Imbrium basin, there are two Th hot spots. The first is associated with the crater Aristillus, and the latter with the Apennine Bench Formation. Adjacent to these two hot spots are craters with a lower Th signature: Archimedes and Autolycus. We observe in the ejecta of Aristillus, a region of significantly lower FeO (10-14 wt%) relative to the surrounding mare basalt. The crater Autolycus, 50 km to the south, did not excavate similar low-FeO material. We suggest that the lower-FeO material in the ejecta of Aristillus corresponds to Th-rich material; the FeO content observed in Aristillus ejecta is comparable to that of KREEP basalt or mafic impact melt breccia (10-12 wt% FeO). We determine that this low FeO, Th-rich material is volcanic KREEP, as opposed to Imbrium impact melt, on the basis that the low-Fe material is exposed more prominently in ejecta in the northern portion of Aristillus. Our assumption is that if the layer underlying Aristillus was continuous, a more widespread and uniform low-Fe signature wouldbe observed in the ejecta deposit. Archimedes, 110 km southwest of Aristillus, impacted the northern portion of the Apennine Bench prior to the eruption of KREEP basalt. Archimedes rim material is not as enriched in Th as the Apennine Bench, and there are differences between the two in FeO concentration and in their continuum slope. Archimedes exhibits a much steeperor "redder" continuum slope than the Apennine Bench. This steepslope suggests the presence of glassy material. The glassy material is concentrated around an unnamed crater on the southern rim of Archimedes (4.5W, 28.2N) and along the northern rim of Archimedes. We suggest two possibilities, or a combination of the two, to explain the low-Th signal from Archimedes: (1) The Apennine Bench prior to KREEP basalt eruption was lower in Th (4-7 ppm, e.g., similar to the Apennine massifs) and KREEP basalts are absent in the rim of Archimedes; or (2) the glassy (possibly pyroclastic) material layering the rim of the Archimedes, dilutes any high-Th material present with low-Th material. (Additional information is contained in the original)

Gillis, J. J.↗