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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.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Determining initial enrichment, burnup, and cooling time of pressurized-water reactor spent fuel assemblies by analyzing passive gamma spectra measured at the Clab interim-fuel storage facility in Sweden

The purpose of the Next Generation Safeguards Initiative (NGSI)–Spent Fuel (SF) project is to strengthen the technical toolkit of safeguards inspectors and/or other interested parties. The NGSI–SF team is working to achieve the following technical goals more easily and efficiently than in the past using nondestructive assay measurements of spent fuel assemblies: (1) verify the initial enrichment, burnup, and cooling time of facility declaration; (2) detect the diversion or replacement of pins; (3) estimate the plutonium mass [which is also a function of the variables in (1)]; (4) estimate the decay heat; and (5) determine the reactivity of spent fuel assemblies. Since August 2013, a set of measurement campaigns has been conducted at the Central Interim Storage Facility for Spent Nuclear Fuel (Clab), in collaboration with Swedish Nuclear Fuel and Waste Management Company (SKB). One purpose of the measurement campaigns was to acquire passive gamma spectra with high-purity germanium and lanthanum bromide scintillation detectors from Pressurized Water Reactor and Boiling Water Reactor spent fuel assemblies. The absolute 137 Cs count rate and the 154 Eu/ 137 Cs, 134 Cs/ 137 Cs, 106 Ru/ 137 Cs, and 144 Ce/ 137 Cs isotopic ratios were extracted; these values were used to construct corresponding model functions (which describe each measured quantity’s behavior over various combinations of burnup, cooling time, and initial enrichment) and then were used to determine those same quantities in each measured spent fuel assembly. Furthermore, the results obtained in comparison with the operator declared values, as well as the methodology developed, are discussed in detail in the paper.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

TEM Video Compressive Sensing

One of the main limitations of imaging at high spatial and temporal resolution during in-situ TEM experiments is the frame rate of the camera being used to image the dynamic process. While the recent development of direct detectors has provided the hardware to achieve frame rates approaching 0.1ms, the cameras are expensive and must replace existing detectors. In this paper, we examine the use of coded aperture compressive sensing methods [1, 2, 3, 4] to increase the framerate of any camera with simple, low-cost hardware modifications. The coded aperture approach allows multiple sub-frames to be coded and integrated into a single camera frame during the acquisition process, and then extracted upon readout using statistical compressive sensing inversion. Our simulations show that it should be possible to increase the speed of any camera by at least an order of magnitude. Compressive Sensing (CS) combines sensing and compression in one operation, and thus provides an approach that could further improve the temporal resolution while correspondingly reducing the electron dose rate. Because the signal is measured in a compressive manner, fewer total measurements are required. When applied to TEM video capture, compressive imaging couled improve acquisition speed and reduce the electron dose rate. CS is a recent concept, and has come to the forefront due the seminal work of Candès [5]. Since the publication of Candès, there has been enormous growth in the application of CS and development of CS variants. For electron microscopy applications, the concept of CS has also been recently applied to electron tomography [6], and reduction of electron dose in scanning transmission electron microscopy (STEM) imaging [7]. To demonstrate the applicability of coded aperture CS video reconstruction for atomic level imaging, we simulate compressive sensing on observations of Pd nanoparticles and Ag nanoparticles during exposure to high temperatures and other environmental conditions. Figure 1 highlights the results from the Pd nanoparticle experiment. On the left, 10 frames are reconstructed from a single coded frame—the original frames are shown for comparison. On the right a selection of three frames are shown from reconstructions at compression levels 10,20,30. The reconstructions, which are not post-processed, are true to the original and degrade in a straightforward manner. The final choice of compression level will obviously depend on both the temporal and spatial resolution required for a specific imaging task, but the results indicate that an increase in speed of better than an order of magnitude should be possible for all experiments. References: [1] P Llull, X Liao, X Yuan et al. Optics express 21(9), (2013), p. 10526. [2] J Yang, X Yuan, X Liao et al. Image Processing, IEEE Trans 23(11), (2014), p. 4863. [3] X Yuan, J Yang, P Llull et al. In ICIP 2013 (IEEE), p. 14. [4] X Yuan, P Llull, X Liao et al. In CVPR 2014. p. 3318. [5] EJ Candès, J Romberg and T Tao. Information Theory, IEEE Trans 52(2), (2006), p. 489. [6] P Binev, W Dahmen, R DeVore et al. In Modeling Nanoscale Imaging in Electron Microscopy, eds. T Vogt, W Dahmen and P Binev (Springer US), Nanostructure Science and Technology (2012). p. 73. [7] A Stevens, H Yang, L Carin et al. Microscopy 63(1), (2014), pp. 41.

Stevens, Andrew↗
DOE OSTI2017

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO2

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H2O is well known to be systematically correlated with the hydration free energy of the interlayer cation, in environments dominated by non-polar solvents (i.e. CO2), uptake into the interlayer is not well-understood. Using novel high pressure capabilities, we investigated the interaction of super-critical CO2 with Na+-, NH4+-, and Cs+-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend in H2O, and that cation solvation energies in CO2 suggest a stronger interaction with Na+, both the NH4+- and Cs+-clays readily absorbed CO2 and expanded while the Na+-clay did not. The apparent inertness of the Na+-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO2 intercalation in the Na+-clay, but little or no energy barrier for the NH4+- and Cs+-clays. Consequently, we have shown for the first time that in the presence of a low dielectric constant gas swelling depends more on the strength of the interaction between interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicates swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semi-permeable reactive barriers.

CO2, montmorillonite, molecular dynamics↗
DOE OSTI2020

Suppressing Cation Migration in Triple-Cation Lead Halide Perovskites

Ion migration represents an intrinsic instability of metal halide perovskite solar cells. In this work, we show that triple-cation FA x MA y Cs 1–x–y PbI 3 [FA + = (NH 2 ) 2 CH + , MA + = CH 3 NH 3 + ] active layers with mixed orthorhombic, post-perovskite (δ ortho -CsPbI 3 ), and cubic perovskite (α) phases (i.e., α/δ-phase FA x MA y Cs 1–x–y PbI 3 ) exhibit improved cation stability against applied bias relative to pure α-phase perovskites (i.e., FA 0.85 Cs 0.15 PbI 3 and FA 0.76 MA 0.15 Cs 0.09 PbI 3 ). Infrared photothermal heterodyne imaging and time-of-flight secondary ion mass spectrometry are used to visualize exclusive α-phase perovskite lateral device A + cation accumulation (depletion) at perovskite negative (positive) electrode interfaces. The resulting compositional heterogeneities lead to degradation. Operational stability testing of solar cells reveals similar degradation behavior; α/δ-phase FA x MA y Cs 1–x–y PbI 3 lateral devices/solar cells, by contrast, show improved stabilities. Enhanced α/δ-FA x MA y Cs 1–x–y PbI 3 stability is rationalized by δortho-phase inclusions, acting as barriers through which A + cations do not easily migrate. This study thus provides new insights into cation migration in FA x MAyCs 1–x–y PbI 3 perovskites and suggests a materials design strategy toward suppressing cation instabilities in hybrid perovskites.

14 SOLAR ENERGY↗
DOE OSTI2023

Morphology Dependent Reactivity of CsO $x$ Nanostructures on Au(111): Binding and Hydrogenation of CO 2 to HCOOH

Cesium oxide (CsO $x$ ) nanostructures grown on Au(111) behave as active centers for CO 2 binding and hydrogenation reactions. The morphology and reactivity of these CsO $x$ systems were investigated as a function of alkali coverage using scanning tunnelling microscopy (STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and density functional theory (DFT) calculations. STM results show that initially (0.05 - 0.10 ML) cesium oxide clusters (Cs 2 O 2 ) grow at the elbow sites of the herringbone of Au(111), subsequently transforming into two-dimensional islands with increasing cesium coverage (> 0.15 ML). XPS measurements reveal the presence of suboxidic (Cs $y$ O; $y$ ≥ 2) species for the island structures. The higher coverages of cesium oxide nanostructures contain a lower O/Cs ratio resulting in a stronger binding of CO 2 . Moreover, the O atoms in the Cs $y$ O structure undergo a rearrangement upon the adsorption of CO 2 which is a reversible phenomenon. Under CO 2 hydrogenation conditions, the small Cs 2 O 2 clusters are hydroxylated, thereby preventing the adsorption of CO 2 . However, the hydroxylation of the higher coverages of Cs $y$ O did not prevent CO 2 adsorption, and the adsorbed CO 2 transformed to HCOO species that eventually yield HCOOH. DFT calculations further confirm that the dissociated H 2 attacks the C in the adsorbate to produce formate, which is both thermodynamically and kinetically favored during the CO 2 reaction with hydroxylated Cs $y$ O. These results demonstrate that cesium oxide by itself is an excellent catalyst for CO 2 hydrogenation that could produce formate, an important intermediate for the generation of value-added species. The role of the alkali oxide nanostructures as active centers, not merely as promoters, may have broad implications wherein the alkali oxides can be considered in the design of materials tuned for specific applications in heterogeneous catalysis.

03 NATURAL GAS↗
DOE OSTI2025

Connectivity-Dependent Exciton–Phonon Coupling in Cesium Bismuth Halide Quantum Dots

Metal halide octahedra form the fundamental functional building blocks of metal halide perovskites, dictating their structures, optical properties, electronic structures, and dynamics. Here, in this study, we show that the connectivity of bismuth halide octahedra in Cs 3 Bi 2 Br 9 and Cs 3 Bi 2 I 9 quantum dots (QDs) changes with different halide elements. We use first-principles calculations to reveal the key role of the connectivity of bismuth halide octahedra on the wave function symmetry, Huang-Rhys factor, and exciton-phonon interaction strength. Following QD synthesis via a ligand-mediated transport method, the effect of connectivity is verified with transient absorption spectroscopy, where we contrast Cs 3 Bi 2 Br 9 and Cs 3 Bi 2 I 9 QD exciton dynamics. In photoexcited Cs 3 Bi 2 I 9 QDs, phonons related to the vibrational motions of face-sharing [BiI 6 ] 3- bioctahedra couple strongly to the electronic state and drive rapid carrier relaxation. Equivalent signals are not observed for photoexcited Cs 3 Bi 2 Br 9 QDs, implying a lack of phonon involvement in band-edge absorption and subsequent exciton relaxation. Our findings suggest that structural engineering can effectively tune the exciton-phonon coupling and therefore influence exciton relaxation and recombination in perovskite nanomaterials.

TDDFT↗
DOE OSTI2019

Deciphering the degradation mechanism of the lead-free all inorganic perovskite Cs2SnI6

Abstract Organic-inorganic perovskite materials are revolutionizing photovoltaics with high power conversion efficiencies, but experience significant environmental degradation and instability. In this work, the phase stability and decomposition mechanisms of lead-free all inorganic Cs 2 SnI 6 perovskite upon water and moisture exposure were systematically investigated via in situ synchrotron X-ray diffraction, environmental SEM, and micro-Raman spectroscopy. A critical relative humidity (80%) is identified below which Cs 2 SnI 6 perovskite is stable without decomposition. Under higher humidity or aqueous environment, Cs 2 SnI 6 perovskite decomposes into SnI 4 and CsI through etch pits formation and stepwave propagation, leading to rapid crystal dissolution. A partial reversibility of the Cs 2 SnI 6 perovskite upon dissolution and re-precipitation with subsequent dehydration was identified, suggesting a self-healing capability of Cs 2 SnI 6 and thus enhanced air stability. Mechanistic understanding of the Cs 2 SnI 6 degradation behavior can be a vital step towards developing new perovskites with enhanced environmental stability and materials performance.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Jahn–Teller distortion controls electron transfer in photoexcited Cu( I ) donor–acceptor systems

The Jahn–Teller distortion (JTD) is a defining structural response to electronic excitation in Cu( I )-based transition metal complexes, yet its role in photoinduced electron transfer (PET) remains largely unexplored. Here, we demonstrate that the JTD governs charge separation (CS) through a vibronically controlled conical intersection in heteroleptic Cu( I ) bisphenanthroline–naphthalene diimide (CuHETPHEN-NDI) donor–acceptor dyads. Using 20-fs broadband transient absorption spectroscopy combined with coherent vibrational wavepacket (CVWP) analysis and quantum chemical calculations, we directly track nuclear motions that steer the system from the metal-to-ligand charge-transfer ( 1 MLCT) state to the CS state. Steric bulkiness of the pendant groups at the 2,9-positions of the phenanthroline ligand systematically slows both JTD and CS. Short-time Fourier transformation and Fourier filtering analyses identify two key vibrational signatures: a low-frequency breathing mode (∼100 cm −1 ) via a bond distance change between Cu and ligated Ns (Cu–N) that modulates the NDI anion absorption and acts as a vibronic coupling coordinate, and a higher-frequency mode (∼313 cm −1 ) that evolves along the PET trajectory. Normal mode analysis and potential energy surface calculations show that the JTD brings the 1 MLCT and CS states into degeneracy, while the Cu–N breathing motion dynamically modulates donor–acceptor electronic coupling to enable ultrafast nonadiabatic electron transfer. Steric hindrance exerted by the groups at the 2,9 positions of the phenanthroline ligands suppresses this vibronic coupling, leading to faster CVWP decoherence for the 313 cm −1 mode and slower CS. These findings unravel JTD-controlled vibronic coupling at conical intersection as a governing factor for CS and provide insight into designing Cu-based photosensitizers by harnessing structural dynamics to control PET.

Kim, Pyosang [Argonne National Laboratory (ANL), A↗
DOE OSTI2016

Effects of cesium ion-implantation on mechanical and electrical properties of organosilicate low-k films

The effects of cesium (Cs) ion-implantation on uncured plasma-enhanced chemical-vapor-deposited organosilicate low dielectric constant (low-k) (SiCOH) films have been investigated and compared with an ultraviolet (UV) cured film. The mechanical properties, including the elastic modulus and hardness, of the SiCOH low-k films are improved by up to 30% with Cs implantation, and further up to 52% after annealing at 400 °C in a N{sub 2} ambient for 1 h. These improvements are either comparable to or better than the effects of UV-curing. They are attributed to an enhancement of the Si-O-Si network structure. The k-value of the SiCOH films increased slightly after Cs implantation, and increased further after annealing. These increases are attributed to two carbon-loss mechanisms, i.e., the carbon loss due to Si-CH{sub 3} bond breakage from implanted Cs ions, and the carbon loss due to oxidation during the annealing. The time-zero dielectric breakdown strength was improved after the Cs implantation and the annealing, and was better than the UV-cured sample. These results indicate that Cs ion implantation could be a supplement to or a substitution for the currently used UV curing method for processing SiCOH low-k films.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Harvesting electrons and holes from photodriven symmetry-breaking charge separation within a perylenediimide photosynthetic model dimer

Understanding how to utilize symmetry-breaking charge separation (SB-CS) offers a path toward increasingly efficient light-harvesting technologies. This process plays a central role in the first step of photosynthesis, in which the dimeric “special pair” of the photosynthetic reaction center enters a coherent SB-CS state after photoexcitation. Previous research on SB-CS in both biological and synthetic chromophore dimers has focused on increasing the efficiency of light-driven processes. In a chromophore dimer undergoing SB-CS, the energy of the radical ion pair product is nearly isoenergetic with that of the lowest excited singlet (S 1 ) state of the dimer. This means that very little energy is lost from the absorbed photon. In principle, the relatively high energy electron and hole generated by SB-CS within the chromophore dimer can each be transferred to adjacent charge acceptors to extend the lifetime of the electron–hole pair, which can increase the efficiency of solar energy conversion. To investigate this possibility, we have designed a bis-perylenediimide cyclophane (mPDI 2 ) covalently linked to a secondary electron donor, peri-xanthenoxanthene (PXX) and a secondary electron acceptor, partially fluorinated naphthalenediimide (FNDI). Upon selective photoexcitation of mPDI 2 , transient absorption spectroscopy shows that mPDI 2 undergoes SB-CS, followed by two secondary charge transfer reactions to generate a PXX •+ -mPDI 2 -FNDI •– radical ion pair having a nearly 3 µs lifetime. In conclusion, this strategy has the potential to increase the efficiency of molecular systems for artificial photosynthesis and photovoltaics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Resonant x-ray emission across the L 3 edge of uranium compounds

A narrow bandwidth x-ray beamline and a multi-crystal von Hamos spectrometer were used to record x-ray absorption and x-ray emission (XES) across the uranium L 3 edge of UO 2 , UO 3 , Cs 2 UO 2 Cl 4 , and Cs 2 UCl 6 . Measurements were made over 17150–17250 eV with an instrumental resolution of ∼2 eV. This resolution allowed the use of Lorentzian peak fits to the L 3 N 4 and L 3 N 5 characteristic x-ray fluorescence lines that have ∼12–13 eV lifetime widths. The fluorescence yields of the four compounds display strong white lines near threshold and multiple scattering features at higher energies. The XES spectra were fit with three Lorentzians, two for the L 3 N 4 and L 3 N 5 lines and one for inelastic scattering by 2p–6d excitations and 4d–6d final states. The intensities of the white lines were largely due to the inelastic scattering component. To support the measurements, relativistic equation-of-motion coupled-cluster and restricted active space configuration interaction calculations were performed for uranium core-excitation energies in Cs 2 UO 2 Cl 4 and Cs 2 UCl 6 . These calculations with rigorous treatments of relativistic effects are shown to provide accurate uranium L 3 -edge binding energies, L 3 N 5 emission energies, as well as the energy losses in the inelastic scattering process. The measured and calculated results show variations between compounds with U(IV) oxidation states that contain 6d 0 5f 2 electrons in their ground configurations (UO 2 and Cs 2 UCl 6 ) compared with U(VI) compounds (UO 3 and Cs 2 UO 2 Cl 4 ) with empty 5f and 6d configurations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Thermodynamic assessment of the hollandite high‐level radioactive waste form

Abstract Hollandite has been studied as a candidate ceramic waste form for the disposal of high‐level radioactive waste due to its inherent leach resistance and ability to immobilize alkaline‐earth metals such as Cs and Ba at defined lattice sites in the crystallographic structure. The chemical and structural complexity of hollandite‐type phases developed for high‐level waste immobilization limits the systematic experimental research that is required to understand phase development due to the large number of potential additives and compositional ranges that must be evaluated. Modeling the equilibrium behavior of the complex hollandite‐forming oxide waste system would aid in the design and processing of hollandite waste forms by predicting their thermodynamic stability. Thus, a BaO–Cs 2 O–TiO 2 –Cr 2 O 3 –Al 2 O 3 –Fe 2 O 3 –FeO–Ga 2 O 3 thermodynamic database was developed in this work according to the CALPHAD methodology. The compound energy formalism was used to model solid solution phases such as hollandite while the two‐sublattice partially ionic liquid model characterized the oxide melt. Results of model optimizations are presented and discussed including a 1473 K isothermal BaO–Cs 2 O–TiO 2 pseudo‐ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.

Utlak, Stephen A.↗
DOE OSTI2016

SU-F-T-377: Monte Carlo Re-Evaluation of Volumetric-Modulated Arc Plans of Advanced Stage Nasopharygeal Cancers Optimized with Convolution-Superposition Algorithm

Background: Commercial treatment planning system Pinnacle3 (Philips, Fitchburg, WI, USA) employs a convolution-superposition algorithm for volumetric-modulated arc radiotherapy (VMAT) optimization and dose calculation. Study of Monte Carlo (MC) dose recalculation of VMAT plans for advanced-stage nasopharyngeal cancers (NPC) is currently limited. Methods: Twenty-nine VMAT prescribed 70Gy, 60Gy, and 54Gy to the planning target volumes (PTVs) were included. These clinical plans achieved with a CS dose engine on Pinnacle3 v9.0 were recalculated by the Monaco TPS v5.0 (Elekta, Maryland Heights, MO, USA) with a XVMC-based MC dose engine. The MC virtual source model was built using the same measurement beam dataset as for the Pinnacle beam model. All MC recalculation were based on absorbed dose to medium in medium (Dm,m). Differences in dose constraint parameters per our institution protocol (Supplementary Table 1) were analyzed. Results: Only differences in maximum dose to left brachial plexus, left temporal lobe and PTV54Gy were found to be statistically insignificant (p> 0.05). Dosimetric differences of other tumor targets and normal organs are found in supplementary Table 1. Generally, doses outside the PTV in the normal organs are lower with MC than with CS. This is also true in the PTV54-70Gy doses but higher dose in the nasal cavity near the bone interfaces is consistently predicted by MC, possibly due to the increased backscattering of short-range scattered photons and the secondary electrons that is not properly modeled by the CS. The straight shoulders of the PTV dose volume histograms (DVH) initially resulted from the CS optimization are merely preserved after MC recalculation. Conclusion: Significant dosimetric differences in VMAT NPC plans were observed between CS and MC calculations. Adjustments of the planning dose constraints to incorporate the physics differences from conventional CS algorithm should be made when VMAT optimization is carried out directly with MC dose engine.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Finalized configuration of magnetic shielding for LEReC cooling section

In the LEReC Cooling Section (CS) the RHIC ions are traveling together with and getting cooled by the LEReC electrons. The required cooling rate sets the limit of 150 urad on tolerable angles of the electrons in the CS. One of the components of overall electron angle is the angle of the e-beam trajectory with respect to the ion beam trajectory. We set the limit for electron trajectory angle to 100 urad. It is critical for preserving small trajectory angle to keep the transverse magnetic field inside the CS drifts within +/- 2.3 mG. The drifts in the CS must be shielded from the ambient magnetic fields of the RHIC tunnel, which can be as high as 0.5 G, to minimize the transverse field inside the CS vacuum chamber. In this paper we present the final design of the magnetic shielding of the LEReC CS and discuss the results of tests dedicated to studies of the shielding effectiveness.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

Assessment of Cold Spray Technology for Nuclear Power Applications

This report provides an overview of cold spray (CS) technology as it relates to repair and fabrication of metal alloys in the nuclear power industry. CS is a relatively new technology with applications established in other industries (e.g., aerospace, defense), and greater use of CS is anticipated within the nuclear power industry. This report is prepared in support of the United States Nuclear Regulatory Commission (NRC) Action Plan for Advanced Manufacturing Technologies (AMTs) Rev. 1, which includes objectives to identify the AMTs most likely to be used for nuclear power applications that require NRC approval, and to prepare NRC staff to review regulatory submittals containing components manufacturing using AMTs. In addition to providing an overview of CS technology, this report highlights engineering and scientific knowledge gaps of CS and rates the size of the knowledge gaps. It also assesses importance rankings of the knowledge gaps as they relate to several application categories. The application categories considered in this exercise include factory-applied CS for chloride induced stress corrosion cracking (CISCC) mitigation, field CISCC repair, light water reactor (LWR) factory structural fabrication, and LWR field dimensional restoration and corrosion protection. The combination of a knowledge gap size rating and importance ranking for an application can be used to prioritize additional data or information gathering efforts.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2022

Literature Review on Next Generation Solvent Isopar ® L Vapor Pressure Curve and the Partitioning of its Modifier and Extractant

The Next Generation Solvent (NGS) is set to replace the Original Caustic Side Solvent Extractant (CSSX) at the Salt Waste Processing Facility (SWPF). The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC), formerly Savannah River Remediation (SRR), to perform a literature review on the following topics to address flammability concerns with the current solvent: Isopar ® L vapor pressure curve for NGS, partitioning ratio for the extractant MaxCalix and the modifier Cs-7SB, and high cesium concentration impacts on NGS radiolysis and potential solvent degradation rates in high cesium concentrations. The following conclusions and recommendations are made based on previous experimental work and literature: (1) Current SWPF flammable gas generation calculations use an Isopar ® L vapor pressure curve based on experimental testing with the Original CSSX solvent. No such testing to date has been performed with NGS. It is suggested that the decrease in Cs-7SB concentration for NGS compared to the Original CSSX solvent would lead to a slightly higher vapor pressure at all temperatures in SWPF vessels. A bounding NGS vapor pressure curve has been provided; it is recommended to see if these values would challenge current flammability controls and to perform testing if needed.(2) The partitioning ratio for Cs-7SB is known in the Original CSSX solvent with dilute nitric acid and caustic solutions. No tests could be found for the partitioning of Cs-7SB to dilute boric acid solutions; however, a similar partitioning ratio is expected. Due to the lipophilic alkyl chains on MaxCalix, it is expected to be even less soluble than BOBCalixC6 in the aqueous phase and should not be considered a significant contributor to the f organic term. Additionally, the reaction rate of N,N’,N’’-Tris(3,7-dimethyloctyl)guanidine (TiDG) or its degradation products with a hydrogen radical should be estimated/determined if they are found to be significant contributors to the f organic term. (3) NGS is expected to see much higher Cs concentrations at SWPF in comparison to its use at the Modular CSSX Unit (MCU). These higher Cs concentrations could influence radiolytic degradation rates of the solvent. NGS appears to be fairly stable to radiolytic degradation based on previous testing and its use at MCU. However, there has not been radiolytic flammable gas generation testing with NGS to date. There is a risk that the continued use of G-values obtained for flammable gases produced from the irradiation of the Original CSSX solvent is not bounding for NGS, but this is considered a very low risk due to the similarities in the composition of the solvents, as well as the conservatisms in the experimental design of the Original CSSX testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Options for the Removal of Cesium and Strontium from Acidic Uranyl Sulfate Solutions from Molybdenum-99 Production: Part II The Effect of Sodium Carbonate Adjustment to pH 9 on Strontium Removal

A small laboratory-scale column process aimed at removing fission products from prototypical acidic sulfate solution wastes from a prototypical Mo-99 recovery process has been operated in a radioactive materials hood at Savannah River National Laboratory. This equipment has been operated with realistic concentrations of uranium (0.4 wt % 235 U), plutonium ( 239 Pu), neptunium ( 237 Np), non-radioactive surrogates of common fission products (including Cs and Sr) and two promising absorbents – AMP-PAN and CST R9120-B. The goal of this work was to demonstrate the removal and concentration of high specific activity isotopes which are expected to dominate the classification of the low-level waste from the production of 99 Mo. Both AMP-PAN and CST R9120-B are attractive absorbents for the removal of 137 Cs from an acidic sulfate waste stream. They do not provide a solution for the removal of 90 Sr from the acidic solutions. CST was shown to be useful at removing both Cs and Sr after adjustment of the acidic sulfate solution with sodium carbonate to pH 9. Limited removal of transuranic species and almost no removal of uranium was observed for CST R9120B absorbent. This could be important due to the relatively large amount of uranium expected to be present in such waste streams. The capacity of these absorbents for 137 Cs will likely be dependent on the Cs concentration in the solutions processed but loading in excess of 0.7 mg Cs per gram of CST absorbent while loading 0.14 mg Sr per gram of CST absorbent appears to be achievable from pH 9 carbonate solution.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Non-Neutron Transmutation of Used Nuclear Fuel (Final Report)

The primary goal of this study is to develop a national facility concept for transmuting long-lived fission products (LLFP) to substantially reduce the disposal impact by minimizing the need for a geologic-timescale repository. As a charter for this study, the national transmutation facility was required to reduce the radiotoxicity and decay heat of LLFP isotopes by at least 90% relative to their values at discharge from a commercial LWR, while consuming less than 10% of the reactor's energy. The identified LLFP isotopes are Se-79, Zr-93, Tc-99, I-129, Sn-126, and Cs-135, whose radiotoxicity is about 99% of the total radiotoxicity of all fission products at 1,000 years. Approximately ~72 kg of LLFPs is discharged every year from a 1,000 MWe commercial or advanced nuclear reactor. First, LLFP transmutation options with non-neutron beams (photons and protons) were explored. The study concluded that LLFP transmutation is feasible with high-energy, high-intensity photons or protons, but impractical on an engineering scale due to low transmutation rates and the high energy requirements to produce the desired photon or proton beams. As alternatives, LLFP transmutation options with neutrons from fission, fusion, and spallation reactions were additionally explored. The transmutation options using advanced critical reactors are attractive only for selective LLFP isotopes because the production rates of several LLFP isotopes (Zr-93, Sn-126, and Cs-135) from fission reactions are larger than the transmutation rates. The transmutation options with only spallation neutrons are favorable to transmute all LLFP isotopes, but as a tradeoff, the net transmutation rates are reduced. The national transmutation facility concept was developed following an exploration of transmutation options using various incident particles. The proposed national LLFP transmutation comprises a dedicated molten-salt reactor (MSR), a proton accelerator, and a spallation neutron-based transmuter. The MSR power was set at 300 MWt and 120 MWe, with the thermal power approximately 10% of that of a commercial 1,000 MWe PWR. The electricity generated by the MSR powers the accelerator and transmuter. The accelerator produces 1 GeV, 30 mA protons, which are introduced into the spallation neutron-based transmuter. The spallation neutron-based transmuter consists of a central spallation target and LLFP target pins merged in a heavy water tank. The six LLFP isotopes are separated into two groups. Tc-99, I-129, and Se-79, having larger neutron cross sections, belong to group A, while Zr-93, Sn126, and Cs-135, having smaller neutron cross sections, belong to group B. Then, for effective transmutation, LLFPs in groups A and B are transmuted in the dedicated MSR and in a spallation neutron-based transmuter, respectively. The estimated capital cost of the national transmutation facility is approximately $\$$3.1B, and its annual O&M cost is expected to be ~$\$$182M. Radiotoxicity and decay heat of LLFPs were calculated and compared with those of the original LLFPs. It was assumed that the targets were made with elementwise LLFP rather than isotopic LLFP, owing to the potentially high cost of isotopic separation from used nuclear fuels. The decay heat of LLFPs can be reduced by more than 90% using a single national transmutation facility. However, radiotoxicity decreases by 79–84%, which does not meet the transmutation performance requirement, primarily because Cs-135 is produced rather than depleted. Thus, to meet the design requirement, Cs-135 should be separated from other Cs isotopes and irradiated in a spallation neutron-based transmuter. Then, radiotoxicity decreases by ~92%.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗