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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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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Post-process annealing of large-scale 3D printed polyphenylene sulfide composites

Large-scale extrusion-based additive manufacturing of high-performance thermoplastic composites like fiber reinforced polyphenylene sulfide (PPS) is well-suited for tooling applications to lower manufacturing costs and lead times. Autoclave tooling requires good mechanical performance at temperatures even above the glass transition temperature (T g ). In this work, the authors have investigated a post-process isothermal annealing technique to improve the mechanical properties of various grades of carbon fiber reinforced PPS components printed on the Big Area Additive Manufacturing (BAAM) system. Since PPS is a semi-crystalline polymer, crystallinity can change during annealing and affect the mechanical properties of the part. In addition, isothermal annealing can also lead to solid-state structural changes in the form of thermal and oxidative branching and/or crosslinking reactions in some grades of PPS which can alter the crystallization process. This work reports the effect of annealing on dynamic mechanical properties of BAAM printed components, along with studies to determine the effect of annealing on crystallinity and the occurrence of oxidative reactions. Results showed that isothermal annealing at 250 °C for 18 h improved the storage modulus of all selected grades (neat and reinforced) of PPS at temperatures above T g . Annealing led to an overall increase in the degree of crystallinity, with secondary crystallization taking place. Although oxidative structural changes were observed to occur more on the surface of the PPS parts, they primarily influenced the size of crystals formed and did not significantly alter the degree of crystallinity at various regions within the sample.

36 MATERIALS SCIENCE↗
DOE OSTI2022

MoO x S y /Ni 3 S 2 Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

Hydrogen energy derived from water splitting is the cleanest renewable energy source, but it is also very challenging to achieve because the hydrogen evolution reaction (HER) requires highly efficient and low-cost electrocatalysts. Here, we have fabricated a novel hierarchical system of amorphous molybdenum oxy/sulfide microspheres with crystalline Ni 3 S 2 intergrown in situ on Ni foam (MoO x S y /Ni 3 S 2 /NF) as an outstanding electrocatalyst for HER. The MoO x S y /Ni 3 S 2 /NF demonstrates an ultra-low overpotential of 58 mV at a current density of 10 mA cm -2 and extremely durable stability (>200 h), suggesting superior performance comparable to that of Pt-C/NF under acidic conditions. The X-ray absorption fine structure (XAFS) determines the average valence state of Mo to be +(5 + δ), with a coordination motif by O and S. To explain such high HER activity, a [Mo 2 O 2 (S,O) 4 ] dimer-based periodic model structure with the average composition of [Mo 4 O 8 S 4 ] interfaced with the Ni 3 S 2 (101) surface is proposed. The interactions between the Ni of Ni 3 S 2 and bridging S/O of [Mo 4 O 8 S 4 ] result in an average formal Mo charge state between +5 and +6, and significant charge transfer from Ni 3 S 2 to [Mo 4 O 8 S 4 ] activates the Mo = O bonds. The calculated |ΔG H* | of less than 50 meV suggests that the double-bonded O is the most active site. This work points to the importance of oxy/sulfides with Mon+ (+5 < n < +6) as exceptional electrochemical catalysts for HER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Supramolecular meso -Trick: Ambidextrous Mirror Symmetry Breaking in a Liquid Crystalline Network with Tetragonal Symmetry

Bicontinuous and multicontinuous network phases are among nature's most complex structures in soft matter systems. Here, a chiral bicontinuous tetragonal phase is reported as a new stable liquid crystalline intermediate phase at the transition between two cubic phases, the achiral double gyroid and the chiral triple network cubic phase with an I 23 space group, both formed by dynamic networks of helices. The mirror symmetry of the double gyroid, representing a meso -structure of two enantiomorphic networks, is broken at the transition to this tetragonal phase by retaining uniform helicity only along one network while losing it along the other one. This leads to a conglomerate of enantiomorphic tetragonal space groups, P 4 1 2 1 2 and P 4 3 2 1 2. Phase structures and chirality were analyzed by small-angle X-ray scattering (SAXS), grazing-incidence small-angle X-ray scattering (GISAXS), resonant soft X-ray scattering (RSoXS) at the carbon K-edge, and model-dependent SAXS/RSoXS simulation. In conclusion, our findings not only lead to a new bicontinuous network-type three-dimensional mesophase but also reveal a mechanism of mirror symmetry breaking in soft matter by partial meso -structure racemization at the transition from enantiophilic to enantiophobic interhelical self-assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Dynamical symmetry indicators for Floquet crystals

Various exotic topological phases of Floquet systems have been shown to arise from crystalline symmetries. Yet, a general theory for Floquet topology that is applicable to all crystalline symmetry groups is still in need. In this work, we propose such a theory for (effectively) non-interacting Floquet crystals. We first introduce quotient winding data to classify the dynamics of the Floquet crystals with equivalent symmetry data, and then construct dynamical symmetry indicators (DSIs) to sufficiently indicate the inherently dynamical Floquet crystals. The DSI and quotient winding data, as well as the symmetry data, are all computationally efficient since they only involve a small number of Bloch momenta. We demonstrate the high efficiency by computing all elementary DSI sets for all spinless and spinful plane groups using the mathematical theory of monoid, and find a large number of different nontrivial classifications, which contain both first-order and higher-order 2+1D anomalous Floquet topological phases. Using the framework, we further find a new 3+1D anomalous Floquet second-order topological insulator (AFSOTI) phase with anomalous chiral hinge modes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Dynamic behavior of reversible oxygen migration in irradiated-annealed high temperature superconducting wires

Large-scale extrusion-based additive manufacturing of high-performance thermoplastic composites like fiber reinforced polyphenylene sulfide (PPS) is well-suited for tooling applications to lower manufacturing costs and lead times. Autoclave tooling requires good mechanical performance at temperatures even above the glass transition temperature (T g ). In this work, the authors have investigated a post-process isothermal annealing technique to improve the mechanical properties of various grades of carbon fiber reinforced PPS components printed on the Big Area Additive Manufacturing (BAAM) system. Since PPS is a semi-crystalline polymer, crystallinity can change during annealing and affect the mechanical properties of the part. In addition, isothermal annealing can also lead to solid-state structural changes in the form of thermal and oxidative branching and/or crosslinking reactions in some grades of PPS which can alter the crystallization process. This work reports the effect of annealing on dynamic mechanical properties of BAAM printed components, along with studies to determine the effect of annealing on crystallinity and the occurrence of oxidative reactions. Results showed that isothermal annealing at 250 °C for 18 h improved the storage modulus of all selected grades (neat and reinforced) of PPS at temperatures above T g . Annealing led to an overall increase in the degree of crystallinity, with secondary crystallization taking place. Although oxidative structural changes were observed to occur more on the surface of the PPS parts, they primarily influenced the size of crystals formed and did not significantly alter the degree of crystallinity at various regions within the sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Characterization and CST Batch Contact Equilibrium Testing of Modified Tank 9H Process Supernate Samples in Support of TCCR

The Tank Closure Cesium Removal (TCCR) system uses ion exchange columns filled with crystalline silicotitanate (CST) media to process radioactive waste solutions for the removal of ¹³⁷Cs. TCCR currently focuses on dissolving Savannah River Site (SRS) radioactive tank waste (primarily sodium saltcake solids) within Tank 10H followed by at-tank ion exchange column treatment. Two supernate batches from Tank 10H have been processed through the TCCR unit and processing of a third batch is expected soon. After processing of this supernate batch, plans are to replace the CST columns and process dissolved salt solution from Tank 9H through Tank 10H and then through the new CST columns installed in the TCCR unit. The new columns are expected to contain either a media similar to an archived CST batch (IE-911) or the R9120-B CST media used in the current TCCR columns (the two materials are fundamentally the same; just different specifications, product names, and preconditioning steps). Samples of Tank 9H dissolved saltcake were received at the Savannah River National Laboratory (SRNL) and characterized. The Tank 9H supernate contained a high sodium concentration (~9.6 M Na⁺) and will require dilution to near 6 M [Na⁺] prior to processing through the TCCR unit. The cesium concentration in Tank 9H is currently significantly higher than was observed with Tank 10H. Three dilutions of the Tank 9H supernate were conducted to mimic possible dilutions that could be conducted in the tank farm prior to TCCR processing using inhibited water, sodium hydroxide, and sodium nitrate solutions. Dilution #1 was prepared by diluting the Tank 9H supernate by a factor of 1.6 with inhibited water, Dilution #2 was prepared by diluting the Tank 9H supernate by a factor of 3.7 with a mixed sodium hydroxide/sodium nitrate diluent, and Dilution #3 was prepared by also diluting by a factor of 3.7 but with sodium hydroxide only. All three dilutions have similar Na⁺ concentrations (~6 M), but Dilutions #2 and #3 contain significantly less cesium. Major and key minor components of the diluted Tank 9H supernate samples are provided in Table ES-1. Batch contact equilibrium tests were conducted with the Tank 9H dilutions and the two different CST media batches being considered for use in the new TCCR columns. Results are summarized in Table ES-2 and compared to ZAM model predictions. The highest cesium distribution coefficient and percent removal were observed with Dilution #3. IE-911 CST (an archived CST media batch) was more effective at removing cesium than the more recently prepared R9120-B CST media, though both media samples removed >88% of the cesium and the differences may not be statistically different considering the overall uncertainty. Based on the results, maximum cesium loadings were calculated for each CST media type and Tank 9H dilution. In general, maximum cesium loadings from dilutions of this supernate batch are quite high (approaching 0.1 mmol total Cs⁺/g CST for Dilution #1). The highest calculated maximum ¹³⁷Cs loading for the Tank 9H dilutions using the ZAM model with input of the tank compositions and batch contact results was 207 Ci/kg CST (Dilution #1 with IE-911 CST). In all cases, higher maximum cesium loading values were predicted for IE-911 CST versus R9120-B, although the differences varied considerably between the dilutions. The maximum loading value for IE-911 CST with Tank 9H Dilution #1 was only 7% higher than the maximum loading for R9120-B. The maximum loading value for IE-911 CST with Dilution #3 was 24% higher than the maximum loading for R9120-B. Dilution #2 was intermediate between these values. Note that these maximum loading values are the theoretical calculated values, and actual operating conditions will cause differences. A CST binder dilution (correction) factor near 0.7 (relative to pure powder CST) was required for each batch contact test with IE-911 engineered CST using the three Tank 9H dilutions. Correction factors calculated for R9120-B CST ranged from 0.56 to 0.66 for the three dilutions. Following the batch contact tests, the CST samples were isolated from the Tank 9H solution, washed, dried, and digested in acid following established procedures. The analysis results are provided in Table ES-3. Total cesium loading values determined by CST digestion were similar to the calculated loading values based on solution analysis (Table ES-2) for all samples. In addition, the CST was observed to load calcium (R9120-B sample only), iron, strontium, lead, uranium, and plutonium after contact with the waste supernate, as has been observed previously.

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

Size dependent lattice pseudosymmetry for frustrated decahedral nanoparticles

Geometric frustration—where geometry prevents simultaneous satisfaction of local interactions—generates pseudosymmetry and emergent behaviors across physical and biological systems. At the nanoscale, pseudosymmetric features in crystalline materials manifest as local strain and distortion, but how they depend on particle size and control structural stability remains unclear. Here, we report the first study of a size-dependent crossover in pseudosymmetry in multi-twinned gold nanoparticles (NPs), combining four-dimensional scanning transmission electron microscopy with nanoscale strain mapping grounded in continuum solid mechanics. Analysis of more than 20 decahedral NPs (20–55 nm) reveals pronounced heterogeneity in multiple modes of in-plane strain and displacement field in small NPs as five tetrahedral grains close the geometric gap, without extended defects. With increasing particle size, strain fields homogenize across grains and local phases shift from predominantly low-symmetry body-centered tetragonal motifs at small sizes to face-centered cubic character approaching the bulk limit. We identify a crossover particle size of ~35 nm, well below bulk, correlating with a transition from modified-Wulff shapes to pentagonal bipyramids, consistent with finite element predictions. This quantitative framework for mapping size-dependent strain and pseudosymmetry enables precise design and control of functional crystalline solids and phase transformation for catalysis, photonics, electronics, and energy storage.

Lin, Oliver [University of Illinois at Urbana-Cham↗
NASA NTRS1972

Developable Images Produced by X-rays Using the Nickel Hypophosphite System. 1 X-ray Sensitive Salts

Twenty-eight crystalline salts were X-irradiated and treated with an ammoniacal nickel hypophosphite solution. Treatment (development) of six of the salts resulted in precipitation of nickel metal. The developable salts were four hypophosphites, sodium phosphite, and nickel formate. A mechanism is proposed for the process based on the postulate that micro amounts of hydrogen atoms are formed during the radiation step. During development, these hydrogen atoms cause the formation of nucleation sites of nickel metal. In turn, these sites catalyze further reduction of the nickel cations by the hypophosphite. The results are discussed in terms of application of the process to the formation of developable latent images.

May, C. E.↗
NASA NTRS1993

Attenuation of Glass Dissolution in the Presence of Natural Additives

The study described here explored the dissolution kinetics of glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase. The results demonstrated the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. The study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses as well as to better understanding of the environmental degradation of natural and ancient glasses.

Sang, Jing C.↗
NASA NTRS2002

A Parametric Assessment of the Mission Applicability of Thin-film Solar Arrays

Results are presented from a parametric assessment of the applicability and spacecraft-level impacts of very lightweight thin-film solar arrays with relatively large deployed areas for representative space missions. The most and least attractive features of thin-film solar arrays are briefly discussed. A calculation is then presented illustrating that from a solar array alone mass perspective, larger arrays with less efficient but lighter thin-film solar cells can weigh less than smaller arrays with more efficient but heavier crystalline cells. However, a spacecraft-level systems assessment must take into account the additional mass associated with solar array deployed area: the propellant needed to desaturate the momentum accumulated from area-related disturbance torques and to perform aerodynamic drag makeup reboost. The results for such an assessment are presented for a representative low Earth orbit (LEO) mission, as a function of altitude and mission life, and a geostationary Earth orbit (GEO) mission. Discussion of the results includes a list of specific mission types most likely to benefit from using thin-film arrays. The presentation concludes with a list of issues to be addressed prior to use of thin-film solar arrays in space and the observation that with their unique characteristics, very lightweight arrays using efficient, thin film cells on flexible substrates may become the best array option for a subset of Earth orbiting and deep space missions.

Hoffman, David J.↗
NASA NTRS2009

Radiation-Induced Amorphization of Crystalline Ice

We study radiation-induced amorphization of crystalline ice, ana lyzing the resu lts of three decades of experiments with a variety of projectiles, irradiation energy, and ice temperature, finding a similar trend of increasing resistance of amorphization with temperature and inconsistencies in results from different laboratories. We discuss the temperature dependence of amorphization in terms of the 'thermal spike' model. We then discuss the common use of the 1.65 micrometer infrared absorption band of water as a measure of degree of crystallinity, an increasingly common procedure to analyze remote sensing data of astronomical icy bodies. The discussion is based on new, high quality near-infrared refl ectance absorption spectra measured between 1.4 and 2.2 micrometers for amorphous and crystalline ices irradiated with 225 keV protons at 80 K. We found that, after irradiation with 10(exp 15) protons per square centimeter, crystalline ice films thinner than the ion range become fully amorphous, and that the infrared absorption spectra show no significant changes upon further irradiation. The complete amorphization suggests that crystalline ice observed in the outer Solar System, including trans-neptunian objects, may results from heat from internal sources or from the impact of icy meteorites or comets.

Fama, M.↗
NASA NTRSDate not supplied

Impact of Thermoplastic Composites: Testing and Modeling

Thermoplastic Composites (TPCs) are being increasingly considered for aerospace applications given their faster manufacturing cycles and lower cost. The NASA High-Rate Composite Aircraft Manufacturing (HiCAM) project aims to evaluate and mature thermoplastic manufacturing technologies to achieve a 4X – 6X increase in the production rate of Next Generation Single Aisle (NGSA) commercial aircraft. Within the purview of the NASA HiCAM project, this work investigates the response of thermoplastic composites under High Energy Dynamic Impact (HEDI) conditions. HEDI tests were conducted on panels fabricated with a carbon fiber reinforced low melt semi-crystalline resin TC1225 LMPAEK T700G (T700/LMPAEK) material system. A blunt metal projectile was chosen as the impactor which impacted the T700/LMPAEK panels over a range of impact velocities imparted by a gas gun test setup. As expected, lower velocity impacts caused the projectile to rebound, whereas higher velocity impacts resulted in the projectile penetrating the test panels. For the test cases in which the projectile rebounded, the predominant damage modes recorded with Ultrasonic (UT) scans included interlaminar delaminations which exhibited a “rotating fan” like structure when viewed in the through-thickness direction. Additionally, the dynamic deflection of the center point of the back face of the test panels and the velocity of the projectile was also measured during the test. Finite element models were developed to model a test case in which the projectile rebounded. These models were developed using LS-DYNA® wherein the primary objective was to evaluate the ability of the material model MAT299 to capture the dynamic response and damage modes in the T700/LMPAEK test panels. MAT299 is a Deformation Gradient Decomposition (DGD) based Continuum Damage Mechanics (CDM) material model. The interlaminar delaminations were modeled using the cohesive contact formulation available within LS-DYNA, wherein the mixed-mode fracture is captured via the Benzegaggh-Kenane (B-K) mode-dependent fracture energy interpolation law. The above-mentioned modeling methods have mostly been applied to thermoset composites and adapting them to TPCs involves addressing challenges associated with appropriately representing material behavior. Therefore, the proposed paper would discuss the systematic approach taken to adapt thermoset composites modeling practices for applications to TPCs, while appropriately addressing material behavior. The proposed paper would show that the predicted back face center point deflection correlated reasonably well with experimental data and the peak deflection was predicted to be within 5% of the experimental measurements. The projectile rebound velocity, while predicted to be higher than the experimental measurement, was within reasonable bounds. Additionally, it will be shown that the predicted delamination shapes were in reasonable agreement with experimental data.

Composite Materials↗
DOE OSTI2021

Vanadium oxide for infrared coatings and methods thereof

The present invention relates to vanadium oxide and methods of controlling reaction processes for making such materials (e.g., powders). In particular embodiments, the method includes control of oxygen partial pressure in order to kinetically control the oxidation species of the crystalline vanadium oxide material. Other methods, uses, systems, protocols, and coatings are also described.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Crystalline Disposal R&D at LBNL: FY20 Progress Report

Within the Spent Fuel & Waste Science and Technology (SFWST) Program, research work continues further with the goal to better understand long-term performance of disposal systems in three main geologic rock types: clay/shale, salt, and crystalline rock. This report documents LBNL’s research activities related to investigations of crystalline host rock according to the scope of two work packages: SF-20LB01030207 “Crystalline International Collaborations – LBNL,” and SF-20LB01030203 “Crystalline Disposal R&D – LBNL.” These research activities correspond are related to key Features, Events, and Processes (FEPs), ranked in importance from medium to high, as listed in Table 7 of the Used Fuel Disposition Campaign Disposal Research and Development Roadmap (FCR&D-USED-2011-000065 REV0) (Nutt, 2011). Specifically, these research activities address FEP 2.2.01, Excavation Disturbed Zone (EZD). The results of these research activities provide important insights into understanding and predicting flow and transport processes that could occur in low-permeability crystalline rocks, in which fractures might serve as main conduits for fluid flow and radionuclide transport. The evolution of the EDZ during the excavation of the tunnel as well as the evolution of microcrack growth within the EDZ after the emplacement of backfill are critical for predicting the long- term behavior of the EDZ. A number of factors including stress, temperature, water activity, capillary pressure, chemistry, and mineralogy can affect the rock evolution, which require advanced experimental tools to study it.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Engineered Barrier System R&D and International Collaborations – LANL (FY20): Spent Fuel and Waste Disposition

The United States Department of Energy’s Spent Fuel and Waste Disposition (SFWD) program is investigating the design and safety function of generic nuclear geologic repositories in a variety of geologic settings (salt, argillite, and crystalline rock). Different configurations and loadings of spent nuclear fuel and waste within disposal canisters are also being investigated, some of which have the potential to generate repository temperatures higher than previously considered (i.e., temperatures >100ºC) by foreign and domestic concepts. This report expands on engineered barrier material stability in a high temperature crystalline rock repository through high temperature hydrothermal experiments. Experiments were designed to develop engineered barrier system (EBS) concepts in a hightemperature crystalline environment in 1) bentonite-Grimsel Granodiorite interactions, 2) bentonite-cement reactions, and 3) interaction between waste canister materials and bentonite. Experiment results are applied to understanding long-term repository performance in terms of radionuclide isolation. One hydrothermal experiment was completed in the rocking autoclaves at LANL in FY-20: IEBS-6 (Grimsel Granodiorite + Wyoming bentonite + cured ordinary Portland cement + Grimsel Granodiorite synthetic groundwater, 250ºC/150 bar, 8 weeks). Several other experiments were planned but were delayed due to the COVID-19 pause in laboratory work. In addition, some characterization of the reaction products of experiments conducted in FY-20 was prevented by COVID-19. Mineral phase chemistry was not measured via electron microprobe analyses for IEBS-6. Quantitative X-ray diffraction results from IEBS-6 and HBT-1 were not completed. The missing analyses and discussion of the results will be included in next year’s report. New characterization that was completed includes scanning electron microscopy of reaction products from IEBS-6, quantitative X-ray diffraction results are presented from IEBS-1 through IBES-5, preliminary scanning electron microscope images and chemical analyses for IEBS-6, X-ray diffraction of the clay fraction from all experiments, measurement/imaging of mineral growth on the surface of steel coupons. Major observations pertaining to bentonite stability in a Grimsel Granodiorite environment include the stability of Na-montmorillonite at 250°C, the formation of trace CSH phases, and the formation of bentonite colloids on experiment cooling. The addition of a cured chip of Portland cement to the bentonite-Grimsel system results in slightly higher pH values and the formation of diverse secondary mineral phases that were not observed in the previous experiments (e.g., analcime, garronite, CSH phases). The new characterization efforts related to the interaction of stainless-steel coupons and bentonite clay focused on thickness and mineralogy of phases that formed at the steel surface. In Wyoming bentonite + Grimsel Granodiorite systems, newly formed minerals at the bentonitesteel coupon interface included alteration of the outermost steel edge to Fe,Cr-oxide phases, followed by Fe-rich phyllosilicates (Fe-saponite, chlorite) and interbedded Fe,Cr,Ni-sulfide phases (pentlandite). Hydrothermal experiments were completed to assess uranium-carbonate complexation at conditions relevant to high-temperature disposal. Autoclave solubility experiments were conducted at 150 to 250ºC with a range of carbonate and uranium concentrations. The experiment results were characterized via situ UV-Visible spectroscopy and synchrotron-based in situ XAS techniques. Results show a significant decrease in the stability of uranyl-carbonate complexes at temperatures above 100ºC along with the precipitation of uranium oxides. Further, at T > 200ºC, results show that uranyl-hydroxyl complexes control solubility of uranium instead of the previously predicted uranyl-carbonate species. These results are significant for understanding the mobility of uranium in the EBS, which will likely contain carbonate-rich fluids. International research efforts focused on three main areas: 1) participation in international conferences, 2) building collaborations with foreign repository programs, and 3) the initiation of an experimental program to complement the full-scale HotBENT test at the Grimsel test site. This experiment included Wyoming bentonite + low carbon steel + Grimsel Granodiorite synthetic groundwater and was run at the planned maximum temperature of the HotBENT test (200°C). Complete characterization of reaction products was hindered by disruptions to laboratory work but will be reported in the next FY. The experimental results obtained in FY-20 continue to document the wide-ranging effects of bulk composition and pressure-temperature conditions in the mineralogical and geochemical evolution of a high-temperature repository environment. Concepts developed will be used to inform models of long-term material stability in a generic crystalline rock-hosted repository.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Preliminary Determination of the Impact of Alkaline Earth Metals on Crystalline Silicotitanate

Savannah River Remediation (SRR) recently deployed the Tank Closure Cesium Removal (TCCR) system which utilizes an ion exchange process to remove 137 Cs from tank waste supernate. In TCCR, salt solution is filtered and then passed through ion exchange columns containing crystalline silicotitanate (CST) media, commercially known as UOP IONSIV™ R9120-B, which is highly selective for removing cesium. The current process focuses on dissolving salt in Savannah River Site (SRS) Tank 10H, followed by processing in the TCCR skid located near the tank. Prior to processing each batch of waste generated in Tank 10H, the projected maximum cesium loading on the CST is determined using an in-tank batch contact equilibrium test. This involves placing a small amount (~0.1 g) of CST in a “teabag” device and submerging it in the tank waste for a period of 10 days. Results from those earlier teabag tests had indicated much lower cesium loading than predicted by the equilibrium sorption model (ZAM). There are numerous possible explanations for this result; however, based on the observed loadings of Ca (and other metals) on the CST from the teabag tests, it was hypothesized that competition from these other ions may be limiting the cesium loadings.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Elemental characterization of crystalline silicotitanate following Hanford tank waste processing

To expedite vitrification of low activity waste at the Hanford Site, a Tank-Side Cesium Removal system is being evaluated. This method utilizes an inorganic ion exchange (IX) media, crystalline silicotitanate (CST), to remove 99.9% of the 137Cs from tank waste supernate. Laboratory scale testing of the ion exchange process has been conducted by Pacific Northwest National Laboratory to evaluate Cs removal with CST in supernates collected from Hanford tanks 241-AP-107 and 241-AW-102 under prototypic plant operating conditions. In an effort to understand the selectivity and partitioning of other analytes toward CST, specifically Resource Conservation and Recovery Act (RCRA) hazardous metals, selected +2 cations, and transuranic elements, a method for the complete dissolution of CST and Cs removal from the digestate was applied to the spent CST post-processing Hanford tank waste. The CST was shown to adsorb a relevant fraction of Ca, Cd, Pb, Sr, and potentially Fe by IX and/or other mechanisms. The spent CST also adsorbed actinides, including U, Pu, Np, and Am. This work discusses digestion of CST and removal of Cs from the digestate allowing effective analysis and provides insight as to what analytes may be competing for IX sites on the CST media.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Symmetry-specific orientational order parameters for complex structures

A comprehensive framework of characterizing complex self-assembled structures with a set of orientational order parameters is presented. It is especially relevant in the context of using anisotropic building blocks with various symmetries. Two classes of tensor order parameters are associated with polyhedral nematic and bond orientational order. For the latter, a variation of classical bond order parameters (BOPs) is introduced, which takes advantage of the symmetry of constituent particles and/or expected crystalline phases. These symmetrized BOPs can be averaged over an entire system or assigned locally to an individual bond. By combining that with the bond percolation procedure, one is able to identify coherent domains within a self-assembled structure. As a demonstration of the proposed framework, we apply it to a simulated hybrid system that combines isotropic and patchy particles with octahedral symmetry. In conclusion, not only does the methodology allow one to identify individual crystalline domains but also it detects coherent clusters of a peculiar compact amorphous structure that is not space-filling and lacks any long-range order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗