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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

On the three-dimensional spatial correlations of curved dislocation systems

Abstract Coarse-grained descriptions of dislocation motion in crystalline metals inherently represent a loss of information regarding dislocation-dislocation interactions. In the present work, we consider a coarse-graining framework capable of re-capturing these interactions by means of the dislocation-dislocation correlation functions. The framework depends on a convolution length to define slip-system-specific dislocation densities. Following a statistical definition of this coarse-graining process, we define a spatial correlation function which will allow the arrangement of the discrete line system at two points—and thus the strength of their interactions at short range—to be recaptured into a mean field description of dislocation dynamics. Through a statistical homogeneity argument, we present a method of evaluating this correlation function from discrete dislocation dynamics simulations. Finally, results of this evaluation are shown in the form of the correlation of dislocation densities on the same slip-system. These correlation functions are seen to depend weakly on plastic strain, and in turn, the dislocation density, but are seen to depend strongly on the convolution length. Implications of these correlation functions in regard to continuum dislocation dynamics as well as future directions of investigation are also discussed.

Anderson, Joseph Pierre (ORCID:0000000329760903)↗
DOE OSTI2023

Evolution of the Cellulose Microfibril through Gamma-Valerolactone-Assisted Co-Solvent and Enzymatic Hydrolysis

Biomass recalcitrance during deconstruction remains a key bottleneck to affordable biomass processing technologies. A clear connection between the cell wall structure and biomass deconstruction is necessary to understand how lignocellulosic material is broken down to valuable monomeric components. Here, we monitor changes in the cellulose microfibril domains of poplar, sorghum, and switchgrass throughout gamma-valerolactone (GVL)–water co-solvent pretreatment and enzymatic hydrolysis using solid-state 13 C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS 13 C-NMR) and wide-angle X-ray scattering (WAXS). Spectral fitting of NMR peaks corresponding to different cellulose microenvironments at the C 4 carbon center suggests that a mildly acidic GVL–water co-solvent pretreatment of poplar leads to nearly full removal of xylan–cellulose linkages, which primes the cellulose for enzymatic attack. The spectral fitting also suggests that the pretreatment causes significant depletion of the inaccessible fibril surface domains with an increase in more thermally stable crystalline resonances (I β ). WAXS confirmed a decrease in the lattice spacing between (200) crystalline planes with increasing co-solvent pretreatment severity. These results are interpreted as an opening of bound microfibril surfaces previously inaccessible to the co-solvent system, which leaves behind a more thermally stable, crystalline domain that is potentially prone to relaxation and recrystallization. Full conversion of residual GVL-pretreated biomass was achieved after the GVL co-solvent pretreatment at 140 °C using a commercial enzyme cocktail, CTec2, which contains different cellulases and other enzymes. Spectral fitting of enzymatically hydrolyzed samples by a single engineered cellulase, CelR, suggests that the residual cellulose recalcitrance is mainly due to the inability of CelR to digest the I β crystalline domain present in pretreated samples. This work helps to provide new information regarding the structure of the cell wall and recalcitrance throughout GVL–water mild acidolysis and CelR enzymatic biomass deconstruction by tracking the evolution of structural domains within the cellulose microfibril. This work further directs recommendations for improving the conversion and sugar yields in future studies. Finally, our findings inform inquiry into larger questions of cellulose recalcitrance through GVL pretreatment and CelR enzymatic hydrolysis and give insight into subsequent required steps for full cellulose conversion with attention to the most recalcitrant cellulose structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Synchrotron‐source micro‐x‐ray computed tomography for examining butterfly eyes

Comparative anatomy is an important tool for investigating evolutionary relationships among species, but the lack of scalable imaging tools and stains for rapidly mapping the microscale anatomies of related species poses a major impediment to using comparative anatomy approaches for identifying evolutionary adaptations. We describe a method using synchrotron source micro-x-ray computed tomography (syn-μXCT) combined with machine learning algorithms for high-throughput imaging of Lepidoptera (i.e., butterfly and moth) eyes. Our pipeline allows for imaging at rates of ~15 min/mm 3 at 600 nm 3 resolution. Image contrast is generated using standard electron microscopy labeling approaches (e.g., osmium tetroxide) that unbiasedly labels all cellular membranes in a species-independent manner thus removing any barrier to imaging any species of interest. To demonstrate the power of the method, we analyzed the 3D morphologies of butterfly crystalline cones, a part of the visual system associated with acuity and sensitivity and found significant variation within six butterfly individuals. Despite this variation, a classic measure of optimization, the ratio of interommatidial angle to resolving power of ommatidia, largely agrees with early work on eye geometry across species. We show that this method can successfully be used to determine compound eye organization and crystalline cone morphology. Our novel pipeline provides for fast, scalable visualization and analysis of eye anatomies that can be applied to any arthropod species, enabling new questions about evolutionary adaptations of compound eyes and beyond.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Controlling the Self-Assembly of DNA Origami Octahedra via Manipulation of Inter-Vertex Interactions

Recent studies have demonstrated novel strategies for the organization of nanomaterials into three-dimensional (3D) ordered arrays with prescribed lattice symmetries using DNA-based self-assembly strategies. In one approach, the nanomaterial is sequestered into DNA origami frames or “material voxels” and then coordinated into ordered arrays based on the voxel geometry and the corresponding directional interactions based on its valency. While the lattice symmetry is defined by the valency of the bonds, a larger-scale morphological development is affected by assembly processes and differences in energies of anisotropic bonds. To facilely model this assembly process, we investigate the self-assembly behavior of hard particles with six interacting vertices via theory and Monte Carlo simulations and exploration of corresponding experimental systems. We demonstrate that assemblies with different 3D crystalline morphologies, but the same lattice symmetry can be formed depending on the relative strength of vertex-to-vertex interactions in orthogonal directions. We observed three distinct assembly morphologies for such systems: cube-like, sheet-like, and cylinder-like. A simple analytical theory inspired by well-established ideas in the areas of protein crystallization, based on calculating the second virial coefficient of patchy hard spheres, captures the simulation results and thus represents a straightforward means of modeling this self-assembly process. To complement the theory and simulations, experimental studies were performed to investigate the assembly of octahedral DNA origami frames with varying binding energies at their vertices. In conclusion, x-ray scattering confirms the robustness of the formed nanoscale lattices for different binding energies, while both optical and electron microscopy imaging validated the theoretical predictions on the dependence of the distinct morphologies of assembled state on the interaction strengths in the three orthogonal directions.

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

Motility of acoustically powered micro-swimmers in a liquid crystalline environment

Suspensions of microswimmers in liquid crystals demonstrate remarkably complex dynamics and serve as a model system for studying active nematics. So far, experimental realization of microswimmers suspended in liquid crystalline media has relied on biological microorganisms that impose strict limitations on the compatible media and makes it difficult to regulate activity. Here, we demonstrate that acoustically powered bubble microswimmers can efficiently self-propel in a lyotropic liquid crystal. The velocity of the swimmers is controlled by the amplitude of the acoustic field. Histograms of swimming directions with respect to the local nematic field reveal a bimodal distribution: the swimmers tend to either fully align with or swim perpendicular to the director field of the liquid crystal, occasionally switching between these two states. The bubble-induced streaming from a swimmer locally melts the liquid crystal and produces topological defects at the tail of the swimmer. Further, we show that the defect proliferation rate increases with the angle between the swimmer's velocity and the local orientation of the director field.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Smartly Optimizing Crystallinity, Compatibility, and Morphology for Polymer Solar Cells by Small Molecule Acceptor with Unique 2D-EDOT Side Chain

A desired morphology is essential for achieving efficient polymer solar cells. Donors and acceptors with appropriate crystallization can lead to a suitable phase-separated morphology for effective photocurrent generation process. Inspired by the success of Y6 acceptors and the 2D side chain engineering on popular polymer donors and small molecule acceptors, the usage of unique 2D 3,4-ethylene dioxythiophene (EDOT) side chains on Y6 to regulate its crystallinity, compatibility, and thus the related blend morphology is explored. Here, in this study, two molecules of BTP-EDOT-4F and BTP-EDOT-4Cl with such unique 2D EDOT side chains are designed and synthesized. Due to the advantage of EDOT side chain, when these molecules are blended with PM6, the decent power conversion efficiencies (PCEs) of 16.78% and 15.87% are obtained. Furthermore, BTP-EDOT-4F is selected as the third component and added into PM6:L8-BO binary system to form ternary blends. The optimized crystallinity, compatibility, and morphology of such ternary blend are discovered in the presence of BTP-EDOT-4F, which enables efficient exciton dissociation and charge transport as well as decreased recombination, resulting in higher short circuit current density (J sc ) and fill factor. Finally, the outstanding PCE of 18.56% is achieved in ternary blends containing PM6, L8-BO, and BTP-EDOT-4F.

2D EDOT side chains↗
DOE OSTI2023

Cesium Removal from SY-101 Tank Waste Using Crystalline Silicotitanate

The newly operational Tank Side Cesium Removal (TSCR) system removes radioactive cesium-137 ( 137 Cs) and solids from tank waste supernate in the 200 east area of the Hanford site. Efforts to expand the removal capabilities to the 200 west area are underway by a system anticipated to be called the West Area Risk Management (WARM) system. Laboratory-scale ion exchange processing using expected WARM unit operations were conducted to contribute toward Washington River Protection Solutions (WRPS) establishing accurate process flowsheets for the individual feed campaigns planned for the west area supernate pretreatment. This report describes the small-scale ion exchange testing with 8.0 L of filtered supernate from tank 241-SY-101 (referred to as SY-101) at 16 °C (62 °F) to demonstrate processing conditions that would be prototypic of what the WARM system may experience. One of the waste acceptance criteria (WAC) for the Waste Treatment Plant (WTP) Low-Activity Waste Facility is that the waste must contain less than 3.18×10 -5 Ci 137 Cs per mole of Na. For the SY-101 tank waste to meet this criterion, only 0.44% of the influent 137 Cs concentration may be delivered to the WTP; this requires a Cs decontamination factor of 227. Testing with SY-101 matched current TSCR prototypic operations where a lead-lag configuration is used until the lag column reached the WAC limit. Neither the lead nor lag columns reached the WAC, so a polish column was never utilized during this test. Feed was processed at 1.9 bed volumes (BVs) per hour; the flowrate, in terms of contact time with the crystalline silicotitate (CST) bed, matched the current flowrate at TSCR (an expected flowrate to be used at WARM). The lead column only reached 0.09% Cs breakthrough after processing ~1363 BVs of feed. Cesium breakthrough from the lag column was not observed during the entire processing. Table S.1 and Figure S.1 summarize the observed column performance and relevant Cs loading characteristics. Table S.1 and Figure S.1 also summarize the measured SY-101 Cs load performance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Cesium Exchange onto Crystalline Silicotitanate from Blended Hanford Tank Wastes

The Tank Side Cesium Removal (TSCR) system was developed to filter and remove cesium (Cs and 137 Cs) from Hanford tank waste supernate in preparation for vitrification. The Cs removal will be conducted with crystalline silicotitanate (CST) ion exchange media. Under the planned waste-processing strategy, the tank waste supernate will be queued for TSCR processing in tank 241-AP-107 (AP-107). Once AP-107 tank waste volume is sufficiently depleted, the waste supernate from tank 241-AP-105 (AP-105, the holding tank before transfer to AP-107) will be transferred to tank AP-107. Supernate from another tank will be transferred to the holding tank, AP-105, for eventual transfer to tank AP-107. These supernate streams will undergo blending in tanks AP-107 and AP-105; the volume blend ratios will be driven by how much the tank waste supernate volumes are depleted before the next tank waste is added. The consequence of tank waste blending on Cs uptake by CST was of interest and was tested via batch contacts; results are reported herein.

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