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All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Lead free, air stable perovskite derivative Cs2SnI6 as HTM in DSSCs employing TiO2 nanotubes as photoanode

Highlights: • Cs{sub 2}SnI{sub 6} HTM layer was deposited onto titania nanotube photoanode through dip coating to fabricate all solid state DSSCs. • Enhanced photo conversion efficiency was obtained through varying dip coating time for Cs{sub 2}SnI{sub 6} HTM on TNT photoanode. • ss-DSSCs with lead-free perovskite derivative Cs{sub 2}SnI{sub 6} as HTM shows stable performance up to 10 days. - Abstract: Cs{sub 2}SnI{sub 6} is an air-stable and non-toxic perovskite variant photovoltaic material which exhibits p-type conductivity under doped conditions. In this work, we report the synthesis and stability studies of Cs{sub 2}SnI{sub 6} towards its application as a solid-state Hole Transport Material (HTM) in Titania Nanotube (TNT) based Dye Sensitized Solar Cells (DSSCs). Cs{sub 2}SnI{sub 6} crystals were synthesized using precipitation method and its stability was assessed using X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and Thermogravimetric Analysis (TGA). Cs{sub 2}SnI{sub 6} doped with SnI{sub 2} was deposited onto the TNT photo-anode as the HTM layer through dip coating. Deposition time was varied to obtain a continuous layer of Cs{sub 2}SnI{sub 6} HTM over TNT photo-anode and cell characteristics were studied. We were able to fabricate air stable, all solid-state solar cells with a Jsc of 6 mA/cm{sup 2}, Voc of 536 mV and PCE of 1.3%. The study propounds contemporary analysis on Sn based perovskite systems, in the field of DSSCs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Anion Distribution, Structural Distortion, and Symmetry-Driven Optical Band Gap Bowing in Mixed Halide Cs2SnX6 Vacancy Ordered Double Perovskites

Mixed anion compounds in the Fm$\bar{3}$m vacancy ordered perovskite structure were synthesized and characterized experimentally and computationally with a focus on compounds where A = Cs + . Pure anion Cs 2 SnX 6 compounds were formed with X = Cl, Br, and I using a room temperature solution phase method. Mixed anion compounds were formed as solid solutions of Cs 2 SnCl 6 and Cs 2 SnBr 6 and a second series from Cs 2 SnBr 6 and Cs 2 SnI 6 . Single phase structures formed across the entirety of both composition series with no evidence of long-range anion ordering observed by diffraction. A distortion of the cubic A 2 BX 6 structure was identified in which the spacing of the BX 6 octahedra changes to accommodate the A site cation without reduction of overall symmetry. Optical band gap values varied with anion composition between 4.89 eV in Cs 2 SnCl 6 to 1.35 eV in Cs 2 SnI 6 but proved highly nonlinear with changes in composition. In mixed halide compounds, it was found that lower energy optical transitions appeared that were not present in the pure halide compounds, and this was attributed to lowering of the local symmetry within the tin halide octahedra. The electronic structure was characterized by photoemission spectroscopy, and Raman spectroscopy revealed vibrational modes in the mixed halide compounds that could be assigned to particular mixed halide octahedra. This analysis was used to determine the distribution of octahedra types in mixed anion compounds, which was found to be consistent with a near-random distribution of halide anions throughout the structure, although some deviations from random halide distribution were noted in mixed iodide–bromide compounds, where the larger iodide anions preferentially adopted trans configurations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Surface Termination of CsPbBr 3 Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy

Cesium lead halide perovskite quantum dots (QDs) have gained significant attention as next-generation optoelectronic materials; however, their properties are highly dependent on their surface chemistry. The surfaces of cuboidal CsPbBr 3 QDs have been intensively studied by both theoretical and experimental techniques, but fundamental questions still remain about the atomic termination of the QDs. The surface binding sites and modes of ligands at the surface remain unproven. Herein, we demonstrate that solid-state NMR spectroscopy allows the unambiguous assignment of organic surface ligands via 1 H, 13 C, and 31 P NMR. Surface-selective 133 Cs solid-state NMR spectra show the presence of an additional 133 Cs NMR signal with a unique chemical shift that is attributed to Cs atoms terminating the surface of the particle and which are likely coordinated by carboxylate ligands. Dipolar dephasing curves that report on the distance between the surface ammonium ligands and Cs and Pb were recorded using double resonance 1 H{ 133 Cs} and 1 H{ 207 Pb} RESPDOR experiments. Model QD surface slabs with different possible surface terminations were generated from the CsPbBr 3 crystal structure and theoretical RESPDOR dipolar dephasing curves considering all possible 1 H- 133 Cs/ 207 Pb spin pairs were then calculated. Comparison of the calculated and experimental RESPDOR curves indicates the particles are CsBr terminated (not PbBr 2 terminated) with alkylammonium ligands substituting into some surface Cs sites, consistent with the surface-selective 133 Cs NMR experiments. Lastly, these results highlight the utility of high-resolution solid-state NMR spectroscopy for studying ligand binding and the surface structure of nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Time evolution of negative ion profile in a large cesiated negative ion source applicable to fusion reactors

To understand the physics of the cesium (Cs) recycling in the large Cs-seeded negative ion sources relevant to ITER and JT-60SA with ion extraction area of 45-60 cm × 110-120 cm, the time evolution of the negative ion profile was precisely measured in JT-60SA where the ion extraction area is longitudinally segmented into 5. The Cs was seeded from the oven at 180 °C to the ion source. After 1 g of Cs input, surface production of the negative ions appeared only in the central segment where a Cs nozzle was located. Up to 2 g of Cs, the negative ion profile was longitudinally expanded over full ion extraction area. The measured time evolution of the negative ion profile has the similar tendency of distribution of the Cs atoms that is calculated. From the results, it is suggested that Cs atom distribution is correlated with the formation of the negative ion profile.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Search for hidden-charm tetraquark with strangeness in e + e - → $K$ + $D^{*}_{s}$ - $D$ *0 + c.c.*

We report a search for a heavier partner of the recently observed Z cs (3985) - state, denoted as $Z^{'-}_{cs}$, in the process e + e - → $K$ + $D^{*}_{s}$ - $D$ *0 + c.c., based on e + e - collision data collected at the center-of-mass energies of $\sqrt{s}$ = 4.661, 4.682 and 4.699 GeV with the BESIII detector. The $Z^{'-}_{cs}$ is of interest as it is expected to be a candidate for a hidden-charm and open-strange tetraquark. A partial-reconstruction technique is used to isolate K + recoil-mass spectra, which are probed for a potential contribution from $Z^{'-}_{cs}$ → $D^{*}_{s}$ - $D$ *0 + (c.c.). We find an excess of $Z^{'-}_{cs}$ → $D^{*}_{s}$ - $D$ *0 + (c.c.) candidates with a significance of 2.1σ, after considering systematic uncertainties, at a mass of 4123.5 ± 0.7 stat. ± 4.7 syst. ) MeV/c 2 . As the data set is limited in size, the upper limits are evaluated at the 90% confidence level on the product of the Born cross sections (σ BORN ) and the branching fraction ($\mathcal{B}$) of $Z^{'-}_{cs}$ → $D^{*}_{s}$ - $D$ *0 , under different assumptions of the $Z^{'-}_{cs}$ mass from 4.120 to 4.140 MeV and of the width from 10 to 50 MeV at the three center-of-mass energies. The upper limits of σ BORN ∙ $\mathcal{B}$ are found to be at the level of $\mathcal{O}$(1) pb at each energy. Larger data samples are needed to confirm the $Z^{'-}_{cs}$ state and clarify its nature in the coming years.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2016

Could multiple voids explain the cosmic microwave background Cold Spot anomaly?

Understanding the observed Cold Spot (CS) (temperature of ~ -150 mu K at its centre) on the Cosmic Microwave Background (CMB) is an outstanding problem. Explanations vary from assuming it is just a ≳ 3σ primordial Gaussian fluctuation to the imprint of a supervoid via the Integrated Sachs-Wolfe and Rees-Sciama (ISW+RS) effects. Since single spherical supervoids cannot account for the full profile, the ISW+RS of multiple line-of-sight voids is studied here to mimic the structure of the cosmic web. Two structure configurations are considered. The first, through simulations of 20 voids, produces a central mean temperature of ~-50 mu K. In this model the central CS temperature lies at ~ 2σ but fails to explain the CS hot ring. An alternative multi-void model (using more pronounced compensated voids) produces much smaller temperature profiles, but contains a prominent hot ring. Arrangements containing closely placed voids at low redshift are found to be particularly well suited to produce CS-like profiles. We then measure the significance of the CS if CS-like profiles (which are fitted to the ISW+RS of multi-void scenarios) are removed. Furthermore, the CS tension with the LCDM model can be reduced dramatically for an array of temperature profiles smaller than the CS itself.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

The effect of alkali-soluble lignin on purified core cellulase and hemicellulase activities during hydrolysis of extractive ammonia-pretreated lignocellulosic biomass

Removing alkali-soluble lignin using extractive ammonia (EA) pretreatment of corn stover (CS) is known to improve biomass conversion efficiency during enzymatic hydrolysis. In this study, we investigated the effect of alkali-soluble lignin on six purified core glycosyl hydrolases and their enzyme synergies, adopting 31 enzyme combinations derived by a five-component simplex centroid model, during EA-CS hydrolysis. Hydrolysis experiment was carried out using EA-CS(-) (approx. 40% lignin removed during EA pretreatment) and EA-CS(+) (where no lignin was extracted). Enzymatic hydrolysis experiments were done at three different enzyme mass loadings (7.5, 15 and 30 mg protein g -1 glucan), using a previously developed high-throughput microplate-based protocol, and the sugar yields of glucose and xylose were detected. The optimal enzyme combinations (based on % protein mass loading) of six core glycosyl hydrolases for EA-CS(-) and EA-CS(+) were determined that gave high sugar conversion. The inhibition of lignin on optimal enzyme ratios was studied, by adding fixed amount of alkali-soluble lignin fractions to EA-CS(-), and pure Avicel, beechwood xylan and evaluating their sugar conversion. The optimal enzyme ratios that gave higher sugar conversion for EA-CS(-) were CBH I: 27.2–28.2%, CBH II: 18.2–22.2%, EG I: 29.2–34.3%, EX: 9.0–14.1%, βX: 7.2–10.2%, βG: 1.0–5.0% (at 7.5–30 mg g -1 protein mass loading). Endoglucanase was inhibited to a greater extent than other core cellulases and xylanases by lignin during enzyme hydrolysis. We also found that alkali-soluble lignin inhibits cellulase more strongly than hemicellulase during the course of enzyme hydrolysis.

09 BIOMASS FUELS↗
DOE OSTI2019

Towards predictive band gaps for halide perovskites: Lessons from one-shot and eigenvalue self-consistent GW

Halide perovskites constitute a chemically diverse class of crystals with great promise as photovoltaic absorber materials, featuring band gaps between about 1 and 3.5 eV depending on composition. Their diversity calls for a general computational approach to predicting their band gaps. However, such an approach is still lacking. Here, we use density functional theory (DFT) and ab initio many-body perturbation theory within the GW approximation to compute the quasiparticle or fundamental band gap of a set of ten representative halide perovskites: CH 3 NH 3 PbI 3 ( MAPbI 3 ), MAPbBr 3 , CsSnBr 3 , ( MA ) 2 BiTlBr 6 , Cs 2 TlAgBr 6 , Cs 2 TlAgCl 6 , Cs 2 BiAgBr 6 , Cs 2 InAgCl 6 , Cs 2 SnBr 6 , and Cs 2 Au 2 I 6 . Comparing with recent measurements, we find that a standard generalized gradient exchange-correlation functional can significantly underestimate the experimental band gaps of these perovskites, particularly in cases with strong spin-orbit coupling (SOC) and highly dispersive band edges, to a degree that varies with composition. We show that these nonsystematic errors are inherited by one-shot G 0 W 0 and eigenvalue self-consistent GW 0 calculations, demonstrating that semilocal DFT starting points are insufficient for MAPbI 3 , MAPbBr 3 , CsSnBr 3 , ( MA ) 2 BiTlBr 6 , Cs 2 TlAgBr 6 , and Cs 2 TlAgCl 6 . On the other hand, we find that DFT with hybrid functionals leads to an improved starting point and G W 0 results in better agreement with experiment for these perovskites. Our results suggest that G W 0 with hybrid functional-based starting points are promising for predicting band gaps of systems with large SOC and dispersive bands in this technologically important class of semiconducting crystals.</

36 MATERIALS SCIENCE↗
DOE OSTI2015

An active site-tail interaction in the structure of hexahistidine-tagged Thermoplasma acidophilum citrate synthase

Citrate synthase (CS) plays a central metabolic role in aerobes and many other organisms. The CS reaction comprises two half-reactions: a Claisen aldol condensation of acetyl-CoA (AcCoA) and oxaloacetate (OAA) that forms citryl-CoA (CitCoA), and CitCoA hydrolysis. Protein conformational changes that `close' the active site play an important role in the assembly of a catalytically competent condensation active site. CS from the thermoacidophile Thermoplasma acidophilum (TpCS) possesses an endogenous Trp fluorophore that can be used to monitor the condensation reaction. The 2.2 Å resolution crystal structure of TpCS fused to a C-terminal hexahistidine tag (TpCSH6) reported here is an `open' structure that, when compared with several liganded TpCS structures, helps to define a complete path for active-site closure. One active site in each dimer binds a neighboring His tag, the first nonsubstrate ligand known to occupy both the AcCoA and OAA binding sites. Solution data collectively suggest that this fortuitous interaction is stabilized by the crystalline lattice. In conclusion, as a polar but almost neutral ligand, the active site-tail interaction provides a new starting point for the design of bisubstrate-analog inhibitors of CS.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Uncoordinated Spectrum Sharing in Millimeter Wave Networks Using Carrier Sensing

Here, we propose using Carrier Sensing (CS) for distributed interference management in millimeter-wave (mmWave) cellular networks where spectrum is shared by multiple operators that do not coordinate among themselves. In addition, even the base station sites can be shared by the operators. We describe important challenges in using traditional CS in this setting and propose enhanced CS protocols to address these challenges. Using stochastic geometry, we develop a general framework for downlink coverage probability analysis of our shared mmWave network in the presence of CS and derive the downlink coverage probability expressions for several CS protocols. Our work is the first to investigate and analyze (using stochastic geometry) CS for mmWave networks with spectrum and BS sites shared among non-coordinating operators. We evaluate the downlink coverage probability of our shared mmWave network using simulations as well as numerical examples based on our analysis. Our evaluations show that our proposed approach leads to an improvement in coverage probability, compared to the coverage probability with no CS, for higher values of signal-to-interference and noise ratio (SINR). Interestingly, our evaluations also reveal that for lower values of SINR, not using any CS is the best strategy in terms of the downlink coverage probability.

42 ENGINEERING↗
DOE OSTI2025

Modification and analysis of context-specific genome-scale metabolic models: methane-utilizing microbial chassis as a case study

ABSTRACT Context-specific genome-scale model (CS-GSM) reconstruction is becoming an efficient strategy for integrating and cross-comparing experimental multi-scale data to explore the relationship between cellular genotypes, facilitating fundamental or applied research discoveries. However, the application of CS modeling for non-conventional microbes is still challenging. Here, we present a graphical user interface that integrates COBRApy, EscherPy, and RIPTiDe, Python-based tools within the BioUML platform, and streamlines the reconstruction and interrogation of the CS genome-scale metabolic frameworks via Jupyter Notebook. The approach was tested using -omics data collected for Methylotuvimicrobium alcaliphilum 20Z R , a prominent microbial chassis for methane capturing and valorization. We optimized the previously reconstructed whole genome-scale metabolic network by adjusting the flux distribution using gene expression data. The outputs of the automatically reconstructed CS metabolic network were comparable to manually optimized i IA409 models for Ca-growth conditions. However, the CS model questions the reversibility of the phosphoketolase pathway and suggests higher flux via primary oxidation pathways. The model also highlighted unresolved carbon partitioning between assimilatory and catabolic pathways at the formaldehyde-formate node. Only a very few genes and only one enzyme with a predicted function in C1 metabolism, a homolog of the formaldehyde oxidation enzyme ( fae1-2 ), showed a significant change in expression in La-growth conditions. The CS-GSM predictions agreed with the experimental measurements under the assumption that the Fae1-2 is a part of the tetrahydrofolate-linked pathway. The cellular roles of the tungsten (W)-dependent formate dehydrogenase ( fdhAB ) and fae homologs ( fae1-2 and fae3 ) were investigated via mutagenesis. The phenotype of the f dhAB mutant followed the model prediction. Furthermore, a more significant reduction of the biomass yield was observed during growth in La-supplemented media, confirming a higher flux through formate. M. alcaliphilum 20Z R mutants lacking fae1-2 did not display any significant defects in methane or methanol-dependent growth. However, contrary to fae1, the fae1-2 homolog failed to restore the formaldehyde-activating enzyme function in complementation tests. Overall, the presented data suggest that the developed computational workflow supports the reconstruction and validation of CS-GSM networks of non-model microbes. IMPORTANCE The interrogation of various types of data is a routine strategy to explore the relationship between genotype and phenotype. An efficient approach for integrating and cross-comparing experimental multi-scale data in the context of whole-genome-based metabolic network reconstruction becomes a powerful tool that facilitates fundamental and applied research discoveries. The present study describes the reconstruction of a context-specific (CS) model for the methane-utilizing bacterium, Methylotuvimicrobium alcaliphilum 20Z R . M. alcaliphilum 20Z R is becoming an attractive microbial platform for the production of biofuels, chemicals, pharmaceuticals, and bio-sorbents for capturing atmospheric methane. We demonstrate that this pipeline can help reconstruct metabolic models that are similar to manually curated networks. Furthermore, the model is able to highlight previously overlooked pathways, thus advancing fundamental knowledge of non-model microbial systems or promoting their development toward biotechnological or environmental implementations.

Kulyashov, M. A.↗
DOE OSTI2018

Cesium Ion Exchange Using Crystalline Silicotitanate with 5.6 M Sodium Simulant

The Low-Activity Waste Pretreatment System (LAWPS) facility is planned to pretreat Hanford tank waste supernate by filtering to remove solids and processing through ion exchange columns to remove cesium. The ion exchange media is currently (since 2018) targeted to be crystalline silicotitanate (CST). This material has been produced as an engineered form (generally spherical beads) by Honeywell UOP LLC (Des Plaines, IL). Previous forms of this media have been tested in a wide array of simulants and process scales, but column breakthrough and batch contact testing to date on actual tank waste has been limited to a few tank wastes. Washington River Protection Solutions requested a series of studies to demonstrate Cs load behavior in a small column format and determine if a simple batch contact test with CST can be used to qualify tank waste supernate prior to processing it in the LAWPS. The goal of the batch contact testing is to determine if there are any issues with the tank waste that would preclude Cs removal by the ion exchanger. Testing was conducted with IONSIV TM R9140-B CST provided by Honeywell UOP in 2018 (Batch 2081000057). The CST was received in the sodium (Na) form, so no pretreatment conditioning to convert to the Na form was required. Before use in testing, the CST was passed through a #25 sieve (710-micron openings) and collected on a #60 sieve (250-micron openings) with the intent of removing any large and fine particles. Physical properties were measured on the CST including particle size distribution (d50 = 570 microns) and scanning electron micrographic examination. The CST was rinsed with water until the contact solution was visually nearly clear. The CST bed density (1.00 g/mL) and CST bed void fraction (0.656) were measured on the sieved and rinsed CST. The batch contact testing varied Cs concentration in a 5.6 M Na simple simulant solution. Testing was conducted in a liquid volume to solids mass ratio of 200. The distribution coefficient (K d ) was determined to be 770 mL/g at the Cs equilibrium condition of 8.0 μg/mL; with a bed density of 1.00 g/mL, this corresponds to a predicted 50% Cs breakthrough of 770 bed volumes (BVs). The Cs load capacity at 8.0 μg/mL equilibrium condition was determined to be 6.16 mg Cs/g dry CST. The column testing was prototypic to the intended LAWPS operations in a lead-lag column format, albeit on a small-scale basis with 10-mL CST beds. The feed was processed downflow through the lead column and then through the lag column. Three flowrates were tested: 1.19, 1.99, and 4.56 BV/h. The feed was displaced with 0.1 M NaOH, and then the columns were rinsed with water sequentially through the lead then lag columns. One column system was evaluated top to bottom with a gamma scanner to assess the axial Cs loading. Table ES.1 summarizes the relevant Cs loading characteristics.

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

Small to Full Height Scale Comparisons of Cesium Ion Exchange Performance with Crystalline Silicotitanate

The U.S. Department of Energy’s (DOE) Hanford Site houses 56 million gallons of high-level radioactive waste generated from plutonium production from 1944 to 1988. The supernatant waste, currently stored in underground tanks, is intended to be vitrified following filtration and 137 Cs removal at the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Vitrification Facility. The WTP Pretreatment Facility will not be operational for several years. The Tank Side Cesium Removal (TSCR) system is a technology demonstration that will remove cesium from tank waste supernate to support directly feeding LAW to the vitrification facility. The 137 Cs removal is important to meet the WTP LAW contract specification and ultimately for creating a contact-handled waste form. The waste acceptance criteria (WAC) limit for the WTP LAW Facility is <3.18E-5 Ci 137 Cs per mole Na. The TSCR system is skid mounted and employs two key technologies: dead end filtration for solids removal and ion exchange (IX) for cesium removal. Filtration is necessary to protect the functionality of the IX columns. The IX process utilizes sodium form crystalline silicotitanate (CST) IX media produced by UOP Honeywell, LLC (Des Plaines, IL) under the product name IONSIV R9140-B, 18 x 50 mesh, in a lead-lag-polish column configuration. Each column contains a CST bed height of 92 inches and a volume of approximately 157 gallons of CST IX media. The full-scale TSCR operation will run at a residence time of 1.9 bed volumes (BV)/h, which results in a superficial velocity of 7.3 cm/min and a flowrate of ~5 gal/min. Column testing at small (2.5% of the full bed height), medium (12% of the full bed height), and full-height scales has been previously conducted to evaluate process variables and scale up performance of Cs exchange onto the CST. Cesium load performances from various sieve cuts at the small scale indicated that a 30-mesh sieve cut be tested to determine if it better reflects the 12% and full-height column performances at the small scale. Two process flowrates were tested in the small-column configuration with <30-mesh CST and simulant solutions. These tests were compared to full-height column tests at the same residence times to assess CST particle size effect on column scaling. Table S.1 summarizes the observed column performance determined for the two flowrates juxtaposed to the previous work with 5.6 M Na simulant at higher scales (used as benchmarks). The WAC breakthroughs between the small and full-height tests at 1.3 BV/h differed by ~59 BVs. The WAC breakthroughs for small, medium, and full-height tests at 1.8 BV/h were consistent at 240 BVs. The 50% Cs breakthroughs were nominally equivalent for all column tests. The common transition zones and onsets of Cs breakthrough at the 1.8 BV/h tests indicated that the Cs mass transfers were equivalent and thus the <30-mesh CST Cs load performance at the small scale successfully modeled that of the full-height system. It is recommended that the <30-mesh CST be used in subsequent 10-mL CST bed tests.

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

Ion Exchange Processing of AP-105 Hanford Tank Waste through Crystalline Silicotitanate in a Staged 2- then 3-Column System (Rev.1)

The Tank Side Cesium Removal (TSCR) system, under development by Washington River Protection Solutions LLC (WRPS), will send initial low-activity Hanford waste tank supernate feeds to the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility. In addition to entrained solids removal from the supernate, the primary goal of TSCR is to remove cesium-137 ( 137 Cs) by ion exchange, allowing contact handling of the liquid effluent product at the WTP. Crystalline silicotitanate (CST) ion exchange media, manufactured by Honeywell UOP, LLC (product IONSIVTM R9140-B), was selected as the ion exchange media at TSCR. CST is a non-elutable inorganic material that has demonstrated robust chemical, physical, and radiation tolerance while maintaining functionality. However, exchange kinetics of Cs onto CST is slow, resulting in low utilization of the CST Cs load capacity before unacceptable Cs breakthrough. Two process flow designs have been tested, as follows. 1. Lead-lag column processing: The lead column was removed after the lag column effluent reached the waste acceptance criteria (WAC) limit, the lag column was moved into the lead position, and a new lag column was installed. This format used ~52% Cs load capacity on the lead column. 2. Lead-lag-polish column processing: The processing was stopped when the polish column effluent reached the WAC limit. This format resulted in 81% Cs load capacity on the lead column. Testing with diluted feed from Hanford tank AP-105 (AP-105DF) incorporated a nuanced change to the lead-lag-polish column system where the polish column was inserted when the lag column effluent reached WAC limit. A 10.9-L volume of AP-105DF (diluted to 5.6 M Na) was processed through the Direct Feed Test Platform system, established at Pacific Northwest National Laboratory to support small-scale waste qualification efforts. The columns consisted of 10-mL CST beds (CST Lot 2002009604, sieved to screen out >30-mesh particles) placed in 1.5-cm-inner-diameter columns. Feed was processed at 1.83 bed volumes (BV) per hour; the flowrate, in terms of contact time with the CST bed, matched the expected flowrate at TSCR. The <30-mesh CST sieve cut was expected to provide appropriate performance scaling to a full-height column. The installation of the polish column later in processing (after processing 523 BVs) did not appear to fundamentally change the utilization of the lead column for Cs exchange nor did it extend the total feed processing volume when compared to the previous test with AP-107 feed. Table ES.1 and Figure ES.1 summarize the measured AP-105DF Cs load performance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Community Solar and Community Solar+Storage: A Roadmap of Barriers and Solutions for Commercial Systems in NYC

Sustainable CUNY worked with decision makers and subject matter experts (SME's) to identify the barriers to and solutions for advancing commercial Community Solar (CS) and CS+Storage (CS+S) in urban areas. This roadmap captures the key challenges and solutions identified by New York City (NYC) stakeholders, including the Real Estate Board of New York (REBNY), through a collaborative process. Solar, as well as storage, are among the fastest growing energy segments in the United States, with CS, also known as Community Distributed Generation (CDG), gaining popularity with those who may not own or have access to a viable roof. Urban areas like NYC, which have a large population of renters, are particularly well suited for CS projects where credits from the power produced by a large remote installation are offered on a subscription basis to residents or businesses in the community. However, CS and CS+S projects have stalled at the doorstep of many cities. Host site owners, particularly those with large rooftops, have been slow to commit to installing CS due to competing rooftop usage and programs, limited knowledge about incentives, lack of economic data, and a complicated implementation process.

14 SOLAR ENERGY↗
NASA NTRS1983

Coherent structures - Reality and myth

Large-scale coherent structures (CS) in turbulent shear flows are characterized, reviewing recent theoretical and experimental investigations. The use of computers as a research tool and the flow-visualization experimental technique are introduced, CS are defined, the history of their discovery is traced, and their main characteristics are listed. Topics discussed and illustrated include the initial condition of the free shear layer, triple and double decomposition, topological features of CS, detection and eduction of CS, phase alignment via cross correlation, induced versus natural structures, the bursting phenomenon, turbulent spot, streaks, bursting frequency, the axisymmetric mixing layer, vortex pairing in an axisymmetric jet, CS and jet noise, broadband noise amplification via pure-tone excitation, CS interaction in a plane-jet near field, the Taylor hypothesis applied to CS, negative production, and the validity of the Reynolds-number similarity hypothesis. It is found that the coherent Reynolds stress, vorticity, and production are not much greater than the time-averaged values for fully developed flows with significant incoherent turbulence, suggesting that the importance of CS may have been exaggerated in some recent studies.

Hussain, A. K. M. F.↗
NASA NTRS2013

Using Combustion Synthesis to Reinforce Berms and Other Regolith Structures

The Moonraker Excavator and other tools under development for use on the Moon, Mars, and asteroids will be employed to construct a number of civil engineering projects and to mine the soil. Mounds of loose soil will be subject to the local transport mechanisms plus artificial mechanisms such as blast effects from landers and erosion from surface vehicles. Some of these structures will require some permanence, with a minimum of maintenance and upkeep. Combustion Synthesis (CS) is a family of processes and techniques whereby chemistry is used to transform materials, often creating flame in a hard vacuum. CS can be used to stabilize civil engineering works such as berms, habitat shielding, ramps, pads, roadways, and the like. The method is to unroll thin sheets of CS fabric between layers of regolith and then fire the fabric, creating a continuous sheet of crusty material to be interposed among layers of loose regolith. The combination of low-energy processes, ISRU (in situ resource utilization) excavator, and CS fabrics, seems compelling as a general method for establishing structures of some permanence and utility, especially in the role of robotic missions as precursors to manned exploration and settlement. In robotic precursory missions, excavator/ mobility ensembles mine the Lunar surface, erect constructions of soil, and dispense sheets of CS fabrics that are covered with layers of soil, fired, and then again covered with layers of soil, iterating until the desired dimensions and forms are achieved. At the base of each berm, for example, is a shallow trench lined with CS fabric, fired and filled, mounded, and then covered and fired, iteratively to provide a footing against lateral shear. A larger trench is host to a habitat module, backfilled, covered with fabric, covered with soil, and fired. Covering the applied CS fabric with layers of soil before firing allows the resulting matrix to incorporate soil both above and below the fabric ply into the fused layer, developing a very irregular surface which, like sandpaper, can provide an anchor for loose soil. CS fabrics employ a coarse fiberglass weave that persists as reinforcement for the fired material. The fiberglass softens at a temperature that exceeds the combustion temperature by factors of two to three, and withstands the installation process. This type of structure should be more resistant to rocket blast effects from Lunar landers.

Rodriquez, Gary↗
DOE OSTI2016

Behavior of Radioactive Cesium in Municipal Solid Waste of Thermal Treatment Plants after Fukushima Nuclear Power Plant Accident - 16626

Municipal solid waste (MSW) contaminated by radioactive cesium (r-Cs) has been treated by various thermal treatment facilities in Japan. However, the behavior of r-Cs in their plants is scarcely known. Therefore, we investigated 4 types of the thermal treatment plants to understand the r-Cs behavior during different thermal treatments of the MSW. The distribution of r-Cs between residue discharged from bottom of furnace (bottom ash, non-combustibles or slag) and fly ash was affected by furnace type. The leaching rate of r-Cs from the fly ash and the bottom residues were measured. The leaching rate from the former was high and ranged from 40 to 100%. In contrast, the most of r-Cs in the latter did not dissolve into water. Furthermore, we evaluated whether baghouse (an air-pollution control equipment) successfully removed r-Cs compound in flue gas. R-Cs was efficiently removed regardless of thermal treatment type. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗