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At least 307 records · Page 17

Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity

Functional organic–inorganic hybrid materials with tunable properties are useful across many application areas, ranging from gas storage to electronics, flame retardants, separations, and catalysis. Combining polymers, with a suite of functional groups and conformational flexibility, and inorganic nanoparticles, with tunable surface chemistry and composition, yields hybrids with novel functional properties. Specifically, in catalysis, control of the electronic environment at a metal interface is paramount in determining the catalytic properties. In this contribution, we describe a modular process to prepare porous polymer–nanocrystal (NC) composites in a hierarchical, multilayered synthesis, in which multiple parameters can be accurately tuned: polymer functional groups and the corresponding pore structure, the polymer layer thickness, and the NC size, shape, and composition. This process provides for a variety of controlled materials with high surface area, tunable chemistry, and thermal and chemical stabilities. Furthermore, we demonstrate their utility for shape- and size-selective catalytic conversions both in oxidation and hydrogenation reactions, where they show increased selectivity by orders of magnitude compared to conventional polymer-supported metal catalysts. In light of the high degree of control in the composite structure, this method allows for the design and realization of catalysts for several reactions and reaction environments and for nanomaterials with other applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Riverine dissolved organic matter transformations increase with watershed area, water residence time, and Damköhler numbers in nested watersheds

Abstract Quantifying the relative influence of factors and processes controlling riverine ecosystem function is essential to predicting future conditions under global change. Dissolved organic matter (DOM) is a fundamental component of riverine ecosystems that fuels microbial food webs, influences nutrient and light availability, and represents a significant carbon flux globally. The heterogeneous nature of DOM molecular composition and its propensity for interaction (i.e., functional diversity) can characterize riverine ecosystem function across spatiotemporal scales. To investigate fundamental drivers of DOM diversity, we collected seasonal water samples from 42 nested locations within five watersheds spanning multiple watershed sizes (~ 5 to 30,000 km 2 ) across the United States. Patterns in DOM molecular richness, aromaticity, relative abundance of N-containing formulas, and putative biochemical transformations derived from high-resolution mass spectrometry were assessed across gradients of explanatory variables associated with watershed characteristics (e.g., watershed area, water residence time, land cover). We found that putative biochemical transformations were more strongly related to explanatory variables across watersheds than common bulk DOM parameters and that watershed area, surface water residence time and derived Damköhler numbers representing DOM reactivity timescales were strong predictors of DOM diversity. The data also indicate that catchment-specific land cover factors can significantly influence DOM diversity in diverging directions. Overall, the results highlight the importance of considering water residence time and land cover when interpreting longitudinal patterns in DOM chemistry and the continued challenge of identifying generalizable drivers that are transferable across watershed and regional scales for application in Earth system models. This work also introduces a Findable Accessible Interoperable Reusable (FAIR) dataset (> 300 samples) to the community for future syntheses.

54 ENVIRONMENTAL SCIENCES↗

Operando carbon corrosion measurements in fuel cells using boron-doped carbon supports

Carbonaceous materials are the most common catalyst supports in proton exchange membrane fuel cell (PEMFCs), yet their corrosion is one of the limiting factors in achieving high durability. Herein, we doped carbon supports with boron (B) to increase the corrosion-resistance of the support. Two types of B-doped carbons were synthesized and studied as platinum support materials. Further, they varied in their morphologies, surface areas, and the types of boron species. The durability of Pt/B-doped carbon catalysts was investigated using the US-DOE catalysts’ supports accelerated stress test (AST) and a mass-spectrometer connected to the fuel cell effluent stream to quantify the mass of corroded carbon support in operando. The addition of boron to the carbon increased the stability of Pt catalysts in long-term usage of PEMFC. After 4000 AST cycles, more than 50% of initial current density was preserved for the boron-containing systems, while less than 30% of it remained with Vulcan carbon (Pt/V). Also, the Pt/B-doped carbon samples demonstrated better electrochemical active surface area (ECSA) stability when compared to Pt/V. Carbon loss measurements showed that B-doped carbons have higher resistance to electrochemical corrosion than unmodified carbon. Specifically, the substitutional boron-doped carbon demonstrated an extremely high stability and low corrosion rate.

25 ENERGY STORAGE↗

Accelerating Hydrogen Absorption and Desorption Rates in Palladium Nanocubes with an Ultrathin Surface Modification

Exploiting the high surface-area-to-volume ratio of nanomaterials to store energy in the form of electrochemical alloys is an exceptionally promising route for achieving high-rate energy storage and delivery. Nanoscale palladium hydride is an excellent model system for understanding how nanoscale-specific properties affect the absorption and desorption of energy carrying equivalents. Hydrogen absorption and desorption in shape-controlled Pd nanostructures does not occur uniformly across the entire nanoparticle surface. Instead, hydrogen absorption and desorption proceed selectively through high-activity sites at the corners and edges. Such a mechanism hinders the hydrogen absorption rates and greatly reduces the benefit of nanoscaling the dimensions of the palladium. To solve this, we modify the surface of palladium with an ultrathin platinum shell. This modification nearly removes the barrier for hydrogen absorption (89 kJ/mol without a Pt shell and 1.8 kJ/mol with a Pt shell) and enables diffusion through the entire Pd/Pt surface.

25 ENERGY STORAGE↗

Degradation and recovery of solid oxide fuel cell performance by control of cathode surface acidity: Case study – Impact of Cr followed by Ca infiltration

Solid oxide fuel cells (SOFC) have attracted attention as clean and efficient energy conversion devices with low emissions. However, several degradation mechanisms limit the electrochemical performance of current SOFCs, with cathode degradation due to Cr-poisoning from metal interconnects particularly problematic. The acidity/basicity of binary additives has been found to be a sensitive descriptor of the oxygen exchange kinetics, indicating that acidic Cr-species/basic Ca-species can be expected to deactivate/activate the cathode surface, respectively. Inspired by recent advances, the feasibility of relative acidity as a tool for reviving degraded SOFCs is demonstrated by neutralizing Cr-poisoned SOFCs by subsequent serial infiltration of Ca-species. Furthermore, a model mixed ionic and electronic conducting oxide, Pr 0.1 Ce 0.9 O 2-δ (PCO), is selected as the cathode material. Area-specific resistances (ASR) of symmetric cells obtained by electrochemical impedance spectroscopy show that Cr-infiltration results in a seven-fold increase in ASR, while subsequent infiltration of Ca-species leads to complete recovery. Performance degradation and recovery are attributed to depressed/enhanced redox properties at the PCO surface, as supported by XPS analysis. Experiments using anode-supported fuel cells show a reduction in peak power density by 26% upon Cr-infiltration, reversed following Ca-infiltration, after which no degradation is observed during subsequent operation for 100 h.

(Pr,Ce)O2-δ↗

Capacitance of Carbon Nanotube/Graphene Composite Electrodes with [BMIM + ][BF$_4^–$]/Acetonitrile: Fixed Voltage Molecular Dynamics Simulations

The capacitance of nanoporous carbon electrode materials is dictated by the physical interactions with electrolyte ions and molecules at the accessible interior electrode surface. While significant progress has been made in designing and synthesizing carbon materials with well-defined and relatively homogeneous nanoporosity, the majority of materials remain heterogeneous, and the resulting properties reflect an average over this distribution. In this regard, computer simulations can be a valuable tool to predict or validate structure/property relationships by systematically investigating well-defined, model electrode morphologies. In this work, we utilize fixed-voltage molecular dynamics simulations to predict structure/capacitance relationships for five different model morphologies of carbon nanotube/graphene (CNT/G) composite electrodes with 1-butyl-3-methylimidazolium tetrafluoroborate/acetonitrile electrolyte. The CNT/G electrode models are inspired by experimental “layer-by-layer” syntheses and strike a balance between realism and computational tractability. Comparison between different model electrode architectures elucidates important structure/property relationships. We find that CNT/graphene contact points serve as “hot spots” with significantly enhanced charge separation relative to the rest of the electrode. Furthermore, we demonstrate a specific nanoconfinement motif that provides substantial 3–4$\times$ enhancement of local capacitance, resulting in a ~40% increase of the total electrode differential capacitance. Because the accessible surface area of the model CNT/G electrodes is precisely determined, a comparison of per-area capacitance across systems is unambiguous. Our results thus complement a prior computational demonstration of capacitance enhancement in nanoconfinement while elucidating additional interaction motifs at CNT/G electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Wildfires Temperature Estimation by Complementary Use of Hyperspectral PRISMA and Thermal (ECOSTRESS & L8)

This paper deals with detection and temperature analysis and of wildfires using PRISMA imagery. Precursore IperSpettrale della Missione Applicativa (Hyperspectral Precursor of the Application Mission, PRISMA) is a new hyperspectral mission by ASI (Agenzia Spaziale Italiana, Italian Space Agency) launched in 2019. This mission provides hyperspectral images with a spectral range of 400–2,500 nm and an average spectral resolution less than 12 nm and a spatial resolution of 30 m/pixel. This study focuses on the wildfire temperature estimation over the Bootleg Fire, US 2021. The analysis starts by considering the Hyperspectral Fire Detection Index (HFDI) which is used to analyze the informative content of the images, along with the analysis of some specific visible, near-infrared and shortwave-infrared bands. This first analysis is used as input to perform a temperature estimation of the areas with active wildfire. Surface temperature is retrieved using PRISMA radiance and a linear mixing model based on two background components (vegetation and burn scar) and two active fire components. PRISMA temperatures are compared with LST (Land Surface Temperature) products from NASA's ECOSTRESS and Landsat 8 which imaged the Bootleg Fire before and after PRISMA. A critical discussion of the results obtained with PRISMA is presented, followed by the advantages and limitation of the proposed approach.

54 ENVIRONMENTAL SCIENCES↗

Tuning electrochemical and transport processes to achieve extreme performance and efficiency in solid oxide cells

Solid oxide cells (SOCs) have important applications as fuel cells and electrolyzers. The application for storage of renewable electricity is also becoming increasingly relevant; however, it is difficult to meet stringent area-specific resistance (ASR) and long-term stability targets needed to achieve required efficiency and cost. Here we show a new SOC that utilizes a very thin Gd-doped ceria (GDC)/yttria-stabilized zirconia (YSZ) bi-layer electrolyte, Ni–YSZ cell support with enhanced porosity, and electrode surface modification using PrO x and GDC nanocatalysts to achieve unprecedented low ASR values < 0.1 Ω cm 2 , fuel cell power density ~3 W cm –2 , and electrolysis current density ~4 A cm –2 at 800 °C. Besides this exceptionally high performance, fuel cell and electrolysis life tests suggest very promising stability in fuel cell and steam electrolysis modes. Furthermore, electrochemical impedance spectroscopy analysis done using a novel impedance subtraction method shows how rate-limiting electrode processes are impacted by the new SOC materials and design.

25 ENERGY STORAGE↗

Atomically Precise Nanoclusters as Co‐Catalysts for Light‐Activated Microswimmer Motility

Microswimmers are self-propelled particles that navigate fluid environments, offering significant potential for applications in environmental pollutant decomposition, biosensing, and targeted drug delivery. Their performance relies on engineered catalytic surfaces. Gold nanoclusters (AuNCs), with atomically precise structures, tunable optical properties, and high surface area-to-volume ratio, provide a new optimal catalyst for enhancing microswimmer propulsion. Unlike bulk gold or nanoparticles, AuNCs may deliver tunable photocatalytic activity and increased catalytic specificity, making them ideal co-catalysts for hybrid microswimmers. For the first time, this study combines AuNCs with TiO 2 /Cr 2 O 3 Janus microswimmers, combining the unique properties of both materials. This hybrid system capitalizes on the tuned optical properties of AuNCs and their role as co-catalysts with TiO 2 , driving enhanced photocatalytic performance under ultraviolet (UV) excitation. Using motion analysis, it is shown that the AuNC-microswimmers exhibit significantly greater propulsion and mean squared displacement (MSD) as compared to controls. These findings suggest that the integration of nanoclusters with semiconductor materials enables state of the art, light-switchable microswimmers. These AuNC-microswimmer systems may thus offer new opportunities for environmental catalysis and other applications, providing precise control over catalytic and motile behaviors at the microscale.

36 MATERIALS SCIENCE↗

PCP consensus protein/peptide alphavirus antigens stimulate broad spectrum neutralizing antibodies

Vaccines based on proteins and peptides may be safer and if calculated based on many sequences, more broad-spectrum than those designed based on single strains. Physicochemical Property Consensus (PCP con ) alphavirus (AV) antigens from the B-domain of the E2 envelope protein were designed, synthesized recombinantly and shown to be immunogenic (i.e. sera after inoculation detected the antigen in dotspots and ELISA). Antibodies in sera after inoculation with B-region antigens based on individual AV species (eastern or Venezuelan equine encephalitis (EEEV con , VEEV con ), or chikungunya (CHIKV con ) bound only their cognate protein, while those designed against multiple species (Mosaik con and EVC con ) recognized all three serotype specific antigens. The VEEV con and EEEV con sera only showed antiviral activity against their related strains (in plaque reduction neutralization assays (PRNT 50/80 ). Peptides designed to surface exposed areas of the E2-A-domain of CHIKV con were added to CHIKV con inocula to provide anti-CHIKV antibodies. EVC con , based on three different alphavirus species, combined with E2-A-domain peptides from AllAV con , a PCPcon of 24 diverse AV, generated broad spectrum, antiviral antibodies against VEEV, EEEV and CHIKV, AV with less than 35% amino acid identity to each other (>65% diversity). This is a promising start to a molecularly defined vaccine against all AV. A further study with these antigens can illuminate what areas are most important for a robust immune response, resistant to mutations in rapidly evolving viruses. The validated computational methods can also be used to design broad spectrum antigens against many other pathogen families.

59 BASIC BIOLOGICAL SCIENCES↗

Genome-Resolved Metaproteomics Decodes the Microbial and Viral Contributions to Coupled Carbon and Nitrogen Cycling in River Sediments

Rivers have a significant role in global carbon and nitrogen cycles, serving as a nexus for nutrient transport between terrestrial and marine ecosystems. Although rivers have a small global surface area, they contribute substantially to worldwide greenhouse gas emissions through microbially mediated processes within the river hyporheic zone. Despite this importance, research linking microbial and viral communities to specific biogeochemical reactions is still nascent in these sediment environments. To survey the metabolic potential and gene expression underpinning carbon and nitrogen biogeochemical cycling in river sediments, we collected an integrated data set of 33 metagenomes, metaproteomes, and paired metabolomes. We reconstructed over 500 microbial metagenome-assembled genomes (MAGs), which we dereplicated into 55 unique, nearly complete medium- and high-quality MAGs spanning 12 bacterial and archaeal phyla. We also reconstructed 2,482 viral genomic contigs, which were dereplicated into 111 viral MAGs (vMAGs) of >10 kb in size. As a result of integrating gene expression data with geochemical and metabolite data, we created a conceptual model that uncovered new roles for microorganisms in organic matter decomposition, carbon sequestration, nitrogen mineralization, nitrification, and denitrification. We show how these metabolic pathways, integrated through shared resource pools of ammonium, carbon dioxide, and inorganic nitrogen, could ultimately contribute to carbon dioxide and nitrous oxide fluxes from hyporheic sediments. Further, by linking viral MAGs to these active microbial hosts, we provide some of the first insights into viral modulation of river sediment carbon and nitrogen cycling.

54 ENVIRONMENTAL SCIENCES↗

In‐Scribe Silane Bonding for Mechanical Reinforcement of Perovskite Photovoltaic Modules

Despite the extraordinary rise in power conversion efficiency over the last decade, metal halide perovskite (MHP) photovoltaics remain more mechanically fragile than other PV technologies. In this work, the scribe area, created by the monolithic interconnection of thin-film solar cells, is used to extrinsically reinforce the mechanical robustness of packaged MHP solar modules. In contrast to the epoxy-based chemistries often leveraged in the MHP literature, silane-grafted polyolefin encapsulants are designed to form strong covalent bonds to oxide surfaces, specifically to glass and the transparent conductive oxide at the base of the scribe line. Pseudo-modules encapsulated with silane-grafted polyolefin are measured with more than an order-of-magnitude enhancement infracture energy from 0.27 ± 0.01 J·m −2 (no scribes) to 5.97 ± 0.42 J·m −2 (scribes perpendicular to delamination directioncovering ≈2.2% of the module area). The silane-grafted polyolefin retains strong adhesion even after undergoing an accelerated IEC 61215 thermal cycling test consisting of 250 cycles. We find that the in-scribe bonding allows perovskite modules to have adhesion strength comparable to commercial c-Si and CdTe technologies with only 5% reduction in the active module area. This manufacturing-compatible approach offers a practical solution to address the mechanical integrity challenges in MHP solar modules, regardless of cell architecture.

14 SOLAR ENERGY↗

Coupled effects of future rainfall and land use on urban stormwater drainage system in Tampa, Florida (USA)

Future rainfall and land use are two important factors for flood management since they both directly and indirectly affect the functionality and performance of urban stormwater drainage infrastructures. Although some studies have already examined the coupled effects of future rainfall and land use conditions, they have not concluded how such effects on both surface runoff and flood areas would change with regional surface elevation variation and infrastructure conditions. This paper analyzed the coupled effects of future rainfall and land use on urban drainage systems in terms of surface runoff quantity and flood area changes using EPA SWMM. Future downscaled and bias-corrected precipitation projections for 2040–2060 and 2080–2099 from “Downscaled CMIP3 and CMIP5 Climate and Hydrology Projections” Archive and future land use for 2050 s and 2090 s from EPA ICLUS project were used for the City of Tampa in Florida (USA). It was shown that potential runoff volume and flood area changes ranged from –40% to 160%, and –40% to 400% due to rainfall change, while potential changes induced by land use change ranged from 0% to 3.5%, and 0% to 18% respectively. Additionally, this study examined the coupled effects of future rainfall and land use changes on flood area variations, considering the capacity of drainage infrastructure and elevation variation of study site. Results showed that flood area variations are not solely influenced by runoff quantity changes due to the two external drivers, but also by other factors. Specifically, in low-relief areas with inadequate drainage infrastructure and less elevation variation, these two drivers have no additive effects on the percentage of flood area changes. In contrast, in areas with adequate drainage infrastructure and greater surface elevation variation, there are additive effects from rainfall and land use changes on flood area expansions. These findings have important implications for stakeholders involved in city planning and flooding control, particularly for urban areas facing future precipitation and urbanization challenges.

54 ENVIRONMENTAL SCIENCES↗

VIC-Global Parameter Dataset Sensitivity with the Variable Infiltration Capacity Model: Evaluating the importance of dynamic land surface parameters when using the VIC-Global parameter dataset

Accurate prediction of runoff is essential to water resources management, flood risk assessment, and ecosystem protection. However, many hydrological models still have relatively substantial limitations when representing the influence of land use and land cover (LULC) on runoff generation and routing. Changes in LULC, such as deforestation, urban expansion, agricultural intensification, and wetland loss, have been shown to alter the water balance at the land surface through fundamental hydrologic processes (e.g., interception, infiltration, evapotranspiration, and soil storage). However, it remains an open question what the exact magnitude and timing of these impacts are for the spatial and temporal scales commonly used in engineering applications. In this analysis we focus on one aspect of recent LULC change for assessing human impacts, which is urbanization. Specifically we seek to determine the impacts of urbanization on the magnitude and timing of surface runoff and baseflow in HUC-12 basins in Clark County, Nevada which has experienced rapid urbanization. We use the Variable Infiltration Capacity (VIC) hydrology model with a widely used off-the-shelf dataset of land surface parameters, VIC-Global, both of which have been commonly used in the past for water and energy balance modeling for large scale hydrologic studies. We examine two scenarios where the first scenario removes all urbanized land cover and parameterizes those areas of the basins as barren or open shrubland. The second scenario tests the opposite case where all areas of the basins are classified as urban regardless of their present classification. The results from the VIC model show there is a low sensitivity for daily surface runoff between scenarios. The daily baseflow values indicate similar low sensitivity to the classification change during specific periods, but then have substantial differences during other period when large precipitation events are occurring. This is likely due to the assumed parameter values for the urban land cover classification made by the VIC-Global dataset. Using a static land cover parameterization is reasonable for large domain hydrology models that are being used for near-term planning horizons (<30 years). However, longer planning horizons where feedbacks between the atmosphere and land surface are important, especially in transient climate situations, considerations for how to update land surface parameters should be incorporated.

42 ENGINEERING↗

Anoxia begets anoxia: A positive feedback to the deoxygenation of temperate lakes

Abstract Declining oxygen concentrations in the deep waters of lakes worldwide pose a pressing environmental and societal challenge. Existing theory suggests that low deep‐water dissolved oxygen (DO) concentrations could trigger a positive feedback through which anoxia (i.e., very low DO) during a given summer begets increasingly severe occurrences of anoxia in following summers. Specifically, anoxic conditions can promote nutrient release from sediments, thereby stimulating phytoplankton growth, and subsequent phytoplankton decomposition can fuel heterotrophic respiration, resulting in increased spatial extent and duration of anoxia. However, while the individual relationships in this feedback are well established, to our knowledge, there has not been a systematic analysis within or across lakes that simultaneously demonstrates all of the mechanisms necessary to produce a positive feedback that reinforces anoxia. Here, we compiled data from 656 widespread temperate lakes and reservoirs to analyze the proposed anoxia begets anoxia feedback. Lakes in the dataset span a broad range of surface area (1–126,909 ha), maximum depth (6–370 m), and morphometry, with a median time‐series duration of 30 years at each lake. Using linear mixed models, we found support for each of the positive feedback relationships between anoxia, phosphorus concentrations, chlorophyll a concentrations, and oxygen demand across the 656‐lake dataset. Likewise, we found further support for these relationships by analyzing time‐series data from individual lakes. Our results indicate that the strength of these feedback relationships may vary with lake‐specific characteristics: For example, we found that surface phosphorus concentrations were more positively associated with chlorophyll a in high‐phosphorus lakes, and oxygen demand had a stronger influence on the extent of anoxia in deep lakes. Taken together, these results support the existence of a positive feedback that could magnify the effects of climate change and other anthropogenic pressures driving the development of anoxia in lakes around the world.

54 ENVIRONMENTAL SCIENCES↗

Evaluation of the anisotropic grain boundaries and surfaces of α -U via molecular dynamics

Alloys based on uranium-zirconium are gaining renewed interest as fuels for the Versatile Test Reactor and a number of microreactor designs. Implementing metallic fuel in reactors creates the need for robust descriptive and predictive fuel performance modeling. Here, the current state of metallic fuel performance modeling relies on empirical equations derived from historical experiments, which may be unreliable when applied outside of their temperature, power, and composition phase space. One area where such data is lacking is the irradiation behavior of alpha -U, specifically tearing and porosity formation at the early stages of irradiation. While grain boundaries likely play a key role in this fuel behavior, relatively little is known about grain boundaries in alpha-U. Thus, we evaluate the grain boundary, surface energy, and work of adhesion of alpha -U utilizing molecular dynamics. Symmetric tilt grain boundaries (STGBs) are analyzed with the tilt plane oriented along each major crystallographic axis, for a total of eighty unique grain boundaries. The effect of temperature, tilt plane, and misorientation angle on interfacial energies are analyzed. The interfacial energies typically increase with temperature and there is significant variance as a function of misorientation angle, irrespective of the tilt plane. At 500 K, the average surface energy (1.23 J/m 2 ) is approximately 1.5 times the grain boundary energy (0.79 J/m 2 ), and the work of adhesion is approximately twice the grain boundary energy (1.68 J/m 2 ). Orientations for the likely formation of twins and likely failure planes are identified.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Metallurgical Analysis of the High Flux Isotope Reactor (HFIR) Carrier Lifting Bails (Rev.1)

The dissolution rates of the aluminum alloys in the High Flux Isotope Reactor (HFIR) element carriers and the Material Test Reactor (MTR) L-bundles in the H-Canyon facility have been identified as the possible cause of extended dissolutions that result in significant time and financial expenditures. A study, carried out by Savannah River National Laboratory (SRNL) to determine relationships between the dissolution rates and the metallurgical properties of the aluminum alloy materials of construction of the HFIR carriers and the L-bundles, considered the dissolution rates of aluminum alloy (AA) series 1100, 6061, and 6063. The study determined that the aluminum alloy compositions played a principal role in the dissolution rate of the carrier/bundle components. Higher dissolution rates were correlated with lower concentrations of the minor element additions in the alloys and with specific element concentrations. Aluminum alloys 1100 and 6063 were found to have similar dissolution rates that were approximately two orders of magnitude (100X) greater than those of AA6061. Based on the results of the dissolution behavior study, a Technical Assistance Request (TAR) was first issued to determine if the replacement of AA6061-T6 with AA6063-T6 is feasible for the HFIR carrier lifting bails. A Technical Task Request was then issued to consider AA6063-T5 as well as other alloys to improve possible supply chain issues. The metallurgical properties of the L-bundle (specifically the end caps) were not evaluated in this report because L-Bundle drawings already allow for the use of AA6063-T6 in all structural components. The HFIR carriers are composed of thin-walled components with significant surface areas that allow for relatively quick overall dissolution times. Conversely, the carrier lifting bails and the supporting constituents are composed of solid bars and thick plate regions with relatively small surface areas that experience longer overall dissolution times. While the MTR L-bundle design includes allowances for the materials of construction to be either AA6061-T6 or AA6063-T6, the HFIR carriers are specified to be constructed fully with AA6061-T6 alloy. This report analyzes the recommendations of the dissolution behavior study to replace the materials of construction of the HFIR carrier lifting bails. The analysis considers the operational requirements of the lifting bail and its supporting structures. To decrease dissolution times, the analysis considers direct replacement of the material as well as reductions in the thicknesses of the components to decrease the mass of the elements. Material reductions are considered on options for using either AA6061 and/or AA6063. The calculations are based on specifications from the American Society of Mechanical Engineer (ASME) and The Aluminum Association, Inc. design codes. The analysis finds that direct replacement of the lifting bail material of construction with AA6063-T6, and AA6063-T5 as well as reductions in the dimensions of the lifting bail components are acceptable. Note that this study considers the structural suitability of the alloys. It does not consider their dissolution rates in the dissolvers.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mechanically graded granular scaffolds for osteochondral tissue engineering

Engineered scaffolds designed to approximate the mechanical microenvironment of the osteochondral unit often address this complexity using discrete, two-phase architectures that introduce mechanical discontinuities and interfacial stress concentrations rather than a contiguous stiffness transition. To address this challenge, we created a photoannealed polyethylene glycol (PEG) granular scaffold with a spatially controlled stiffness gradient within a cell-permissive, macroporous architecture. Stiffness was dictated by photoannealing microgels using a photomask. We tuned void volume and available surface area by varying microgel diameter and tested how mesenchymal stromal cells (MSCs) interpret local mechanical environments. MSCs exhibited position-dependent differences in morphology, cytoskeletal structure, matrix deposition, and lineage-specific gene expression within the gradient scaffolds. Softer regions supported rounded cell morphology and deposition of a glycosaminoglycan-rich matrix, whereas stiffer regions promoted cell elongation, increased cytoskeletal tension, and expression of mineral-associated markers. Gradients formed from smaller microgels magnified these spatial responses by increasing cellular confinement and adhesion site availability. Disruption of actomyosin contractility eliminated these regional differences, demonstrating that MSCs rely on tension-dependent mechanotransduction to interpret the gradient. These findings reveal that coupling microgel architecture with continuous stiffness transitions provides a tractable platform to study multiscale mechanobiologic regulation and spatially guide osteochondral tissue formation.

Biological and medical sciences↗