Experimental Testing of the Theoretically Predicted Magnetic Properties for Kagomé Compounds in the Li–Fe–Ge System
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Mantravadi, Aishwarya [Department of Chemistry; Io↗
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Multiple highly expressed phospho enol pyruvate carboxylase genes have divergent enzyme kinetic properties in two C4 grasses
Abstract Background and Aims Phosphoenolpyruvate (PEP) carboxylase (PEPC) catalyses the irreversible carboxylation of PEP with bicarbonate to produce oxaloacetate. This reaction powers the carbon-concentrating mechanism (CCM) in plants that perform C4 photosynthesis. This CCM is generally driven by a single PEPC gene product that is highly expressed in the cytosol of mesophyll cells. We found two C4 grasses, Panicum miliaceum and Echinochloa colona, that each have two highly expressed PEPC genes. We characterized the kinetic properties of the two most abundant PEPCs in E. colona and P. miliaceum to better understand how the enzyme’s amino acid structure influences its function. Methods Coding sequences of the two most abundant PEPC proteins in E. colona and P. miliaceum were synthesized by GenScript and were inserted into bacteria expression plasmids. Point mutations resulting in substitutions at conserved amino acid residues (e.g. N-terminal serine and residue 890) were created via site-directed PCR mutagenesis. The kinetic properties of semi-purified plant PEPCs from Escherichia coli were analysed using membrane-inlet mass spectrometry and a spectrophotometric enzyme-coupled reaction. Key Results The two most abundant P. miliaceum PEPCs (PmPPC1 and PmPPC2) have similar sequence identities (>95 %), and as a result had similar kinetic properties. The two most abundant E. colona PEPCs (EcPPC1 and EcPPC2) had identities of ~78 % and had significantly different kinetic properties. The PmPPCs and EcPPCs had different responses to allosteric inhibitors and activators, and substitutions at the conserved N-terminal serine and residue 890 resulted in significantly altered responses to allosteric regulators. Conclusions The two, significantly expressed C4Ppc genes in P. miliaceum were probably the result of genomes combining from two closely related C4Panicum species. We found natural variation in PEPC’s sensitivity to allosteric inhibition that seems to bypass the conserved 890 residue, suggesting alternative evolutionary pathways for increased malate tolerance and other kinetic properties.
DiMario, Robert J. (ORCID:0000000250566868)↗
Learning interpretable surface elasticity properties from bulk properties via neural network equation learners
Surface elasticity is central to understanding the mechanics and stability of surfaces and interfaces. It is characterized by quantities such as surface tension, residual surface stress, and surface stiffness. However their analytical expressions are typically difficult to derive from atomistic data, and depend strongly on modeling choices. This work presents a neural network-based equation learner which combines customized activation functions and connection-based pruning to discover parsimonious, closed-form equations for surface elasticity from atomistic simulations. Applying the method to seven face-centered cubic (FCC) metals, our equation learner uncovers interpretable equations that describe both low-Miller index and high-Miller index surface properties, capturing long-tail property distributions accurately. The discovered expressions are decoupled into two components: a universal, geometry-driven orientation function, and material-specific baseline coefficients. We find that lower-order properties such as surface tension are fundamentally geometry dependent, while higher-order properties such as surface stress and elasticity show more complex geometry and material dependence. We also relate material dependent coefficients to bulk properties, forming a clear map from bulk material properties to surface elasticity. Overall, this approach demonstrates that interpretable neurosymbolic machine learning can bridge the gap between atomistic simulations and physical laws, enabling the discovery of generalizable structure–property relationships for materials science phenomena such as surface elasticity.
Equation learning↗
JOINT APPOINTEE: Evolution of ferroelectric properties in SmxBi1-xFeO3 via automated Piezoresponse Force Microscopy across combinatorial spread libraries
Combinatorial spread libraries offer a innovative approach to explore the evolution of material properties over broad concentration, temperature, and growth parameter spaces. However, traditional limitation of this approach is the requirement for the read-out of functional properties across the library. Here we develop automated Piezoresponse Force Microscopy (PFM) for the exploration of combinatorial spread libraries and demonstrate its application in the SmxBi1-xFeO3 system with the ferroelectric-antiferroelectric morphotropic phase boundary. This approach relies on the synergy of the quantitative nature of PFM and the implementation of automated experiments that allow PFM-based sampling over macroscopic samples. The concentration dependence of pertinent ferroelectric parameters has been determined and used to develop the mathematical framework based on Ginzburg-Landau theory describing the evolution of these properties across the concentration space. We pose that a combination of automated scanning probe microscope and combinatorial spread library approach will emerge as an efficient research paradigm to close the characterization gap in the high-throughput materials discovery. We make the data sets open to the community and hope that this will stimulate other efforts to interpret and understand the physics of these systems.
Automated Microscopy, Combinatorial Library, Ferro↗
Estimating Vadose Zone Flow Properties at the 100 K-East Soil Flushing Site Using ERT Monitoring Data: 2023 Interim Report - 100 KE Soil Property Estimation
In situ soil flushing is being using at the Hanford 100 K-East (100 KE) area to transport mobile chromium contamination in the vadose zone to the water table, where it can be collected and treat through pump and treat operations. The efficacy of soil flushing is directly related to the volume of clean water that infiltrates through contaminated soils. In practice, it is infeasible to comprehensively monitor which regions of the vadose zone are being infiltrated through direct sampling of pore water. Consequently, there can be significant uncertainty about which regions of the subsurface have been treated, especially if hydrogeologic conditions are favorable for the development of unstable flows and preferred flow pathways through the vadose zone (Jarvis, Koestel, and Larsbo 2016). Current approaches for quantitative monitoring of soil flushing performance rely on contaminant concentration measurements collected from extractions wells. There is no quantitative information on the volume of flush water delivered to targeted regions of the vadose zone at the Hanford Site, leading to significant uncertainty regarding source term removal and long-term impacts to groundwater. If the subsurface hydrogeologic properties at the 100 KE Area were adequately known, qualitative metrics of soil flushing performance could be simulated, thereby negating expenses required to obtain quantitative performance information through borehole drilling/sampling. However, estimating in situ hydrogeologic properties has long proven elusive, due primarily to a lack of sufficient information to constrain heterogeneous property estimates to a useful degree of certainty. Estimating vadose zone hydrogeologic properties is particularly challenging due the dependence of hydraulic conductivity on saturation. This report describes progress toward a first-of-its-kind demonstration using surface time-lapse 3D electrical resistivity tomography (ERT) monitoring data to estimate the hydrogeologic properties that control flush water transport at the 100 KE soil flushing site. The ultimate objective is (1) to verify sufficient information exists in the ERT monitoring data to adequately resolve vadose zone hydraulic properties, and (2) generate a “digital twin” (i.e., a numerical simulator) that can be used to simulate the amount of flush water that has been delivered to each targeted region of the vadose zone, and thereby assess the efficacy of flush water delivery. Resulting performance estimates can be used in leu of comprehensive borehole drilling and direct sampling (or wellbore logging) that would otherwise be required to obtain the same information.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Exploring biofiber properties and their influence on biocomposite tensile properties
Biofibers serve as effective reinforcements for neat polylactic acid (PLA) in biocomposites, offering an attractive opportunity to decarbonize the manufacturing sector of the United States by displacing fossil-based reinforcement fibers such as carbon fibers. Also, biofiber production can stimulate economic growth in rural economies, fueling sustainable development. PLA resins are commonly compounded with biofibers to create biocomposites suitable for additive manufacturing. PLA-biofiber composites often exhibit better overall material properties than neat (pure) PLA, but the associations between biofiber properties and the material properties of their biocomposites remain largely unexplored. Hence, this research delves into a comprehensive exploration of diverse biofibers, scrutinizing their physical and chemical attributes, including size, shape, ash content and biochemical composition. The study meticulously analyzes the flow properties of each biofiber and elucidates the ultimate tensile strengths and Young's modulus of corresponding biocomposite samples. Noteworthy correlations between biofiber and biocomposite tensile properties are uncovered, shedding light on critical interrelationships. The study introduces an approach employing regression models to predict the ultimate tensile strength and Young's modulus of biocomposites. These models, validated with a cross-validation technique, exhibit remarkable predictive accuracy, particularly in estimating ultimate tensile strength. © 2024 Oak Ridge National Laboratory managed by UT-Battelle, LLC and The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
36 MATERIALS SCIENCE↗
Mechanical properties of Zircaloy cladding tubes and contributions to M.E.T.A. mechanical property database
To support a multi-laboratory Methodology, Evaluation, Testing, and Analysis (M.E.T.A.) cladding properties database, Oak Ridge National Laboratory’s (ORNL’s) cladding mechanical test geometries were manufactured from several nuclear-relevant cladding alloys and subsequently tested. These geometries were developed as mechanical test specimens to evaluate the properties of tube materials that may be used for irradiation testing at ORNL’s High Flux Isotope Reactor. They may also be used as test articles to be harvested—via in-cell machining—from commercially irradiated fuel rods and later tested. This report explores the differences among axial, hoop, and SSJ tensile geometries with partially recrystallized Zircaloy-2 to test ORNL correlation-based methods on a plate material that approximates, to the greatest extent possible, the characteristics of nuclear industry tubing. Furthermore, several tests were conducted with ORNL’s Zircaloy-4 tube inventory to (1) develop material properties as a standard for future tests, (2) determine the effect of the US Department of Energy’s Advanced Fuels Campaign coating processes on tube mechanical properties, and (3) evaluate the effect of specimen machining methods on the mechanical properties of tube geometries.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Use of a Lignin-Based Admixture for Tailoring the Rheological Properties of Mortars for 3D Printing: Preprint
Efforts toward decarbonizing construction materials and industrial processes related to cement and concrete can be aided via multifaceted approaches that target alternative admixtures as well as precision control of fabrication. Chemical admixtures for water reduction have played a crucial role in the development of advanced concrete mixtures. Newer biomass processing techniques developed for aviation fuel production from corn stover biomass produce a more reactive lignin byproduct that is suitable for chemical modifications to mimic the properties of polycarboxylate ether admixtures with a smaller carbon footprint. The present study examines the use of lignin-based water-reducing admixture in cement pastes and mortar mixtures for 3D printing. The experimental program explores the use of different dosages of lignin-based admixture to produce 3D-printed samples with appropriate extrudability and buildability. The rheological characterization was performed to determine the flow curve of various mixtures. Finally, the heat of hydration of cement pastes was monitored via isothermal calorimetry to assess the impact of lignin-based admixtures on the hydration process of cement. The results of this study indicate that the use of biomass by-products, such as lignin-based admixtures have great potential to effectively control the fresh-state properties of cement-based materials.
bio-based admixtures↗
The nontrivial effects of annealing on superconducting properties of Nb single crystals
The effect of annealing on the superconducting properties of niobium single crystals was studied using optical, magnetic, and scanning tunneling microscopy (STM) methods. Pieces of the same crystal boule were studied before and after the annealing at 800 ${^\circ}\textrm{C}$, 1400 ${^\circ}\textrm{C}$, and near the melting point of niobium (2477 ${^\circ}\textrm{C}$). The initial samples had a high hydrogen content and low-temperature imaging revealed large hydrides (hundreds of micrometers) appearing below 190 K. The formation of these large precipitates is already completely suppressed by annealing at 800 ${^\circ}\textrm{C}$. However, the overall superconducting properties of the annealed samples did not improve and, in fact, worsened. In particular, the superconducting transition temperature decreased, the upper critical field increased, and the pinning strength increased. In the STM study, the sample was annealed initially at 400 ${^\circ}\textrm{C}$, measured, annealed at 1700 ${^\circ}\textrm{C}$, and measured again. The STM revealed a ‘dirty’ superconducting gap with a significant spatial variation in tunneling conductance after annealing at 400 ${^\circ}\textrm{C}$. The clean gap was recovered after annealing at 1700 ${^\circ}\textrm{C}$. This is likely due to oxygen redistribution near the surface, which is always covered by oxide layers in as-grown crystals. Our results indicate that vacuum annealing at least up to 1400 ${^\circ}\textrm{C}$, while removing a large percentage of hydrogen, introduces additional nanosized defects, likely hydride precipitates, that act as efficient pair-breaking and pinning centers. The dimensionless scattering rate is estimated to have increased from $\Gamma = 0.2$ to about $\Gamma = 0.4$ after annealing at 1400 ${^\circ}\textrm{C}$. These results on single crystals differ drastically from those obtained in polycrystalline bulk niobium (i.e. cut from superconducting radio-frequency cavities), where annealing is known to have a significant positive effect that is attributed to the improvement of the crystalline structure masking the more subtle influence of the hydrides.
43 PARTICLE ACCELERATORS↗
Thermal Property Modeling and Assessment of the Physical Properties of FLiNaK
Here, the thermodynamic properties of the LiF–NaF–KF system and its subsystems were re-evaluated using the CALPHAD method, focusing on the deviations from ideality in the heat capacity [C p (T)] of mixtures, temperature-dependence of mixing enthalpies (Δ mix H), vapor pressures of mixtures, and enthalpies of fusion (ΔH fus ) using reported values and measurements. The results of this work confirmed a pseudoternary eutectic at 732.9 K and 46.5LiF–11.5NaF–42KF mol % (FLiNaK) with determined Cp(T) = 69.822 + 0.000679T + 2,137,152T –2 J mol –1 K –1 (732.9 < T < 1200 K) and ΔH fus = 18,051 J mol –1 in good agreement to the experimental values. The resulting accurate thermodynamic representation can be used to find relevant excess thermochemical properties in the whole pseudoternary space and provide insights into their composition and temperature dependence. A detailed evaluation of select thermophysical properties was also conducted to determine recommended density, thermal diffusivity, thermal conductivity, vapor pressures, and boiling point with calculated uncertainties over the temperature range of interest for FLiNaK–salt energy applications.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Investigation of Arctic Cloud Properties and Surface Radiation Based on MOSAiC Shipborne Observations
The Arctic is rapidly changing due to changes of the Earth system. This study investigates cloud fraction, phase partition, cloud type, and their relationships with surface radiation based on yearlong shipborne observations in the Arctic regions. The Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) campaign provided lidar and radar observations of cloud microphysical properties and surface shortwave (SW) and longwave (LW) radiation. Cloud and radiative properties were examined at daily and monthly resolutions in four seasons. Low clouds were found to be most prevalent throughout the year, followed by deep clouds. The ice phase is the dominant phase except for summer (June–August). Liquid and mixed phases show more significant monthly and annual mean radiative effects in SW and LW than the ice phase. The clouds show net warming effects due to LW heating in most months, while the SW cooling effects of clouds become more dominant for July and August. The cloud and radiation observations from MOSAiC were used to evaluate simulations of the atmospheric component of the Energy Exascale Earth System Model version 2. The simulations show large overestimations of the liquid and mixed phases in the Arctic regions from February to September. The simulations also underestimate the percentages of low clouds and overestimate the percentages of deep clouds throughout the year. Altogether, this work provides a unique analysis of cloud and radiation properties based on high-resolution shipborne observations, which can be used to assist future model evaluation and development.
58 GEOSCIENCES↗
Soil biogeochemical properties and metrics of tree-mycorrhizal dominance for a 25-Ha forest in South Central Indiana, USA.
This data package contains a dataset used in the papers “Seeing the forest for all the trees: Mycorrhizal-associated nutrient economies are modulated by stem density and the synchrony between overstory and understory communities” and “Mycorrhizal associations of tree species influence soil nitrogen dynamics via effects on soil acid–base chemistry”. Four csv files are included along with a dataset. The dataset features chemical soil properties for a single sampling campaign within the 25 Ha Lilly-Dickey Woods Smithsonian Forest Global Earth Observatory (ForestGEO) plot in South Central Indiana, USA (ldw_dat_raw.csv). Also included are separate files focused on pH (pH_data.csv), carbon and nitrogen (CN_data.csv), and nitrification rates (Nitrification_data.csv). These variables are commonly associated with the tree-mycorrhizal dominance of forest stands. In these data subsets, each soil variable was matched to a 10 meter radius neighborhood wherein metrics of tree-mycorrhizal dominance (basal area, stem count, importance value, etc.) were calculated. Models between these soil variables and dominance metrics were used to investigate how different assessments of mycorrhizal associated nutrient economies (MANE) capture these relationships. This research was performed as a part of the Smithsonian ForestGEO project. This data package can be used to explore spatial variability in soil chemistry within a mature hardwood forest, or it can be combined with the included tree data, other fine-scale spatial information, or other tree inventory data for the site to evaluate how soil chemistry varies with tree community composition or edaphic or topographic properties.
Craig, Matthew [ORNL] (ORCID:0000000288907920)↗
Structure-property relationship between lignin structures and properties of 3D-printed lignin composites
Lignin is a low-cost and renewable bioresource with a huge annual production promising to prepare sustainable materials. However, the poor interfacial adhesion between many lignin-polymer pairs deteriorates the mechanical performance of the composites, which seriously limits the application of lignin in 3D printing via fused depositional modeling. This work examined lignin-polyamide 12 (PA 12) intermolecular interactions (e.g., hydrogen bonding) to address the interface challenge. To realize this goal, the phenolic hydroxyl content was increased for a kraft softwood lignin using a LiBr/HBr demethylation procedure, increasing phenoxy content by 61.7%. Increased hydrogen bonding interactions between modified lignin (Pine-Lig-OH) and PA 12 demonstrated a significantly improved molten dynamic modulus by rheological analysis. Regarding mechanical properties, by adding 20 wt% of Pine-Lig-OH, the tensile strength and Young's modulus reached 46.6 MPa and 1.62 GPa, 30.2% and 33.9% higher than PA 12, respectively. Further morphological analysis proved the interfacial interactions are enhanced by showing the difference in the phase gaps. The dynamic mechanical analysis (DMA) supported the conclusion that Pine-Lig-OH could interact with polymer chains, alternating segmental movements due to the strong interaction. Here, this study presents a method to enhance lignin composite properties by promoting interactions with the polymer matrix through modified functional groups, guiding future lignin composite research.
36 MATERIALS SCIENCE↗
H-cluster Intermediates and Catalytic Properties of Clostridium pasteurianum [FeFe]-Hydrogenase III
[FeFe]-Hydrogenases are structurally diverse enzymes that catalyze reversible H2 activation at a catalytic cofactor or H-cluster. The H-cluster is a [4Fe-4S] cubane linked by a cysteine thiolate to a diiron subsite containing unique CO, CN-, and dithiomethylamine ligands. The established H-cluster resting state of [4Fe-4S]2+-[FeII-FeI], or Hox, functions in H2 binding and oxidation, or by proton-coupled reduction initiates H2 evolution. In contrast, in Clostridium pasteurianum [FeFe]-hydrogenase III (CpIII) the resting state of the H-cluster is fully oxidized, [4Fe-4S]2+-[FeII-FeII], or Hox+1. To begin to understand if Hox+1 has a role in the mechanism of CpIII, we determined the spectroscopic and redox properties of CpIII H-cluster states under catalytic conditions. CpIII poised in Hox+1 and either equilibrated under 1 atm of H2 or reduced with sodium dithionite, resulted in a mixture of reduced states including Hox (Em8 = -407 mV), Htrans-like [4Fe-4S]+-[FeII-FeII] (Em8 = -418 mV), Hred [4Fe-4S]+-[FeII-FeI], and HredH+ [4Fe-4S]2+-[FeI-FeI] (Em8 = -455-480 mV). Under H2 the population of the Htrans-like state was >20-fold higher than Hox, implicating a role in CpIII catalysis. Unlike other enzymes, there was no spectral evidence of fully reduced states, such as HsredH+ ([4Fe-4S]+-[FeI-FeI]) or Hhyd ([4Fe-4S]+-[FeII-FeII]-H-). Thus, while the H-cluster states of CpIII encompass most of the catalytic intermediates, it is either unable to form HsredH+ and Hhyd, or these states are highly destabilized in CpIII. Thus, these results demonstrate that catalytic intermediates of reduced CpIII differ from the typical intermediates of other catalytic [FeFe]-hydrogenases and may explain the catalytic preference for H2 production.
08 HYDROGEN↗
Energetic and Electronic Properties of UX +/0/– for X = Li and Be and Comparison of the Properties of the Uranium Atom Binding to 2nd Row Elements Li–F
The bonding and spectroscopic properties of ULi +/0/– and UBe +/0/– to complete the series for UX +/0/– for X = Li to F were investigated by high-level ab initio SO-CASPT2 and CCSD(T) electronic structure calculations. The low-lying spin–orbit states were obtained at the SA-CASPT2/aQ-PP level; bond dissociation energies (BDEs), ionization energies (IEs), adiabatic electronic affinities (AEAs), and vertical detachment energies (VDEs) were calculated at the Feller-Peterson-Dixon (FPD) level. A dense manifold of low-lying states was predicted for ULi +/0/– and UBe +/0/– . Here, the calculated BDEs for ULi (37.7 kJ/mol) and UBe (8.0 kJ/mol) show that UBe is weakly bound. For redox processes, the BDEs increased for ULi + (109.3 kJ/mol), ULi – (47.4 kJ/mol), UBe + (35.6 kJ/mol), and UBe – (72.3 kJ/mol). The IE(ULi) = 4.650 eV is lower than IE(Li); the IE(UBe) = 5.901 eV is close to the IE(U) and to the IEs of UB, UC, UN, UO, and UF. The AEAs of ULi (0.708 eV) and UBe (0.989 eV) are lower than those for UB, UC, UN, and UO but higher than that for EA(UF). Natural bond orbital (NBO) calculations show that ULi has the 5f 3 6d 1 7s 2 configuration for U and 2s 1 for Li, with a small partial negative charge slightly delocalized on U. UBe arises from the U(5f 3 6d 1 7s 2 ) and Be(2s 2 ) electron configurations with no charge separation. The same calculations were made for WX (X = Li, Be, C–F) to enable detailed comparisons of the properties for UX with WX (X = Li–F). For WX, BDE(WX) is higher than that for UX for X = Li to N and lower than BDE(UX) for X = O and F, mostly due to the higher IE of W than U as ionic character becomes more important going from Li to F.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
BEAST DB: Grand-Canonical Database of Electrocatalyst Properties
We present BEAST DB, an open-source database comprised of ab initio electrochemical data computed using grand-canonical density functional theory in implicit solvent at consistent calculation parameters. The database contains over 20,000 surface calculations and covers a broad set of heterogeneous catalyst materials and electrochemical reactions. Calculations were performed at self-consistent fixed potential as well as constant charge to facilitate comparisons to the computational hydrogen electrode. This article presents common use cases of the database to rationalize trends in catalyst activity, screen catalyst material spaces, understand elementary mechanistic steps, analyze the electronic structure, and train machine learning models to predict higher fidelity properties. Users can interact graphically with the database by querying for individual calculations to gain a granular understanding of reaction steps or by querying for an entire reaction pathway on a given material using an interactive reaction pathway tool. BEAST DB will be periodically updated, with planned future updates to include advanced electronic structure data, surface speciation studies, and greater reaction coverage.
database↗
Single-atom alloy structure and unique bonding properties of Au 104 Ag 40 (PET) 60 nanoclusters
X-ray absorption spectroscopy is utilized to study the distribution of Au and Ag within the metal core of the Au 104 Ag 40 (PET) 60 nanocluster, revealing a Ag single-atom alloy structure associated with unique bonding properties.
Chemistry↗