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At least 235 records · Page 13

Super-stretchable self-healing polymer

An elastic composition comprising the following structure: wherein: PDMS is polydimethylsiloxane having at least 5 dimethylsiloxane units; L is a bond or hydrocarbon linker; the asterisk (*) in A units denotes a connection point with an asterisk in B units, and at least one of the following linkages connect between connection points: r is an integer of at least 3; R is a hydrocarbon or siloxane-containing linking moiety; the composition includes a multiplicity of A units and multiplicity of B units; and a portion of the connection points are necessarily terminated by endcapping groups, wherein at least a portion of the endcapping groups are selected from the following structures: The invention also includes methods for making and using the above-described elastic composition.

Saito, Tomonori↗

Targeting hydroxycinnamoyl CoA: shikimate hydroxycinnamoyl transferase for lignin modification in Brachypodium distachyon

Abstract Background Hydroxycinnamoyl CoA: shikimate hydroxycinnamoyl transferase (HCT) is a central enzyme of the so-called “esters” pathway to monolignols. As originally envisioned, HCT functions twice in this pathway, to form coumaroyl shikimate and then, in the “reverse” direction, to convert caffeoyl shikimate to caffeoyl CoA. The discovery of a caffeoyl shikimate esterase (CSE) that forms caffeic acid directly from caffeoyl shikimate calls into question the need for the reverse HCT reaction in lignin biosynthesis. Loss of function of HCT gives severe growth phenotypes in several dicot plants, but less so in some monocots, questioning whether this enzyme, and therefore the shikimate shunt, plays the same role in both monocots and dicots. The model grass Brachypodium distachyon has two HCT genes, but lacks a classical CSE gene. This study was therefore conducted to evaluate the utility of HCT as a target for lignin modification in a species with an “incomplete” shikimate shunt. Results The kinetic properties of recombinant B. distachyon HCTs were compared with those from Arabidopsis thaliana , Medicago truncatula , and Panicum virgatum (switchgrass) for both the forward and reverse reactions. Along with two M. truncatula HCTs, B. distachyon HCT2 had the least kinetically unfavorable reverse HCT reaction, and this enzyme is induced when HCT1 is down-regulated. Down regulation of B. distachyon HCT1, or co-down-regulation of HCT1 and HCT2, by RNA interference led to reduced lignin levels, with only modest changes in lignin composition and molecular weight. Conclusions Down-regulation of HCT1, or co-down-regulation of both HCT genes, in B. distachyon results in less extensive changes in lignin content/composition and cell wall structure than observed following HCT down-regulation in dicots, with little negative impact on biomass yield. Nevertheless, HCT down-regulation leads to significant improvements in biomass saccharification efficiency, making this gene a preferred target for biotechnological improvement of grasses for bioprocessing.

09 BIOMASS FUELS↗

Atomic motifs govern the decoration of grain boundaries by interstitial solutes

Abstract Grain boundaries, the two-dimensional defects between differently oriented crystals, tend to preferentially attract solutes for segregation. Solute segregation has a significant effect on the mechanical and transport properties of materials. At the atomic level, however, the interplay of structure and composition of grain boundaries remains elusive, especially with respect to light interstitial solutes like B and C. Here, we use Fe alloyed with B and C to exploit the strong interdependence of interface structure and chemistry via charge-density imaging and atom probe tomography methods. Direct imaging and quantifying of light interstitial solutes at grain boundaries provide insight into decoration tendencies governed by atomic motifs. We find that even a change in the inclination of the grain boundary plane with identical misorientation impacts grain boundary composition and atomic arrangement. Thus, it is the smallest structural hierarchical level, the atomic motifs, that controls the most important chemical properties of the grain boundaries. This insight not only closes a missing link between the structure and chemical composition of such defects but also enables the targeted design and passivation of the chemical state of grain boundaries to free them from their role as entry gates for corrosion, hydrogen embrittlement, or mechanical failure.

36 MATERIALS SCIENCE↗

Development of High Bs Fe-Ni Based Metal Amorphous Nanocomposite by Optimization of Glass Forming Ability

A growing interest in electric vehicles challenges soft magnetic materials to improve efficiency and power density. Metal amorphous nanocomposites (MANCs) have lower coercivities and eddy current losses, allowing for greater efficiency and higher switching frequency. The later allows for high motor speeds and improved power density. However, commercially available and laboratory demonstrated MANCs have shortcomings. Fe-based MANCs, such as FINEMET have excellent magnetic properties, but mechanical properties limit their application in high speed electric motors (HSMs). Fe-Co based MANCs, such as HITPERM, have high saturation inductions and good mechanical properties, but elevated magnetostrictive losses. Co-based MANCs and more recent Fe-Ni based MANCs have low losses and good mechanical properties, but lower saturation inductions (1-1.2 T), that limit power density in HSMs. Recently, much work has explored improving saturation induction in MANCs by increasing the content of magnetic elements, which comes at the cost of glass-forming ability (GFA). These efforts where generally limited to trial and error testing. Additionally, all work to date has focused on Fe-based alloys. In this work, a method of using Thermocalc simulation to locate near-eutectic compositions has been applied to Fe-Ni based alloys. Minima in liquidus temperature and solidification range were found for a ternary composition range and used to identify compositions that retain good GFA as the percentage of magnetic elements is increased. The (Fe 70 Ni 30 ) x (B-Si-Nb) 100-x alloy system for x=82% and x=85% was explored by Thermocalc simulations. This is an increase in magnetic element content compared to previously developed x=80% alloys. 3 compositions in the x=82% system, and 1 alloy in the x=85% system where identified and successfully cast as amorphous ribbon. The amorphous nature of the ribbon was confirmed by a bend test and XRD. Magnetic testing was performed by PPMS to measure saturation induction and Curie temperature of the amorphous material. The Curie temperatures increased to 407-438 °C for the x=82% alloys, and 462 °C for the x=85% alloy. Saturation induction increased to 1.28-1.36 T for the x=82% alloy and 1.48 T for the x=85% alloy, which is a significant improvement over the ~370 °C Curie temperature and 1.2 T saturation of previous Fe-Ni alloy. Crystallization behavior was studied by XRD for the x=85% alloy, showing that crystallization process follows a 2-step process of Amorphous → BCC+FCC+Amorphous → BCC+FCC+Fe 3 B+Fe 23 B 6 . Post annealing magnetic properties were studied by strip testing, and saturation induction as high as 1.48 T was seen after optimal annealing. TEM was used to study structure of as cast and annealed material. 2 alloys with x=82% compositions were identified with an optimal crystalline size of 10-20 nm, while the x=85% alloy had this structure in the as cast state. This opens the possibility of using the alloy in the as cast state, without requiring annealing. In conclusion, alloys with good GFA and improved magnetic properties were identified by Thermocalc simulation.

Krimer, Yuval↗

Trace Impurities Identified as Forensic Signatures in CMX-5 Fuel Pellets Using X-ray Spectroscopic Techniques

We report that small-particle analysis is a highly promising emerging forensic tool for analysis of interdicted special nuclear materials. Integration of microstructural, morphological, compositional, and molecular impurity signatures could provide significant advancements in forensic capabilities. We have applied rapid, high-sensitivity, hard X-ray synchrotron chemical imaging to analyze impurity signatures in two differently fabricated fuel pellets from the 5th Collaborative Materials Exercise (CMX5) of the IAEA Nuclear Forensics International Working Group. The spatial distributions, chemical compositions, and morphological and molecular characteristics of impurities were evaluated using X-ray absorption near-edge structure (XANES) and X-ray fluorescence chemical imaging to discover principal impurities, their granularity, particle sizes, modes of occurrence (distinct grains vs incorporation in the UO 2 lattice), and sources and mechanisms of incorporation. Differences in UO 2+x stoichiometry were detected at the microscale in nominally identical UO 2 ceramics (CMX5-A and CMX5-B), implying the presence of multiple UO 2 host phases with characteristic microstructures and feedstock compositions. Al, Fe, Ni, W, and Zr impurities and integrated impurity signature analysis identified distinctly different pellet synthesis and processing methods. For example, two different Al, W, and Zr populations in the CMX5-B sample indicated a more complex processing history than the CMX5-A sample. K-edge XANES measurements reveal both metallic and oxide forms of Fe and Ni but with different proportions between each sample. Altogether, these observations suggest multiple sources of impurities, including fabrication (e.g., force-sieving) and feedstock (mineral oxides). This study demonstrates the potential of synchrotron techniques to integrate different signatures across length scales (angstrom to micrometer) to detect and differentiate between contrasting UO 2 fuel fabrication techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-Activity Waste Glass Standards Preparation and Characterization for Calibration of Analytical Instruments

A matrix of seven low-activity waste (LAW) glasses was fabricated and characterized to be used by the Hanford Waste Treatment and Immobilization Plant (WTP) as analytical instrument calibration and matrix interference standards when measuring LAW glass compositions. The matrix of glasses was designed to represent the range of LAW glass compositions that will be generated by the WTP. Samples from each of the seven glasses were measured with electron probe microanalysis (EPMA), ion chromatography (IC), and bulk inductively coupled plasma mass spectroscopy (ICP-MS) to determine the variability and accuracy across batches and within individually poured glass bar samples. High relative percent differences and standard deviations were calculated for components with low concentrations due to instrument detection limits. IC and ICP-MS percent differences and standard deviations were higher at low component concentrations. Otherwise, variability in measured compositions from IC and ICP-MS was generally lower than measurements from EPMA, with the exclusion of Cl, F, Si, and B. Overall, the two methods proved comparable and complementary. From EPMA, IC, and ICP-MS data, volatile elements were underrepresented compared to batched compositions, which suggested loss of these elements during melting. EPMA data was statistically analyzed to evaluate homogeneity within single bars and whole compositions for each of the seven glasses. Most of the variability within glass compositions occurred at the bar-to-bar level; however, no clear systematic trends were observed. Based on these analyses, when using these glasses as reference material, it is recommended that the overall mean and variance of each composition be used for performing instrument calibrations and analytical corrections.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Probiotic composition for enhancing an insects resistance to a pesticide

The present invention provides for a probiotic composition for enhancing a subject's, such as an insect's, resistance to a pesticide comprising: (a) a microorganism capable of expressing one or more enzymes for metabolizing the pesticide, and (b) at least one feed ingredient for a subject. The present invention also provides for a method for enhancing a subject's, such as an insect's, resistance to a pesticide comprising administering to a subject the probiotic composition.

Wan, Kenneth H.↗

Robustness of magnetocrystalline anisotropy and coercivity in Fe–Co–B

As a potential candidate for critical chemical element free permanent magnet, (Fe 0.7 Co 0.3 ) 2 B, shows promising intrinsic magnetic properties, including large magnetization, high Curie temperature and moderate magnetocrystalline anisotropy (MCA). Still, the coercivity that has been achieved is relatively low. To understand and improve coercivity, here we study the robustness of MCA related to the fluctuation of chemical composition and the structural distortion and its effect on coercivity in (Fe 0.7 Co 0.3 ) 2 B from first principles DFT (density functional theory) calculation and micromagnetic simulation. A fluctuation of cobalt content of 10%, or 1% isotropic lattice strain, or 2% tetragonal distortion reduces MCA energy up to 30%. By considering randomly distributed local MCA energy reduction up to 30%, the calculated coercivity of anisotropic bulk magnets reduced from 3.6 kOe to 2.2 kOe. Rational microstructure design, such as grain size refinement and development of strong crystal texture of MCA easy-axis (i.e., degree of alignment for (Fe 0.7 Co 0.3 ) 2 B grains), can enhance coercivity and mitigate the effect of local MCA reduction. In addition to acceptable intrinsic magnetic properties, the promising hard magnetic phase needs good MCA robustness to facilitate the development of practical magnets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Fungal Community, Not Substrate Quality, Drives Soil Microbial Function in Northeastern U.S. Temperate Forests

Mycorrhizal fungi can affect soil organic matter cycling through several mechanisms including priming, nutrient competition, and direct enzyme production. Differences in nutrient foraging strategies between ectomycorrhizal (EcM) and arbuscular mycorrhizal (AM) fungi produce divergent belowground dynamics: where EcM can take up organic nitrogen and directly break down soil organic matter (SOM) by producing enzymes, AM fungi are limited to scavenging mineral N. EcM-associated tree species also have leaf litter with relatively higher ratios of carbon to nitrogen (C:N), and belowground saprotrophic communities more dominated by fungi. Consequently, free-living microbes in EcM-dominated soils should experience nitrogen limitation, with subsequent increases in enzyme production and decreased carbon use efficiency (CUE). However, the relative importance of the effects of substrate quality and fungal community composition on enzyme production and CUE are unclear. To assess this distinction, we sampled the organic horizon and 10 cm of the mineral horizon in northern temperate forest soils along a gradient of EcM dominance. We characterized fungal community composition by measuring EcM relative abundances from extracted fungal DNA and the fungal to bacterial (F:B) ratios from phospholipid fatty acid (PLFA) analysis. We assessed soil substrate quality as the soil C:N ratio. Soil microbial functions were measured as potential activities of five hydrolytic and two oxidative enzymes, and microbial CUE. We found that the fungal community, represented by either the F:B ratio, EcM relative abundance, or both, affected CUE and six measured enzyme activities, while the C:N ratio affected only oxidative and chitin-targeting extracellular enzyme activities. Our results highlight the use of EcM relative dominance as a predictor of soil microbial community composition and function independent of substrate quality.

54 ENVIRONMENTAL SCIENCES↗

Biogeochemistry of Pond B (Savannah River Site, South Carolina, USA): Water column and Sediments

Pond B at Savannah River Site (SRS, South Carolina) is a monomictic reservoir that received SRS R reactor cooling water from 1961–1964. Previous studies conducted between the 1980s–1990s on the water column and sediments of Pond B measured trace amounts of Pu (33 MBq 238Pu and 430 MBq 239,240Pu), 241Am, and 137Cs. Since then, the pond has been relatively isolated and the radionuclide concentrations have not been monitored over time. Herein, about 30 years after the last publication on Pond B, we are re-evaluating the geochemistry and radionuclide distribution within Pond B at five locations along a horizontal transect from the inlet to outlet. In addition, we are conducting the first analysis of the microbial community composition. This data package consists of water column measurements (1) using a multi-probe sonde, (2) plutonium isotopes and total concentrations, (3) total organic/inorganic carbon concentrations, (4) trace metals and major ions concentrations, and (6) microbial community composition. Sediment measurements include (1) plutonium isotopes and total concentrations and (2) microbial community composition.For sediment core and porewater, please see other Pond B data package (ess-dive-60d2352a4495472-20200615T203925174).The data in this package will be submitted for peer review in 2023.

54 ENVIRONMENTAL SCIENCES↗

On the use of charged particles to characterize precipitation in irradiated reactor pressure vessel steels with a wide range of compositions

Nuclear reactor lifetimes may be limited by nano-scale Cu-Mn-Ni-Si precipitates (CRPs and MNSPs) that form under neutron irradiation (NI) of pressure vessel (RPV) steels, resulting in hardening and ductile to brittle transition temperature increases (embrittlement). Physical models of embrittlement must be based on characterization of precipitation as a function of the combination of metallurgical and irradiation variables. Here we focus on rapid and convenient charged particle irradiations (CPI) to both: a) compare to precipitates formed in NI; and, b) use CPI to efficiently explore precipitation in steels with a very wide range of compositions. Atom probe tomography (APT) comparisons show NI and CPI for similar bulk steel solute contents yield nearly the same precipitate compositions, albeit with some differences in their number density, size and volume fraction (f) dose (dpa) dependence. Yet, the overall precipitate evolutions are very similar. Advanced high Ni (>3 wt%) RPV steels, with superior unirradiated properties, were also investigated at high CPI dpa. For typical Mn contents, MNSPs have Ni 16 Mn 6 Si 7 or Ni 3 Mn 2 Si phase type compositions, with f values that are close to the equilibrium phase separated values. In contrast, in steels with very low Mn and high Ni, Ni 2-3 Si silicide phase type precipitate compositions are observed; and when Ni is low, the precipitate compositions are close to the MnSi phase field. Low Mn significantly reduces, but does not eliminate, precipitation in high Ni steels. A comparison of dispersed barrier model predictions with measured hardening data suggests that the Ni-Si dominated precipitates are weaker dislocation obstacles than the G phase type MNSPs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Partial substitution of rice husks for manure in greenhouse vegetable fields: Insight from soil carbon stock and aggregate stability

Abstract Soil aggregate stability and C stock are key factors in greenhouse vegetable production, which are influenced by the application of different organic materials. However, the responses of soil aggregate stability and C stock to organic amendment in greenhouse vegetable fields are not well understood. A 5‐year study was carried out in greenhouse vegetable fields to investigate the effect of partial substitution of rice husks for manure on soil aggregate stability, C compositions, and their relationships. Four treatments included: (a) no organic fertilization (control), (b) 30 t ha −1 chicken manure (CM), (c) 30 t ha −1 rice husks (RH), and (d) 10 t ha −1 chicken manure plus 20 t ha −1 rice husks (MR). Rice husks addition significantly increased the proportion of >2 mm aggregates and mean weight diameter (MWD), while manure addition showed no difference with control. Polysaccharide and humin (HM) were increased with rice husks addition (RH and MR) compared with that in CM treatment. Polysaccharide and HM caused 86.03% variation of soil aggregate, in which polysaccharide and HM contributed 76.3 and 9.7%, respectively. The soil C stock in CM, RH, and MR treatments was increased by 146, 175, and 164% compared with control, respectively. Aliphatic‐C and amorphous Fe‐oxides (Fe‐ox) content were as higher in MR added soil than those in RH treatment. Partial substitution of rice husk for manure improved soil aggregation stability and thus enhanced C stock by suppling more polysaccharide, HM and liberated soil minerals, which was conducive to the sustainable development in greenhouse vegetable production.

Fei, Chao↗

On the dissolution of a borosilicate glass with the use of isotopic tracing – Insights into the mechanism for the long-term dissolution rate

An understanding of the mechanisms responsible for controlling the long-term corrosion rate of nuclear waste glass is paramount if reliable glass dissolution models are to be used to calculate the controlled release of radionuclides from nuclear waste glass under geologic disposal conditions. Additionally, understanding silicate glass dissolution is also important for natural glasses to understand the role from the dissolution of these glasses has on the composition of natural aquatic systems. Two general mechanisms appear to be responsible for the elemental release from glass to the surrounding biosphere - ion exchange (release principally of alkalis) and matrix dissolution (release of the structural components of the glass). Key unknowns related to these mechanisms are the impact of surface layers on the altered glass and how these layers participate in corrosion. To better understand the impact of these layers on glass corrosion, we made two glasses of the same elemental composition, but with selected elements enriched in specific isotopes, e.g. more 10 B than 11 B. We reacted these glasses for 1 y then the solutions from each were exchanged and the chemistry of the solutions and the solids were followed for another 2 y and in some cases 3 y. This allowed us to follow changes in the glasses with respect to these elements and how these elements were transported through the alteration layers with time and, for at least one element, into the glass. Results from these experiments demonstrate that the release behavior of different elements is strongly dependent on their structural role in the glass (e.g. network formers and modifiers), but, more importantly, the role of water transport and subsequent ion exchange has in the long-term dissolution of the glass studied here. In this article, we highlight the behavior of four elements: lithium, sodium, silicon, and boron. Lithium and sodium, network modifying elements, have similar chemistries. The behavior of Li could be tracked in more detail by following both 6 Li and 7 Li; Li penetrates through the gel layer in both directions without hinderance and into and released from the glass deeper than sodium. Silicon, a network forming element, reacts with the silica-rich alteration layer. Boron, a network forming element, does not accumulate in the gel or the pristine glass and has a very sharp elemental profile between the pristine glass and alteration layer. Boron, lithium, and sodium elemental profiles suggest that there is little if any transport control within the alteration layer. The correlation between the Li and Na profiles and that of a water species suggest that the limiting release is a steady state between the diffusion of a water species and matrix dissolution that results in a low release rate for alkali and this provides a steady driving force for the long-term dissolution of glass.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cation Short-Range Ordering of MgAl 2 O 4 and NiAl 2 O 4 Spinel Oxides at High Temperatures via In Situ Neutron Total Scattering

Complex oxides that adopt the isometric spinel structure (AB 2 O 4 ) are important for numerous technological applications and are relevant for certain geological processes, which involve exposure to extreme environments such as high pressures and temperatures. Recent studies have shown that the changes to the spinel structure caused by these environments are complex and depend on the material length scale under consideration. In this study we have expanded this approach to the behavior of spinels under high temperature. In situ neutron total scattering experiments, coupled with pair distribution function analysis, performed on two spinel compositions with various levels of pre-existing disorder (MgAl 2 O 4 and NiAl 2 O 4 ) revealed that both compositions trend to a state of maximum disorder where the A and B cations are randomly distributed amongst the two available sites. Temperature-induced cation inversion, conventionally understood as exchange of cations on the A and B sites, is locally expressed as an atomic rearrangement to a tetragonal symmetry, a correlation that is retained up to the maximum temperature studied (1000 °C). Furthermore, a complex thermal expansion behavior is revealed wherein the oxide materials expand heterogeneously at the level of coordination polyhedral with an apparent dependence on bond strength.

36 MATERIALS SCIENCE↗

Electronic and Thermal Properties of the Cation Substitution-Derived Quaternary Chalcogenide CuInSnSe 4

Quaternary chalcogenides continue to be of interest for a variety of technological applications, with physical properties stemming from their structural complexity and stoichiometric variation. In certain structure types, partial vacancies on specific lattice positions present an opportunity to investigate electrical and thermal properties in light of these lattice defects. In this work, we investigated the structural, thermal, and electronic properties of CuInSnSe 4 , a material that belongs to a relatively unexplored class of quaternary chalcogenides with a defect adamantine crystal structure. First-principles calculations together with experimental measurements revealed a chalcopyrite-like structure with inherent vacancies and characteristic s–p and p–d orbital hybridizations in the electronic structure of the material. Cation disorder and lattice anharmonicity result in very low thermal conductivity with values significantly lower than those for related compositions. In conclusion, this work reveals the fundamental physical properties of a previously uninvestigated quaternary chalcogenide and may aid investigations of similar as well as other quaternary chalcogenide compositions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diamond and methane formation from the chemical decomposition of polyethylene at high pressures and temperatures

Abstract Polyethylene (C 2 H 4 ) n was compressed to pressures between 10 and 30 GPa in a diamond anvil cell (DAC) and laser heated above 2500 K for approximately one second. This resulted in the chemical decomposition of the polymer into carbon and hydrocarbon reaction products. After quenching to ambient temperature, the decomposition products were measured in the DAC at pressures ranging from ambient to 29 GPa using a combination of x-ray diffraction (XRD) and small angle x-ray scattering (SAXS). XRD identified cubic diamond and methane as the predominant product species with their pressure–volume relationships exhibiting strong correlations to the diamond and methane equations of state. Length scales associated with the diamond products, obtained from SAXS measurements, indicate the formation of nanodiamonds with a radius of gyration between 12 and 35 nm consistent with 32–90 nm diameter spherical particles. These results are in good agreement with the predicted product composition under thermodynamic and chemical equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗