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At least 1,495 records · Page 83

Emergent Newtonian dynamics and the geometric origin of mass

We consider a set of macroscopic (classical) degrees of freedom coupled to an arbitrary many-particle Hamiltonian system, quantum or classical. These degrees of freedom can represent positions of objects in space, their angles, shape distortions, magnetization, currents and so on. Expanding their dynamics near the adiabatic limit we find the emergent Newton’s second law (force is equal to the mass times acceleration) with an extra dissipative term. In systems with broken time reversal symmetry there is an additional Coriolis type force proportional to the Berry curvature. We give the microscopic definition of the mass tensor. The mass tensor is related to the non-equal time correlation functions in equilibrium and describes the dressing of the slow degree of freedom by virtual excitations in the system. In the classical (high-temperature) limit the mass tensor is given by the product of the inverse temperature and the Fubini–Study metric tensor determining the natural distance between the eigenstates of the Hamiltonian. For free particles this result reduces to the conventional definition of mass. This finding shows that any mass, at least in the classical limit, emerges from the distortions of the Hilbert space highlighting deep connections between any motion (not necessarily in space) and geometry. We illustrate our findings with four simple examples. -- Highlights: •Derive the macroscopic Newton’s equation from the microscopic many-particle Schrödinger’s equation. •Deep connection between geometry and dynamics. •Geometrical interpretation of the mass of macroscopic object as deformation of Hilbert space. •Microscopic expression for mass and friction tensors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

CO 2 hydrogenation: Selectivity control of CO versus CH 4 achieved using Na doping over Ru/m-ZrO 2 at low pressure

By doping 1%Ru/m-ZrO 2 with sodium, selectivity tuning between CO and CH 4 during CO 2 hydrogenation was achieved by controlling the relative rates of reverse water-gas shift and CO methanation. By increasing basicity through Na loading: (1) the formate C-H bond is weakened in DRIFTS of adsorbed CO, accelerating C-H bond formation of formate and promoting CO formation at the Ru/m-ZrO 2 interface; and (2) the coverage of Na increases on ensembles of Ru atoms responsible for methanation. Increasing Na content shifts selectivity from CH 4 (useful for synthetic natural gas) to CO, which can be used for Fischer-Tropsch synthesis or methanol-to-gasoline. Electronic modification of formate is likely due to enhanced basicity (strengthening bonding between catalyst and the-CO 2 function of formate and weakening C-H). In conclusion, no electron transfer from Na to Ru was detected in XANES. DRIFTS as a function of time and XPS results showed that Na exacerbates site blocking and deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of nitrate on the redox chemistry and solubility of Tc(IV) in alkaline, dilute to concentrated aqueous NaCl solutions

Here, the impact of nitrate on the redox behaviour and solubility of 99 Tc(IV) was investigated in 0.1–5.0 M NaCl–NaNO 3 –NaOH solutions with 0.1 M ≤ [NO 3 – ] ≤ 1.0 M and 8.5 ≤ pH m ≤ 14.5 (with pH m = –log [H + ]) in the presence or absence of reducing agents (as Fe powder, Na 2 S 2 O 4 , Sn(II)). The evolution of the redox conditions as a function of time (for t ≤ 450 days) was investigated: (i) in the absence of technetium (inactive samples), (ii) in the presence of 99 Tc(IV) (added as 1–2 mg of TcO 2 ∙0.6H 2 O(am)), and (iii) in the presence of 137 Cs(I) (and absence of 99 Tc). All experiments were conducted in an Ar-glovebox (O 2 < 1 ppm) at T = (22 ± 2) °C. An improved understanding of Tc redox processes in nitrate-rich alkaline solutions is relevant to predict Tc behaviour in specific nuclear waste disposal scenarios and a topic of fundamental scientific interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new perspective on the initial hydrogenation of $\mathrm{TiFe_{0.9}M_{0.1}}$ ($\mathrm{M = V, Cr, Fe, Co, Ni}$) gained from surface oxide analysis and nucleation thermodynamics

Despite the promise of TiFe-based alloys as low-cost solid-state hydrogen storage materials with mild operating conditions and reasonable hydrogen capacity, their initial hydrogenation process is difficult, hindering broad utilization. The effect of alloying element on the initial hydrogenation kinetics of TiFe alloys, TiFe 0.9 M 0.1 (M = V, Cr, Fe, Co and Ni), was evaluated by analyzing changes to the passivating surface oxide layer that inhibits hydrogen permeation, as well as the ease of initial-stage hydrogen absorption into the underlying matrix. X-ray photoelectron spectroscopy and atom probe tomography revealed key variations in surface oxide compositions and thinning of the passivating oxide layer compared to pure TiFe, which suggests suppressed oxide growth by alloying-induced elemental redistribution. At the same time, density functional theory calculations predicted exothermic formation of hydride nuclei when alloying with V or Cr, as well as a reduced nucleation barrier when alloying with Co or Ni. Overall, these results are consistent with the observed experimental trend of the activation kinetics. We propose that improvements in activation kinetics of TiFe with alloying arises from the combined effect of reduced passivating oxide thickness and easier hydride nucleation, offering a starting point for alloy design strategies towards further improvement.

25 ENERGY STORAGE↗

MafB antagonizes phenotypic alteration induced by GM-CSF in microglia

Microglia are tissue-resident macrophages which are distributed throughout the central nervous system (CNS). Recent studies suggest that microglia are a unique myeloid population distinct from peripheral macrophages in terms of origin and gene expression signature. Granulocyte-macrophage colony-stimulating factor (GM-CSF), a pleiotropic cytokine regulating myeloid development, has been shown to stimulate proliferation and alter phenotype of microglia in vitro. However, how its signaling is modulated in microglia is poorly characterized. MafB, a bZip transcriptional factor, is highly expressed in monocyte-macrophage lineage cells including microglia, although its role in microglia is largely unknown. We investigated the crosstalk between GM-CSF signaling and MafB by analyzing primary microglia. We found that Mafb-deficient microglia grew more rapidly than wild-type microglia in response to GM-CSF. Moreover, the expression of genes associated with microglial differentiation was more downregulated in Mafb-deficient microglia cultured with GM-CSF. Notably, such differences between the genotypes were not observed in the presence of M-CSF. In addition, we found that Mafb-deficient microglia cultured with GM-CSF barely extended their membrane protrusions, probably due to abnormal activation of RhoA, a key regulator of cytoskeletal remodeling. Altogether, our study reveals that MafB is a negative regulator of GM-CSF signaling in microglia. These findings could provide new insight into the modulation of cytokine signaling by transcription factors in microglia. - Highlights: • GM-CSF alters the phenotype of microglia in vitro more potently than M-CSF. • Transcription factor MafB antagonizes the effect of GM-CSF on microglia in vitro. • MafB deficiency leads to RhoA activation in microglia in response to GM-CSF. • We show for the first time the function of MafB in microglia.

60 APPLIED LIFE SCIENCES↗

Recalcitrance and structural analysis by water-only flowthrough pretreatment of 13 C enriched corn stover stem

This article presents high temperature water-only continuous flowthrough pretreatment coupled with nuclear magnetic resonance (NMR) as a promising analytical tool to examine the plant cell wall, to understand its recalcitrance (i.e., cell wall resistance to deconstruction), and to probe the chemistry occurring during batch pretreatment of biomass. 13 C-enriched corn stover stems were pretreated at 170 °C for 60 minutes with a hot-water flow rate of 20 mL/min to control fractionation of the cell wall. This approach helped elucidate the nature of plant cell wall chemical recalcitrance and biomass pretreatment chemistry by tracking cell wall fragmentation as a function of time. Fractions of the reactor effluent were collected in a time-resolved fashion and characterized by various NMR techniques to determine the degree and sequence of fragments released, as well as, the chemical composition, molecular structure, and relative molecular weight of those released fragments.

59 BASIC BIOLOGICAL SCIENCES↗

New Method for Measuring the Anchoring Energy of Strongly-Bound Membrane-Associated Proteins [Method for measuring the anchoring energy of strongly-bound membrane-associated proteins].

Here, we describe a new method to measure the activation energy required to remove a strongly-bound membrane-associated protein from a lipid membrane (anchoring energy). It is based on measuring the rate of release of a liposome-bound protein during centrifugation on a sucrose gradient as a function of time and temperature. The method was used to determine anchoring energy for the soluble dengue virus envelope protein (sE) strongly bound to 80:20 POPC:POPG liposomes at pH 5.5. We also measured the binding energy of sE at the same pH for the initial, predominantly reversible, phase of binding to a 70:30 PC:PG lipid bilayer. The anchoring energy (37 +/- 1.7 kcal/mol, 20% PG) was found to be much larger than the binding energy (7.8 +/- 0.3 kcal/mol for 30% PG, or est. 7.0 kcal/mol for 20% PG). This is consistent with data showing that free sE is a monomer at pH 5.5, but assembles into trimers after associating with membranes. But, trimerization alone is insufficient to account for the observed difference in energies, and we conclude that some energy dissipation occurs during the release process. This new method to determine anchoring energy should be useful to understand the complex interactions of integral monotopic proteins and strongly-bound peripheral membrane proteins with lipid membranes.

59 BASIC BIOLOGICAL SCIENCES↗

Gold nanocatalysts supported on heterostructured PbSO4-MCF mesoporous materials for CO oxidation

Metal oxides are commonly used as the supports of gold nanoparticles for catalytic CO oxidation, whereas metal salts are rarely considered suitable supports. In the present work, we developed a new kind of gold nanocatalyst supported on heterostructured PbSO4-MCF mesoporous materials that was prepared by an in situ growth method using dodecylbenzenesulfonate (SOBS) as a sulfonate precursor. It was found that an Au/PbSO4-MCF (SDBS) catalyst preheated at 300 degrees C showed high CO conversion below 100 degrees C. In addition, the stability of selected catalysts was studied as a function of time on stream. Because of the alteration of surface properties, these Au nanocatalysts were highly sinter-resistant. Published by Elsevier B.V.

Li, Lin↗

A 12 year EDF study of concrete creep under uniaxial and biaxial loading

This paper presents a 12-year-long creep and shrinkage experimental campaign on cylindrical and prismatic concrete samples under uniaxial and biaxial stress, respectively. The motivation for the study is the need for predicting the delayed strains and the pre-stress loss of concrete containment buildings of nuclear power plants. Two subjects are central in this regard: the creep strain's long-term evolution and the creep Poisson's ratio. A greater understanding of these areas is necessary to ensure reliable predictions of the long-term behavior of the concrete containment buildings.Long-term basic creep appears to evolve as a logarithm function of time in the range of 3 to 10 years of testing. Similar trends are observed for drying creep, autogenous shrinkage, and drying shrinkage testing, which suggests that all delayed strains obtained using different loading and drying conditions originate from a common mechanism.The creep Poisson's ratio derived from the biaxial tests is approximately constant over time for both the basic and drying creep tests (creep strains corrected by the shrinkage strain).It is also shown that the biaxial non-drying samples undergo a significant increase in Young's modulus after 10 years.

36 MATERIALS SCIENCE↗

Estimating the mechanical properties of hydrating blended cementitious materials: An investigation based on micromechanics

The hydration model of Parrot & Killoh (1984) has been extended to blended cements and coupled to a micromechanical scheme similar to that of Pichler & Hellmich (2011) to estimate the Young modulus and the compressive strength of cementitious materials as a function of time. A finite aspect ratio of 7 is introduced to describe the shape of the hydrates and improve the estimate of the early age strength by the micromechanical scheme. Furthermore, accounting for the stress fluctuations in the cement paste partly explains the fact that the compressive strength of a concrete can be lower than that of its cement paste. Finally, the estimated physical properties are compared to numerous experimental measurements from the literature and new experimental measurements on blended cement pastes featuring significant weight fractions of limestone filler, fly ash or silica fume. It is shown that the present model slightly overestimates the dilution effect.

36 MATERIALS SCIENCE↗

Anisotropic thermal diffusivity and conductivity in SiC/SiC tubes studied by infrared imaging and X-ray computed tomography

Traditional flash diffusivity evaluation of thermal diffusivity/conductivity of composite tubes require machining of specimens. For a thin-wall tube, this method can only be used to obtain through-thickness transport property. A novel method to evaluate anisotropic thermal diffusivity in a composite tube has been developed. Braided SiC/SiC composite tubes were subjected to a xenon flash heating pulse. A high-speed, high-sensitivity infrared camera was used to measure surface temperature changes as a function of time and nondestructively detect subsurface defects/damages, such as macroscopic pores. Standard reference material (Pyroceram 9606) and curved SiC/SiC composite tube specimens were used to validate thermal diffusivity obtained from infrared imaging. Unlike the traditional method, there is no need prepare special specimens, and thermal diffusivity values in three orientations are obtained after a single flash. A finite element analysis model based on x-ray computed tomography scans was developed to simulate the heat transfer. In conclusion, this technique is significant in assessing thermal conductivity and inspecting the health of ceramic tubes during and after service.

36 MATERIALS SCIENCE↗

Influence of ethylenediaminetetraacetic acid on the long-term oxidation state distribution of plutonium

Here, spectrophotometry was used to study the effect of EDTA on plutonium oxidation state distribution as a function of time, pH, and ligand-to-metal ratio (L/M) under anoxic conditions. Novel Pu(V)-EDTA absorption bands were identified at 571, 993, 1105, and 1150 nm with molar absorption coefficients of 15 ± 1, 6 ± 1, 10 ± 1, and 10 ± 1 cm –1 M –1 , respectively. Pu(V)-EDTA spectral changes occurred at L/M < 1, indicating only Pu V O 2 (EDTA) 3- formed with logK = 3.6 ± 0.3. Time-resolved experiments showed EDTA drastically increased the Pu(V/VI) reduction rate, which we propose is driven by amine lone-pair electron donation and the oxidative decarboxylation of EDTA. Oxidation of Pu(III)-EDTA to Pu(IV)-EDTA occurred on a slower time scale (110–237 days) than previously reported (<15 min) and is hypothesized to be radiolysis driven. Pu(V/VI)-EDTA and Pu(III)-EDTA both approached Pu(IV)-EDTA stabilization over time, yet Pu(V/VI)-EDTA solubility data was ≥ 1.0 log 10 units higher than predicted by Pu(IV)-EDTA solubility models, indicating that current thermodynamic models are incomplete. Ultimately, the data show EDTA preferentially stabilizes Pu(IV) over time regardless of initial oxidation state, but Pu(V)-EDTA can persist under environmentally-relevant conditions, emphasizing the need to continue investigating redox reactions, speciation, and behavior of these complexes to support the transuranic waste disposal and surface remediation/containment efforts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Comparing and contrasting In-Vial and full-scale systems for sparging volatile analytes

Here, in-vial sparging was demonstrated as an effective, practical alternative to a full-scale sparging system for supporting the analysis of volatile constituents. Using elemental mercury (Hg 0 ) and toluene as representative purgeable analytes, the mass removal for various sparge configurations was measured and a reduced order model was developed and validated. In the primary experiments, Hg 0 in the sparge gas was trapped on activated carbon or gold, thermally desorbed, and quantified using atomic absorption or atomic fluorescence spectroscopy. Toluene experiments using the same in-vial sparge apparatus and sparge parameters were performed to demonstrate the applicability of the reduced order model to a broad range of compounds. Toluene removal was tracked by measuring the remaining toluene in sparged aliquots using Ultraviolet-visible (UV–Vis) spectroscopy. For the sparging, flow rates varied from 25 to 75 mL/min for periods from 0 to 30 min. Sparge performance, mass removal as a function of time, and sparge gas volume were measured for both in-vial and full-scale systems. A model based on dimensionless Henry's Law coefficient, normalized sparge gas volume, and fractional extent of equilibrium matched the experimental data for both compounds and provides a practical tool for future applications. For the conditions tested in this study, the calibrated model indicated that the sparge gas in the in-vial system reached approximately 33% of its equilibrium value before exiting the water surface, while a full-scale system reached approximately 100%. The tests validated the quality, reproducibility, and predictability of sparging performance for both full scale and in-vial sparge systems. Related factors such as waste generation, worker risk, and labor were also assessed. Full scale sparge systems provide the advantage of lower detection levels due to larger sample volume, while the in-vial sparge systems provide advantages for most other factors; including automatability, reducing secondary wastes, lessening the need to clean and check the sparge apparatus, and lowering labor and costs. The data and associated reduced order model support continued development and deployment of in-vial sparge platforms as a practical option for analysis of purgeable analytes such as volatile organic compounds and volatile metals/organometallics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of Localized Corrosion Rates at Inclusion Particles in AA7075 by In Situ Three Dimensional (3D) X-ray Synchrotron Tomography

In situ X-ray synchrotron tomography was used to measure the localized corrosion rate of Mg2Si particles present in 7075 aluminum alloys in deionized ultra-filtered (DIUF) water. The evolution of hydrogen bubbles was captured as a function of time and the measured volume was used to calculate the local corrosion rate of Mg2Si particles. It was shown that in the absence of chloride ions, stress was needed to create fresh particle surfaces, either by fracture or debonding, to initiate corrosion at the particles.

A. Aluminum alloys↗

Carburization of austenitic and ferritic stainless steels in liquid sodium: Comparison between experimental observations and simulations

Three steels were exposed in carburizing sodium at 600 and 650 °C. The kinetics and extent of carburization were characterized. Numerical simulations using the coupled thermodynamic-kinetic modeling software DICTRA were performed. It was introduced that the determined carbon diffusion profiles were induced by the combined diffusion of carbon in the grains and at grain boundaries coupled with the slow formation of carbides. The blocking effect of carbides on the carbon diffusion was observed to evolve as a function of time and microstructure. Acceptable agreement among experimental and simulated intragranular carbon profiles was achieved by optimizing the labyrinth factor and phases.

36 MATERIALS SCIENCE↗

Evidence of an oxidation induced phase transformation for a delta phase plutonium-gallium alloy

The oxidation of an ~1.5 at% Ga plutonium metal alloy in dry air as a function of time was studied using a combination of FIB-SEM, AES, and XRD. Analysis of SEM images of FIB cross-sections of the oxide allowed for direct measurement of the oxide thickness as well as determination of heterogeneity in the extent of the oxide. AES analysis performed on cross-sections of the oxide allowed for quantitative analysis of the atomic composition and semi-quantitative analysis of the chemical composition. Initial preparation of the sample was found to induce a martensitic transformation to α' - Pu with an average thickness of 233 nm. Electropolishing was found to be sufficient to fully remove the α' layer with creation of only a minimum oxide layer. Growth of the oxide in dry air was found to initially follow parabolic kinetics, with a parabolic rate constant orders of magnitude higher than expected for δ-Pu but in-line with values extrapolated to room temperature for α-Pu. Following complete oxidation of the initial α` layer, further regions of plutonium metal depleted in gallium were observed to form at the oxide / metal interface. However, gallium, as Ga 2 O 3 , was found to be enriched at the surface and present in the oxide in an amount comparable to the relative Ga:Pu ratio of the bulk metal alloy. Finally, the results presented here serve to bridge a diverse array of previous experimental and theoretical data and provide the first comprehensive view of the fate of the δ-stabilizer during formation of an oxide.

36 MATERIALS SCIENCE↗

Advanced measurement techniques in quantum Monte Carlo: The permutation matrix representation approach

In a typical finite temperature quantum Monte Carlo (QMC) simulation, estimators for simple static observables such as specific heat and magnetization are known. With a great deal of system-specific manual labor, one can sometimes also derive more complicated non-local or even dynamic observable estimators. In contrast, we show that arbitrary static observables can be estimated within the permutation matrix representation (PMR) flavor for any Hamiltonian. We then generalize these results to general imaginary-time correlation functions and non-trivial integrated susceptibilities thereof. Finally, we demonstrate the practical versatility of our method by estimating various non-local, random observables for the transverse-field Ising model on a square lattice and a toy random model.

Permutation matrix representation↗

Mechanically induced thermal runaway severity analysis for Li-ion batteries

Thermal runaway is one of the most important safety concerns in the deployment of Li-ion batteries. For this study, we developed a standardized single-side indentation test protocol to induce an internal short-circuit. Cell voltage, temperature, and applied compressive force are monitored as a function of time. Each cell is given an observed hazard severity (OHS in five categories) modified from the EUCAR table. Meanwhile a calculated hazard severity (CHS) is obtained solely based on temperature and voltage curves. The calculation formula considers the cell temperature, rate of temperature increase, cell capacity, state of charge (SOC), voltage drop, and voltage drop rate. Each term is assigned with an appropriate weight to scale the calculated score from 0 to100. This method was applied to >100 Li-ion batteries with various SOCs and chemistries, and their OHS and CHS were displayed against SOC. The purpose is to provide battery designers, manufacturers, and end-users a clear comparison of thermal runaway severity of different batteries.

25 ENERGY STORAGE↗