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At least 109 records · Page 6

Exploring Charged Defects in Ferroelectrics by the Switching Spectroscopy Piezoresponse Force Microscopy

Monitoring the charged defect concentration at the nanoscale is of critical importance for both the fundamental science and applications of ferroelectrics. However, up-to-date, high-resolution study methods for the investigation of structural defects, such as transmission electron microscopy, X-ray tomography, etc., are expensive and demand complicated sample preparation. Here, with an example of the lanthanum-doped bismuth ferrite ceramics, a novel method is proposed based on the switching spectroscopy piezoresponse force microscopy (SSPFM) that allows probing the electric potential from buried subsurface charged defects in the ferroelectric materials with a nanometer-scale spatial resolution. When compared with the composition-sensitive methods, such as neutron diffraction, X-ray photoelectron spectroscopy, and local time-of-flight secondary ion mass spectrometry, the SSPFM sensitivity to the variation of the electric potential from the charged defects is shown to be equivalent to less than 0.3 at% of the defect concentration. Additionally, the possibility to locally evaluate dynamics of the polarization screening caused by the charged defects is demonstrated, which is of significant interest for further understanding defect-mediated processes in ferroelectrics.

42 ENGINEERING↗

Biophysical analysis of the plant-specific GIPC sphingolipids reveals multiple modes of membrane regulation

The plant plasma membrane (PM) is an essential barrier between the cell and the external environment, controlling signal perception and transmission. It consists of an asymmetrical lipid bilayer made up of three different lipid classes: sphingolipids, sterols, and phospholipids. The glycosyl inositol phosphoryl ceramides (GIPCs), representing up to 40% of total sphingolipids, are assumed to be almost exclusively in the outer leaflet of the PM. However, their biological role and properties are poorly defined. In this study, we investigated the role of GIPCs in membrane organization. Because GIPCs are not commercially available, we developed a protocol to extract and isolate GIPC-enriched fractions from eudicots (cauliflower and tobacco) and monocots (leek and rice). Lipidomic analysis confirmed the presence of trihydroxylated long chain bases and 2-hydroxylated very long-chain fatty acids up to 26 carbon atoms. The glycan head groups of the GIPCs from monocots and dicots were analyzed by gas chromatograph-mass spectrometry, revealing different sugar moieties. Multiple biophysics tools, namely Langmuir monolayer, ζ-Potential, light scattering, neutron reflectivity, solid state 2H-NMR, and molecular modeling, were used to investigate the physical properties of the GIPCs, as well as their interaction with free and conjugated phytosterols. We showed that GIPCs increase the thickness and electronegativity of model membranes, interact differentially with the different phytosterols species, and regulate the gel-to-fluid phase transition during temperature variations. These results unveil the multiple roles played by GIPCs in the plant PM.

59 BASIC BIOLOGICAL SCIENCES↗

The Status of Cross Section Measurements for Neutron-induced Reactions Needed for Cosmic Ray Studies

Cosmic ray interactions with lunar rocks and meteorites produce small amounts of radionuclides and stable isotopes. Advances in Accelerator Mass Spectrometry (AMS) allow production rates to be measured routinely in well-documented lunar rocks and meteorites. These measurements are analyzed using theoretical models to learn about the object itself and the history of the cosmic rays that fell on it. Good cross section measurements are essential input to the theoretical calculations. Most primary cosmic ray particles are protons so reliable cross sections for proton-induced reactions are essential. A cross section is deemed accurate if measurements made by different experimenters using different techniques result in consistent values. Most cross sections for proton induced reactions are now well measured. However, good cross section measurements for neutron-induced reactions are still needed. These cross sections are required to fully account for all galactic cosmic ray interactions at depth in an extraterrestrial object. When primary galactic cosmic ray (GCR) particles interact with an object many secondary neutrons are produced, which also initiate spallation reactions. Thus, the total GCR contribution to the overall cosmogenic nuclide archive has to include the contribution from the secondary neutron interactions. Few relevant cross section measurements have been reported for neutron-induced reactions at neutron energies greater than approximately 20 MeV. The status of the cross section measurements using quasi-monoenergetic neutron energies at iThemba LABS, South Africa and white neutron beams at Los Alamos Neutron Science Center (LANSCE), Los Alamos are reported here.

Sisterson, J. M.↗

First Penning trap mass measurement of 36 Ca

Background: Isobaric quintets provide the best test of the isobaric multiplet mass equation (IMME) and can uniquely identify higher order corrections suggestive of isospin symmetry breaking effects in the nuclear Hamilto nian. The Generalized IMME (GIMME) is a novel microscopic interaction theory that predicts an extension to the quadratic form of the IMME. Only the A = 20, 32 T = 2 quintets have the exotic T z = –2 member ground state mass determined to high-precision by Penning trap mass spectrometry. Purpose: To establish A = 36 as the third high-precision T = 2 isobaric quintet with the T z = –2 member ground state mass measured by Penning trap mass spectrometry and provide the first test of the predictive power of the GIMME. Method: Here, a radioactive beam of neutron-deficient 36 Ca was produced by projectile fragmentation at the National Superconducting Cyclotron Laboratory. The beam was thermalized and the mass of 36 Ca + and 36 Ca 2+ measured by the Time of Flight - Ion Cyclotron Resonance method in the LEBIT 9.4 T Penning trap. Results: We measure the mass excess of 36 Ca to be ME= –6483.6(56) keV, an improvement in precision by a factor of 6 over the literature value. The new datum is considered together with evaluated nuclear data on the A = 36, T = 2 quintet. We find agreement with the quadratic form of the IMME given by isospin symmetry, but only coarse qualitative agreement with predictions of the GIMME. Conclusion: A total of three isobaric quintets have their most exotic members measured by Penning trap mass spectrometry. The GIMME predictions in the T = 2 quintet appear to break down for A = 32 and greater.

20 ≤ A ≤ 38↗

Processing of extraterrestrial materials by high temperature vacuum vaporization

It is noted that problems associated with the extraction and concentration of elements and commpounds important for the construction and operation of space habitats have received little attention. High temperature vacuum vaporization is considered a promising approach; this is a technique for which the space environment offers advantages in the form of low ambient pressures and temperatures and the possibility of sustained high temperatures via solar thermal energy. To establish and refine this new technology, experimental determinations must be made of the material release profiles as a function of temperature, of the release kinetics and chemical forms of material being transported, and of the various means of altering release kinetics. Trace element data determined by neutron activation analysis of meteorites heated to 1400 C in vacuum is summarized. The principal tool, high temperature spectrometry, is used to examine the vaporization thermodynamics and kinetics of major and minor elements from complex multicomponent extraterrestrial materials.

Grimley, R. T.↗

Measurement of material isotopics and atom number ratio with α-particle spectroscopy for a NIFFTE fission Time Projection Chamber actinide target

In this work, we present the results of a measurement of isotopic concentrations and atomic number ratio of a double-sided actinide target using α-spectroscopy and mass spectrometry. The double-sided actinide target, with predominantly 239 Pu on one side and 235 U on the other, was used in the fission Time Projection Chamber (fissionTPC) for a measurement of the neutron-induced fission cross-section ratio between the two isotopes. The measured atomic number ratio is needed to extract an absolute measurement fission cross-section ratio. The 239 Pu/ 235 U atom number ratio was measured with a combination of mass spectrometry and α-spectroscopy with a planar silicon detector achieving uncertainties of less than 1%. Different strategies for estimating isotopic concentration from the α-spectrum are presented to demonstrate the potential of these methods for non-destructive target assay. We found that a combination of fitting spectra with constraints from mass spectrometry, and summing counts in a region of the spectrum provided the most consistent results with the lowest uncertainty.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Performance testing of a Compton suppressed coincidence measurements using the Advanced Radionuclide Gamma-spectrOmeter

A Compton-suppressed multidimensional gamma-spectrometer is being developed within the Shallow Underground Laboratory (SUL) at Pacific Northwest National Laboratory (PNNL, USA). This Advanced Radionuclide Gamma-spectrOmeter (ARGO) system consists of two Broad Energy Germanium (BEGe) detectors, surrounded by a 12-detector sodium iodide (NaI) Compton suppression shield, situated inside a low-background lead and copper shield, fitted with a cosmic veto background reduction system. The detector has advanced functionality, including operation in single or combined detector mode, coincidence mode and Compton suppressed coincidence mode. Validation experiments measuring a neutron irradiated natural uranium sample, have demonstrated order of magnitude improvements in gamma detection sensitivity compared to conventional gamma-spectrometry techniques. Importantly this research demonstrates the feasibility of processing and analysing high-multiplicity datasets and the potential for high-sensitivity radionuclide measurements.

ARGO↗

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH 3 -TPD), and DFT calculations revealed that the supported ZnO x phase was present as isolated surface ZnO x sites on SiO 2 , with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO) 2 Zn 2+ O 2 Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO x sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH) + Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH) + Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO) 2 Zn 2+ O 2 Si= sites were inactive. Greater heterogeneity among all surface ZnO x sites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO x sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO x sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO) 2 Zn 2+ O 2 Si= sites on the silica support caused a greater number of active surface ZnO x sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH) + Si) sites. Such findings suggested that inactive surface ZnO x sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards a mechanistic understanding of the sol–gel syntheses of ternary carbides

Sol–gel chemistry, while being extremely established, is to this day not fully understood, and much of the underlying chemistry and mechanisms are yet to be unraveled. Here, in this work, we elaborate on the sol–gel chemistry of Cr 2 GaC, the first layered ternary carbide belonging to the MAX phase family to ever be synthesized using this wet chemical approach. Leveraging a variety of both in- and ex situ characterization techniques, including X-ray and neutron powder diffraction, X-ray absorption fine structure analyses, total scattering analyses, and differential scanning calorimetry coupled with mass spectrometry, in-depth analyses of the local structures and reaction pathways are elucidated. While the metals first form tetrahedrally and octahedrally coordinated oxidic structures, that subsequently grow and crystallize into oxides, the carbon source citric acid sits on a separate reaction pathway, that does not merge with the metals until the very end. In fact, after decomposing it remains nanostructured and disordered graphite until the temperature allows for the reduction of the metal oxides into the layered carbide. Based on this, we hypothesize that the method is mostly applicable to systems where the needed metals are reducible by graphite around the formation temperature of the target phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Density Measurement of NaCl-MgCl 2 -PuCl 3 and NaCl-UCl 3 -PuCl 3 Molten Salt Systems by Neutron Radiographic Dilatometry

A novel neutron radiographic technique was developed and implemented to measure the change in volume as a function of temperature of select plutonium-containing liquid chloride mixtures from melt to 1250 K. These measurements were performed at Los Alamos National Laboratory by members of the molten salt research group under support from Gateway for Accelerated Innovation in Nuclear (GAIN) voucher NE-21-25117: “Density Measurements of Plutonium Bearing Salts via Neutron Beam Dilatometry”. This technical report contains a description of the experimental method and a summary of the results. Initial characterization of the {NaCl, MgCl 2 , UCl 3 , PuCl 3 } salts used in this experiment includes a combination of x-ray diffraction, differential scanning calorimetry, gamma ray spectroscopy, and inductively coupled plasma mass spectrometry. Four samples of NaCl + MgCl 2 + x mol% PuCl 3 and four samples of NaCl + UCl 3 + x mol% PuCl 3 were prepared at the Plutonium Facility, shipped to the Los Alamos Neutron Science Center (LANSCE), and radiographed with the density via neutron radiography (DvNR) apparatus. Density data in the form of meniscus heights were recorded as a function of temperature. The results show a linear dependence of density with temperature and a third order polynomial dependence of density with composition as a function of PuCl 3 addition in the corresponding halide salt mixture. Additions of PuCl 3 result in a significant increase in density of the salt mixture and a slight reduction in the coefficient of volumetric expansion. These results represent a first measurement of the density of plutonium chloride salt mixtures and, in combination with additional measurements, may lead to a generalized description of the density of such salt systems for arbitrary compositions and temperature.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Correlating Nanoscale Secondary Ion Mass Spectrometry and Atom Probe Tomography Analysis of Uranium Enrichment in Metallic Nuclear Fuel

Distribution and enrichment of 235U within nuclear fuels are essential to material performance and reactor safety. With the development of metallic U fuels, understanding 235U homogeneity has become increasingly important, however, it is difficult to map with high spatial, and mass resolution to analyze both matrix and secondary phase precipitates. Here, we analyze 235U enrichment in matrix and carbide phases in LEU-Mo via two chemical imaging modalities: nanoscale secondary ion mass spectrometry (nanoSIMS) and atom probe tomography (APT). NanoSIMS and APT provided consistent results, with no statistically significant difference between measured and nominal enrichment (19.75 % 235U).

U-10Mo, atom probe tomography, nanoscale secondary↗

Improved chemical and isotopic labeling of biomembranes in Bacillus subtilis by leveraging CRISPRi inhibition of beta-ketoacyl-ACP synthase (fabF)

Assessing the structure of living microbial cell membranes is a challenging analytical goal. The cell membrane is defined by its transverse structure, an approximately 5 nm-thick selectively permeable bilayer that serves many important cellular functions. Compositionally complex, dynamic, and organized in both the transverse and lateral dimensions, understanding the cell membrane structure—and the role that structure plays in cellular function, communication, and environmental sensing is an active scientific effort. Previously, we have devised a novel isotopic labeling approach for membrane lipids to enable direct in vivo structural studies of the cell membrane in the Gram-positive bacterium, Bacillus subtilis , using small-angle neutron scattering. This was accomplished through a genetic inhibition of fatty acid (FA) degradation (Δ fadN ) and a chemical inhibition of FA biosynthesis using cerulenin, an irreversible inhibitor of type II fatty acid synthases. Here, we improve upon the previous system by introducing a dCas9/sgRNA- fabF complex that blocks transcription of the essential fabF gene when under xylose induction. This leads to greater sensitivity to cerulenin in the mutant strain (JEBS102) and more robust cell growth when supplementary FAs are introduced to the culture medium. A subtle change in FA uptake is noted when compared to the prior labeling strategy. This is seen in the gas chromatography/mass spectrometry (GC/MS) data as a higher ratio of n 16:0 to a 15:0, and manifests in an apparent increase in the membrane thickness determined via neutron scattering. This represents an improved method of isotopic labeling for the cell membrane of Bacillus subtilis; enabling improved investigations of cellular uptake and utilization of FAs, cell membrane structure and organization as a phenotypic response to metabolic and environmental changes.

59 BASIC BIOLOGICAL SCIENCES↗

Cosmic-ray-produced Cl-36 and Mn-53 in Allan Hills-77 meteorites

Cosmic-ray-produced Mn-53 has been determined by neutron activation in nine Allan Hills-77 meteorites. Additionally, Cl-36 has been measured in seven of these objects using tandem accelerator mass spectrometry. These results, along with C-14 and Al-26 concentrations determined elsewhere, yield terrestrial ages ranging from 10,000 to 700,000 years. Weathering was not found to result in Mn-53 loss.

Nishiizumi, K.↗

Measurements of I-129 in meteorites and lunar rock by tandem accelerator mass spectrometry

Precise measurements of the half-life of I-129 in three different meteorites and one lunar surface rock are reported. The meteorite source of I-129 was produced by cosmic ray secondary neutron reactions on Te, while the source in lunar materials in spallation on barium and rare earth elements. The Abee, Allende, and Dhajala meteorites were examined, together with the lunar rock 14310. Details of the process used to extract the iodine are provided. The Abee and Allende samples exhibited a production of 0.5 atom/min per gm of Te from the (n,2n) reaction and 0.05 atom/min/gm for the (n,gamma) reaction. The I-129 is concluded to be a viable tool for long-lived cosmogenic nuclide studies. Further work to extend the data to include the constancy of the cosmic ray flux, the meteorite bombardment history, and the cosmic exposure age dating by means of the I-129 and Xe-129 method is indicated.

Nizhiizumi, K.↗

Early Archean spherule beds of possible impact origin from Barberton, South Africa: A detailed mineralogical and geochemical study

The Barberton Greenstone belt is a 3.5- to 3.2-Ga-old formation situated in the Swaziland Supergroup near Barberton, northeast Transvaal, South Africa. The belt includes a lower, predominantly volcanic sequence, and an upper sedimentary sequence (e.g., the Fig Tree Group). Within this upper sedimentary sequence, Lowe and Byerly identified a series of different beds of spherules with diameters of around 0.5-2 mm. Lowe and Byerly and Lowe et al. have interpreted these spherules to be condensates of rock vapor produced by large meteorite impacts in the early Archean. We have collected a series of samples from drill cores from the Mt. Morgan and Princeton sections near Barberton, as well as samples taken from underground exposures in the Sheba and Agnes mines. These samples seem much better preserved than the surface samples described by Lowe and Byerly and Lowe et al. Over a scale of just under 30 cm, several well-defined spherule beds are visible, interspaced with shales and/or layers of banded iron formation. Some spherules have clearly been deposited on top of a sedimentary unit because the shale layer shows indentions from the overlying spherules. Although fresher than the surface samples (e.g., spherule bed S-2), there is abundant evidence for extensive alteration, presumably by hydrothermal processes. In some sections of the cores sulfide mineralization is common. For our mineralogical and petrographical studies we have prepared detailed thin sections of all core and underground samples (as well as some surface samples from the S-2 layer for comparison). For geochemical work, layers with thicknesses in the order of 1-5 mm were separated from selected core and underground samples. The chemical analyses are being performed using neutron activation analysis in order to obtain data for about 35 trace elements in each sample. Major elements are being determined by XRF and plasma spectrometry. To clarify the history of the sulfide mineralization, sulfur isotopic compositions are being determined.

Koeberl, Christian↗

Resonance ionization mass spectrometry for isotopic abundance measurements

Resonance ionization mass spectrometry (RIMS) is a relatively new laser-based technique for the determination of isotopic abundances. The resonance ionization process depends upon the stepwise absorption of photons from the laser, promoting atoms of the element of interest through progressively higher electronic states until an ion is formed. Sensitivity arises from the efficiency of the resonant absorption process when coupled with the power available from commercial laser sources. Selectivity derives naturally from the distinct electronic structure of different elements. This isobaric discrimination has provided the major impetus for development of the technique. Resonance ionization mass spectrometry was used for analysis of the isotopic abundances of the rare earth lutetium. Isobaric interferences from ytterbium severely effect the ability to measure small amounts of the neutron-deficient Lu isotopes by conventional mass spectrometric techniques. Resonance ionization for lutetium is performed using a continuous-wave laser operating at 452 nm, through a sequential two-photon process, with one photon exciting the intermediate resonance and the second photon causing ionization. Ion yields for microgram-sized quantities of lutetium lie between 10(6) and 10(7) ions per second, at overall ionization efficiencies approaching 10(-4). Discrimination factors against ytterbium greater than 10(6) have been measured. Resonance ionization for technetium is also being explored, again in response to an isobaric interference, molybdenum. Because of the relatively high ionization potential for Tc, three-photon, two-color RIMS processes are being developed.

Miller, C. M.↗

Replacing photomultiplier tubes with silicon photomultipliers for nuclear safeguards applications

Photomultiplier tubes (PMTs) have been used for decades as the default light detection technology for scintillator-based radiation monitors. PMTs come with a handful of disadvantages, however, including large volume usage, fragility, high-voltage requirements, and susceptibility to magnetic fields. Arrays of silicon photomultipliers (SiPMs) are a possible alternative to PMTs providing similar performance while offering improvements in the areas listed. We focus on straightforward “drop-in replacement” evaluations by imposing a single channel output of the SiPM signal and a backend electronics data acquisition and analysis routine identical to that used for PMTs. In the realm of nuclear safeguards, the primary performance metric for gamma spectroscopy is detector resolution, and for neutron detection it is pulse shape discrimination (PSD) to separate neutron and gamma signals. In this work we present the results of replacing a PMT with a 2” x 2” SiPM array mounted, in turn, to the same 2” x 2” cylindrical sodium iodide (NaI) crystal. The ultimate comparison for this gamma spectrometry is confirmation of uranium enrichment standards, ranging from depleted uranium to 93% highly enriched uranium (HEU), by analyzing the resulting spectra with both a simple integral scaling in key energy regions of the spectrum, as well as with the NaIGEM software package. In addition to the gamma spectroscopy work, we will present the latest results on comparing the PSD capabilities of a 4” x 4” SiPM array to a 5” PMT. As with the gamma spectroscopy evaluations, the light detectors are mounted in turn to the same liter-scale organic scintillators. This neutron-focused work includes evaluation of prototype SiPM readout boards with a single output signal summed over 256 individual SiPM pixels, and evident tradeoffs between PSD capability and fast response.

42 ENGINEERING↗

Replacing photomultiplier tubes with silicon photomultipliers for nuclear safeguards applications

Photomultiplier tubes (PMTs) have been used for decades as the default light detection technology for scintillator-based radiation monitors. PMTs come with a handful of disadvantages, however, including large volume usage, fragility, high-voltage requirements, and susceptibility to magnetic fields. Arrays of silicon photomultipliers (SiPMs) are a possible alternative to PMTs providing similar performance while offering improvements in the areas listed. We focus on straightforward “drop-in replacement” evaluations by imposing a single channel output of the SiPM signal and a backend electronics data acquisition and analysis routine identical to that used for PMTs. In the realm of nuclear safeguards, the primary performance metric for gamma spectroscopy is detector resolution, and for neutron detection it is pulse shape discrimination (PSD) to separate neutron and gamma signals. In this work we present the results of replacing a PMT with a 2” x 2” SiPM array mounted, in turn, to the same 2” x 2” cylindrical sodium iodide (NaI) crystal. The ultimate comparison for this gamma spectrometry is confirmation of uranium enrichment standards, ranging from depleted uranium to 93% highly enriched uranium (HEU), by analyzing the resulting spectra with both a simple integral scaling in key energy regions of the spectrum, as well as with the NaIGEM software package. In addition to the gamma spectroscopy work, we will present the latest results on comparing the PSD capabilities of a 4” x 4” SiPM array to a 5” PMT. As with the gamma spectroscopy evaluations, the light detectors are mounted in turn to the same liter-scale organic scintillators. This neutron-focused work includes evaluation of prototype SiPM readout boards with a single output signal summed over 256 individual SiPM pixels, and evident tradeoffs between PSD capability and fast response.

Engineering - Instrumentation related to nuclear s↗