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At least 1,117 records · Page 62

A Facile Aqueous Solution Route for the Growth of Chalcogenide Perovskite BaZrS 3 Films

The prototypical chalcogenide perovskite, BaZrS 3 (BZS), with its direct bandgap of 1.7–1.8 eV, high chemical stability, and strong light–matter interactions, has garnered significant interest over the past few years. So far, attempts to grow BaZrS 3 films have been limited mainly to physical vapor deposition techniques. Here, we report the fabrication of BZS thin films via a facile aqueous solution route of polymer-assisted deposition (PAD), where the polymer-chelated cation precursor films were sulfurized in a mixed CS 2 and Ar atmosphere. The formation of a single-phase polycrystalline BZS thin film at a processing temperature of 900 °C was confirmed by X-ray diffraction and Raman spectroscopy. The stoichiometry of the films was verified by Rutherford Backscattering spectrometry and energy-dispersive X-ray spectroscopy. The BZS films showed a photoluminescence peak at around 1.8 eV and exhibited a photogenerated current under light illumination at a wavelength of 530 nm. Temperature-dependent resistivity analysis revealed that the conduction of BaZrS 3 films under the dark condition could be described by the Efros–Shklovskii variable range hopping model in the temperature range of 60–300 K, with an activation energy of about 44 meV.

36 MATERIALS SCIENCE↗

Exploring Mixed Ionic–Electronic-Conducting PVA/PEDOT:PSS Hydrogels as Channel Materials for Organic Electrochemical Transistors

Here, we report the preparation and evaluation of PVA/PEDOT:PSS-conducting hydrogels working as channel materials for OECT applications, focusing on the understanding of their charge transport and transfer properties. Our conducting hydrogels are based on crosslinked PVA with PEDOT:PSS interacting via hydrogen bonding and exhibit an excellent swelling ratio of ~180–200% w/w. Our electrochemical impedance studies indicate that the charge transport and transfer processes at the channel material based on conducting hydrogels are not trivial compared to conducting polymeric films. The most relevant feature is that the ionic transport through the swollen hydrogel is clearly different from the transport through the solution, and the charge transfer and diffusion processes govern the low-frequency regime. In addition, we have performed in operando Raman spectroscopy analyses in the OECT devices supported by first-principle computational simulations corroborating the doping/de-doping processes under different applied gate voltages. The maximum transconductance (gm~1.05 μS) and maximum volumetric capacitance (C*~2.3 F.cm -3 ) values indicate that these conducting hydrogels can be promising candidates as channel materials for OECT devices.

36 MATERIALS SCIENCE↗

The Reactivity of Polyethylene Microplastics in Water under Low Oxygen Conditions Using Radiation Chemistry

Polyethylene (PE) is an intensely utilized polymer, which has consequently led to it becoming a common environmental contaminant. PE and other plastic waste are known to be highly persistent in surface waters; however, chemical and physical changes do take place over time, dependent mostly on highly variable natural conditions, such as oxygen (O2) availability. Gamma radiation was used to generate reactive oxygen species, namely hydroxyl radicals, in initially aerated aqueous solutions to simulate the natural weathering of microplastics in waters where there are fluctuations and often depletions in dissolved O2. The headspace of the irradiated PE-containing solutions was probed for the formation of degradation products using solid-phase microextraction (SPME) fibers in combination with gas chromatography mass spectrometry (GCMS). The major species detected were n-dodecane, with trace levels of tridecane, 2-dodecanone, and hexadecane, which were believed to be predominately adsorbed in the PE microplastics in excess of their aqueous solubility limits. Surface characterization by Raman spectroscopy and light and dark field microscopy indicated no change in the chemical composition of the irradiated PE microplastics under low O2 to anaerobic conditions. However, morphological changes were observed, indicating radical combination reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Exposure of Stainless Steel 316 to Subcritical, Transition, and Near-Supercritical Water

This work investigates the oxidation of austenitic stainless steel 316 at temperatures close to the critical point of water: subcritical water at 330°C and 27 MPa, the transition between subcritical and supercritical water at 374°C and 27 MPa, and supercritical water (SCW) at 380°C and 27 MPa. The surfaces of the samples were characterized using x-ray diffraction, Raman spectroscopy, scanning electron microscopy, and x-ray photoelectron spectroscopy before and after exposure. Magnetite (Fe3O4) was found to be present on all surfaces of all samples. The samples exposed to subcritical water also showed the presence of a nickel-iron chromium mixed spinel Ni(Fe2-xCrx)O4. The oxide morphology was observed to vary based on exposure temperature; an increased nucleation and growth rate, and an increased generation of Fe2+ was observed on samples exposed to the transition region and SCW.

Materials Science↗

Oxidation of Alloy X in Subcritical, Transition, and Supercritical Water

This work investigates the oxidation of a nickel-based superalloy, namely Alloy X, in water at elevated temperatures: subcritical water at 261°C and 27 MPa, the transition between subcritical and supercritical water at 374°C and 27 MPa, and supercritical water at 380°C and 27 MPa for 100 h. The morphology of the sample surfaces were studied using scanning electron microscopy coupled with focused ion beam milling, and the surface chemistry was investigated using x-ray diffraction, Raman spectroscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy before and after exposure studies. Surfaces of all samples were identified to comprise of a ferrite spinel containing aluminum.

Materials Science↗

Chemical abrasion: the mechanics of zircon dissolution

Chemical abrasion is a technique that combines thermal annealing and partial dissolution in hydrofluoric acid (HF) to selectively remove radiation-damaged portions of zircon crystals prior to U–Pb isotopic analysis, and it is applied ubiquitously to zircon prior to U–Pb isotope dilution thermal ionization mass spectrometry (ID-TIMS). The mechanics of zircon dissolution in HF and the impact of different leaching conditions on the zircon structure, however, are poorly resolved. We present a microstructural investigation that integrates microscale X-ray computed tomography (µCT), scanning electron microscopy, and Raman spectroscopy to evaluate zircon dissolution in HF. We show that µCT is an effective tool for imaging metamictization and complex dissolution networks in three dimensions. Acid frequently reaches crystal interiors via fractures spatially associated with radiation damage zoning and inclusions to dissolve soluble high-U zones, some inclusions, and material around fractures, leaving behind a more crystalline zircon residue. Other acid paths to crystal cores include the dissolution of surface-reaching inclusions and the percolation of acid across zones with high defect densities. In highly crystalline samples dissolution is crystallographically controlled with dissolution proceeding almost exclusively along the c axis. Increasing the leaching temperature from 180 to 210 °C results in deeper etching textures, wider acid paths, more complex internal dissolution networks, and greater volume losses. How a grain dissolves strongly depends on its initial radiation damage content and defect distribution as well as the size and position of inclusions. As such, the effectiveness of any chemical abrasion protocol for ID-TIMS U–Pb geochronology is likely sample-dependent. We also briefly discuss the implications of our findings for deep-time (U-Th)/He thermochronology.

58 GEOSCIENCES↗

Petrophysical and geomechanical properties of gas hydrate-bearing sediments recovered from Alaska North Slope 2018 Hydrate-01 Stratigraphic Test Well

Knowledge of petrophysical and geomechanical properties of gas hydrate-bearing sediments are essential for predicting reservoir response due to gas production from gas hydrate reservoirs. That information will be critical parameters for designing production well completion such as specification of depressurization pump, water storage tank, and mesh size of sand screen. In December 2018, Stratigraphic Test Well Hydrate-01 was drilled in the western part of the Prudhoe Bay Unit, Alaska North Slope as part of the technical planning effort for a future long-term production test by collaborative team of DOE/NETL, USGS, and MH21-S (Boswell et al., 2020, Collett et al., 2020, Okinaka et al., 2020). Data set of logging-while-drilling (LWD) were acquired (Haines et al., 2020, Suzuki et al., 2019) and core sampling depth was determined on-site.Side-wall pressure coring was conducted to recover gas hydrate-bearing sediments from two reservoir sections named Unit-B and Unit-D. A total of 34 cores were successfully recovered by 5 runs of a wire-line deployed pressure corer (CoreVault® System - Halliburton). Core analysis scheme of this project are shown in Figure 1. All cores were quenched in liquid nitrogen while at high pressure in the laboratory of Stratum Reservoir, LLC. at Anchorage (Figure 1, a)). And the cores were removed from the pressure corer autoclave with temperature support of dry ice and stored under liquid nitrogen at atmospheric pressure. 19 damaged cores were processed to index property measurements directly such as grain size, grain density. 4 of another 17 cores were depressurized and trimmed for making a plug to analyze petrophysical properties of host sediments. Unsteady-state permeability test was conducted to obtain relative water permeability to gas and core scale NMR T2 distribution measurement was performed for evaluating pore size distribution at Houston (Figure 1, b)). Remained high quality 13 cores were preserved with gas hydrate for advanced laboratory analysis. National Institute of Advanced Industrial Science and Technology, as a part of the Japanese National Hydrate Research Program (MH21-S, funded by Ministry of Economy, Trade and Industry), received the samples at Sapporo, Japan for advanced core analysis. High-resolution X-ray CT was used to analyze the quality of the samples, which showed undisturbed lithological layers. Cores were lathed into cylindrical shape and distributed for multi property measurements (Figure 1, c)).<p>As a result, sediment from Unit-D is categorized as silty sand at ~37% porosity with ~80% gas hydrate saturation. An average hydration number n = 6.16 was measured by Raman spectroscopy. An average intrinsic permeability of ~400 mD and in situ effective permeability (with hydrate) on the order of ~10 mD. The Unit B recovered cores consisted of well sorted sand at ~40% porosity with ~95% gas hydrate saturation. An average intrinsic permeability of ~1 Darcy and in situ effective permeability on the order of ~30 mD was measured for the Unit B cores. There was a small permeability reduction due to porosity loss with increasing effective stress that simulated consolidation behavior along with depressurization in the highly permeable sandy sediment. The apparent minimum change in porosity and permeability may be caused by the low compressibility of quartz sand grains in the recovered cores. XRD and thermal conductivity analysis also suggested high quartz content. Triaxial compression tests established internal friction angles based on the Mohr-Coulomb's failure criterion, which are 40° for hydrate-bearing sediment and 29.8° for hydrate free sediment.</p>

Yoneda, Jun↗

Challenges to detection: Humidity as a spur to chemical agent change

Detecting chemical agents in outdoor environments such as a battlefield is made challenging by not only the spurious signatures from background chemicals and surfaces (e.g. asphalt, dirt, concrete), but also by the chemical transformation of the actual agents. The change of CW agents to other species can be catalyzed by other chemicals present in the scene, by different substrates, as well as by local weather conditions. Some of the final environmental transformation products are known (e.g. for the G agents methylphosphonic acid), but many of the intermediate chemical states are not, nor are the rates of transformation to the other intermediates or the end products. In this study we have made preliminary optical investigations into the degradation products of a G-agent intermediate, namely methylphosphonic anhydride and its rate of conversion to the more stable methylphosphonic acid. Using infrared and Raman spectroscopies, we have found that the relative humidity (RH) greatly affects the rate of change and we report first results from these studies.

: chemical warfare agent detection, Methylphosphon↗

Carbon Anode Material from Biomass Pyrolysis Oil

Lithium-ion batteries (LIB) are an important component of electric vehicles and sodium-ion batteries (SIB) are an attractive alternative for grid electric storage. We are investigating a novel approach to synthesizing the carbon anode materials for these batteries from biomass pyrolysis oil as part of conversion processes to produce biofuels. Graphite is used as anode material in LIB and is exclusively produced from petroleum residue or mined mineral carbon. We have synthesized drop-in graphite by coking the heavy residual oil from the distillation of catalytic fast pyrolysis oil and by catalytic graphitizing raw pyrolysis oil. XRD and Raman spectroscopies were used to verify the production of high purity crystalline graphite. Figure 1 shows typical XRD spectra of the bio-graphite compared to commercial material as well as the charge/discharge cycle. Graphite particle sizes and morphologies were adjusted to improve performance using jet milling and carbon coating. The bio-graphite delivered a high capacity (335 mAh/g) when tested in a graphite half-cell. Full cell coin cell experiments were also conducted to verify the observations from half-cell testing. The high value of graphite (>$9/kg) can positively impact the economics of biofuels production and can be an important part of a future circular carbon economy. We have also investigated synthesizing hard carbon from pyrolysis oil for use as anode material in SIB. These batteries are not commercially mature but have great promise in grid storage and use earth abundant elements. We have demonstrated that pyrolysis oil can be used to synthesize hard carbon, which was subsequently be used in SIB experiments. This material achieved a sodium-ion capacity of 250 mAh/g and a first cycle efficiency of 78%, with opportunities to further optimize this performance from optimizing the composition of the pyrolysis oil to shaping the hard carbon particles. As with graphite, hard carbon is a high value (> $10/kg) material that could facilitate biofuels production.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Search for High-Pressure Silicon Phases: Reaching the Extreme Conditions with High-Intensity Laser Irradiation

Controlling electronic and optical properties of semiconducting materials could substantially expand their functionality and enable new pathways for the formation of ‘smart’ materials for emerging innovative applications. An emerging new path for the synthesis of exotic silicon (Si) polymorphs is irradiation of bulk diamond-cubic Si by ultrashort laser pulses at relativistic intensity above 1019 W/cm2. Exotic polymorphs are formed due to interaction with MeV-energy electrons generated in laser-produced high-temperature plasma state. The unusual Si structures are found in the form of 5–10 nm nanoparticles confined deep in the bulk of 500-μm-thick Si samples. Raman spectroscopy, electron microscopy and X-ray diffraction studies provide an unequivocal evidence of exotic Si phase formation. A key advantage of such relativistic irradiation lies thereby in the fact that large quantities of such exotic Si is synthesised embedded within the bulk diamond-cubic Si and that further the formed Si polymorphs are stable at ambient temperature and pressure. They are thus available for further studies for electronic applications in selective band gap engineering.

Rapp, Ludovic↗

Double-walled containment cell

Double-walled containment cells are described as may be used for storage, transport, and examination of a sample held within the cell by use of optical analysis techniques. A double-walled containment cell can include multiple types of windows that can be located as desired on the containment cells and thereby provide for optical access to a sample for multiple optical analysis techniques. Disclosed containment cells can be sized and designed for use with existing optical analysis systems, e.g., laser ablation, X-ray diffraction, spectral analysis (e.g., Raman spectroscopy, infrared spectroscopy, laser-induced breakdown spectroscopy, etc.), imaging analysis, etc.

Villa-Aleman, Eliel↗

LDRD poster - Identifying the speciation of salt-based actinides in the presence of contaminants

Molten salt reactors (MSRs) are among the most promising Generation IV nuclear reactors. The salts used in these reactors exhibit a high affinity for moisture and oxygen, and heating does not eliminate the oxides that are formed. Additionally, due to the high operating temperatures, reactor parts experience pronounced corrosion, and the resulting corrosion products integrate into the fuel salt system. It is hypothesized that the speciation of f-elements in molten salts would change in the presence of oxides and corrosion products. These changes in local structure can alter the rheological properties, which are critical to the operational and safety parameters of the reactors. Therefore, an in-depth understanding of how corrosion products influence lanthanide/actinide speciation is crucial. To test this hypothesis, lanthanides (as surrogates for actinides) and actinide chlorides were mixed with oxides (such as nickel oxide and lithium oxide) and/or corrosion products (e.g., nickel chloride) and reacted in molten salts. The resulting phases were analyzed using techniques such as powder X-ray diffraction, Raman spectroscopy, UV-Visible spectroscopy, and nuclear magnetic resonance spectroscopy. In the presence of oxides, due to the high oxophilicity of f-elements, these elements capture oxygen from the oxides, forming lanthanide/actinide oxide or oxychloride phases. Specifically, with cerium chloride, the introduction of lithium oxide to the formation of various final products depending on the oxide concentration. At lower oxide concentrations, cerium oxychloride (CeOCl) in the +3 oxidation state was observed, while an increase in the oxide concentration led to the formation of cerium dioxide (CeO2), where cerium is in the +4 oxidation state. In contrast, with nickel oxide, CeOCl formation was consistently observed, regardless of the oxide concentration. This project successfully determined that the speciation of f-elements change in the presence of oxides and different oxides in molten salts result in different final products. When the influence of nickel chloride was examined, changes in f-element speciation were not observed. However, it reacted with lithium chloride to generate a lithium-nickel-chloride (Li6NiCl8) phase, which was also observed when nickel oxide was reacted. Computational models were developed to simulate the phases anticipated under experimental conditions.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Spectroscopic Signatures of MQ-Resins in Silicone Elastomers

Polysiloxane elastomers have a large application space due to their versatile cross-linking chemistry and highly tunable physical and mechanical properties. One approach for improving the mechanical integrity of commercial polysiloxane “silicone” elastomers while maintaining their optical transparency is the addition of small, silicone-resin molecules to the network. However, both the poly(dimethylsiloxane) (PDMS) network and the silicone-resin particles have an amorphous structure and complex chemistry, which makes the characterization of their structural properties and segmental network dynamics difficult. Here, we report the synthesis and characterization of a series of model silicone networks modified with a specific class of silicone-resin known as MQ-resin using Raman and advanced nuclear magnetic resonance (NMR) spectroscopy methods. Raman spectroscopy was successfully used to quantify the contribution of the MQ-resin to the network, to determine the type of MQ-resin present in the network, and to investigate the completeness of the network cross-linking reaction. Furthermore, solid-state and 1H double-quantum (DQ) NMR spectroscopies were used not only as a detection method for the MQ-resins but also to quantify changes in the segmental dynamics of the network as a function of MQ-resin concentration. The combination of Raman and NMR spectroscopies describes a series of samples where the MQ-resin particles and PDMS chains maintain their independent segmental dynamics up to high concentrations of MQ-resins (40–50% MQ), where the physical properties of the resin dominate the physical properties of the overall network. The results from our spectroscopic analyses are consistent with the results from macroscopic characterization techniques such as solvent uptake and mechanical testing. The spectroscopic insights into the structure–property relationships of PDMS-MQ composites presented in this study are a valuable tool not only for the synthesis and reverse engineering of future generations of commercial silicone elastomers but also for understanding the mechanisms of aging and degradation over the material lifetime.

36 MATERIALS SCIENCE↗

Raman and Terahertz Spectroscopy of Low-Frequency Chiral Phonons in Amino Acids

Chiral phonons are mirror-symmetric vibrations with nonzero angular momenta that correspond to twisting and rotational motions of multiple atoms. In chiral crystals, these include low-energy terahertz (THz)-range vibrations of the molecular segments involving dozens of atoms with energies sensitive to molecular chirality. Here, we present spectral signatures of chiral phonons in circularly polarized Raman optical activity (ROA) spectra from enantiomers of amino acid crystals. Along with complementary THz circular dichroism (TCD) measurements, our ROA data reveal several vibrational bands in enantiomers of valine, alanine, tyrosine, and proline between 30 and 150 cm –1 (∼1–4.5 THz) that exhibit opposite intensities. Density functional theory calculations confirm their assignment to twisting and shearing molecular motions. The simultaneous registration of chiral phonon modes by ROA and TCD demonstrates the necessity of these complementary techniques to identify complex mirror-asymmetric vibrational modes and offers new insights into their interactions with circularly polarized light.

36 MATERIALS SCIENCE↗

Simultaneous quantification of uranium( VI ), samarium, nitric acid, and temperature with combined ensemble learning, laser fluorescence, and Raman scattering for real-time monitoring

In this work, laser-induced fluorescence spectroscopy (LIFS), Raman spectroscopy, and a stacked regression ensemble was developed for near real-time quantification of uranium(VI) (1–100 μg mL –1 ), samarium (0–200 μg mL –1 ) and nitric acid (0.1–4 M) with varying temperature (20 °C–45 °C). LIFS applications range from fundamental lab-scale studies to real-time process monitoring at industrial levels, such as nuclear reprocessing applications, provided the phenomena affecting the fluorescence spectrum are accounted for (e.g., absorption, quenching, complexation). Multiple chemometric models were examined and compared to a more traditional multivariate regression approach called partial least squares (PLS). Results obtained on synthetic samples selected using D-optimal experimental design indicated that a stacked regression method, which included ridge regression, random forest, PLS, and an eXtreme gradient boost algorithm, successfully measured uranium(VI) concentrations directly in nitric acid without measuring luminescence lifetimes or standard addition. The top model resulted in percent root-mean-square error of prediction values of 5.2, 1.9, 3.0, and 2.3% for U(VI), Sm 3+ , HNO 3 , and temperature, respectively. The approach may be useful for quantifying fluorescent fission products (e.g., Sm 3+ ) to provide information on burnup of irradiated nuclear fuel. This novel framework reinforces the applicability of LIFS for real-time applications in nuclear fuel cycle applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Caught in the H inact : Crystal Structure and Spectroscopy Reveal a Sulfur Bound to the Active Site of an O 2 -stable State of [FeFe] Hydrogenase

[FeFe] hydrogenases are the most active H 2 converting catalysts in nature, but their extreme oxygen sensitivity limits their use in technological applications. The [FeFe] hydrogenases from sulfate reducing bacteria can be purified in an O 2 -stable state called H inact . To date, the structure and mechanism of formation of H inact remain unknown. Our 1.65 Å crystal structure of this state reveals a sulfur ligand bound to the open coordination site. Furthermore, in-depth spectroscopic characterization by X-ray absorption spectroscopy (XAS), nuclear resonance vibrational spectroscopy (NRVS), resonance Raman (RR) spectroscopy and infrared (IR) spectroscopy, together with hybrid quantum mechanical and molecular mechanical (QM/MM) calculations, provide detailed chemical insight into the Hinact state and its mechanism of formation. This may facilitate the design of O 2 -stable hydrogenases and molecular catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An experimental and computational investigation of the structure and spectroscopic signatures of α -UO 3

α-UO 3 is a common intermediate compound found in the nuclear fuel cycle, yet the exact crystal structure of this material has long been debated. Inconsistent computational and experimental data in previous works has led to varying conclusions between authors. Furthermore, to ensure the validity of our results in this work, the structural and spectroscopic signatures of pure phase α-UO 3 are investigated using powder X-ray diffraction and optical vibrational spectroscopy (infrared and Raman). Rietveld refinement of powder X-ray diffraction data on pure phase α-UO 3 collected in this work allows us to propose an alteration to the currently accepted C2mm structure (a = 3.9705 Å, b = 6.8553 Å, c = 4.15955 Å, α = β = γ = 90°) for α-UO 3 with no uranyl [UO 2 2+ ] bonds. Raman spectra collected using two excitation wavelengths (two instruments using 532 nm and one 785 nm) are presented, and differences with recently published results are discussed. Infrared spectra from two instruments used here agree well with recently published results, but the spectral range encompassed in our data extends past what has been reported with modern techniques. Additionally, we provide tentative vibrational mode assignments based on density functional perturbation theory calculations and resulting phonon eigenvector visualizations. Unexpected features in the optical vibrational spectra of α-UO 3 are explained by unique features in the structure we present.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗