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At least 991 records · Page 55

Resonant radiation from oscillating higher order solitons

We present radiation mechanism exhibited by a higher order soliton. In a course of its evolution the higher-order soliton emits polychromatic radiation resulting in formation of multipeak frequency comb-like spectral band. The shape and spectral position of this band can be effectively controlled by the relative strength of the third order dispersion. An analytical description is corroborated by numerical simulations. Research showed that for longer pulses the described effect persists also under the action of higher order perturbations such as Raman and self-steepening.

36 MATERIALS SCIENCE↗

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↗

Effect of MWCNT Content on the Structure and Properties of Spark Plasma-Sintered Iron-MWCNT Composites Synthesized by High-Energy Ball Milling

The effect of multiwall carbon nanotube (MWCNT) content on the physical and mechanical properties of Fe-MWCNT composites has been studied. High-energy ball milling (HEBM) is employed to produce the composite powder; following this, spark plasma sintering (SPS) process has been adopted for powder consolidation. The composite powder and the sintered products were subjected to structural characterization by XRD. Microstructural studies were carried out by optical, field-emission scanning and high-resolution transmission electron microscopy. While Fourier transform infrared spectroscopic study of composites was done to understand the bonding characteristics, Raman spectroscopy was employed to assess the structural damage of MWCNT after HEBM. The effects of processing on the behavior of C-C, C-O and Fe-O bonds are studied by x-ray photoelectron spectroscopy. Microhardness and compressive strength of composites are also determined. Finally, magnetic and electrical properties of the composites were characterized. It was observed that optimized ball milling conditions help to preserve the structural identity of MWCNT. Consolidation by SPS insured good interfacial bonding. The microhardness and compression strength are significantly improved in MWCNT-reinforced iron matrix composite. MWCNT has appreciably improved the electrical conductivity of the composites. Tethering of MWCNT by iron oxide has led to appreciable improvement in saturation magnetization till 3 wt.% MWCNT.

36 MATERIALS SCIENCE↗

Enhanced stimulated Raman scattering during intense laser propagation

Stimulated Raman scattering is ubiquitous in many high-intensity laser environments. Parametric four-wave mixing between the pump and Raman sidebands can affect the Raman gain, but stringent phase matching requirements and strongly nonlinear dynamics obscure clear understanding of its effects at high laser powers. Here we investigate four-wave mixing in the presence of strong self-focusing and weak ionization at laser powers above the Kerr critical power. Theoretical analysis shows that the plasma generated at focus naturally leads to phase matching conditions suitable for enhanced Raman gain, almost without regard to the initial phase mismatch. Multidimensional nonlinear optical simulations with multiphoton and collisional ionization confirm the enhancement and suggest that it may lead to significantly higher Raman losses in some high-intensity laser environments.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Hydrogen Annealing Effect on the Magnetic Properties of ZnCoO/MoS{sub 2} Hybrid

The ZnCoO/MoS{sub 2} hybrid is successfully synthesized through a general and facile process. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectra reveal that the hybrid consists of wurtzite ZnCoO and few layers of MoS{sub 2}, which shows a paramagnetic property. In contrast, the hybrid presents clear magnetic hysteresis at room temperature with a H{sub 2} post-annealing process. No Co metal nanoclusters can be identified by XRD and HRTEM. The red shift of E{sub 2g}{sup 1} and A{sub 1g} peak indicates the strain effect induced by H{sub 2} annealing. On the other hand, the disappeared peak at 477 cm{sup −1} can be ascribed to the modification of the interface and surface state of the ZnCoO. Temperature-dependent Raman spectroscopies demonstrate the significant H{sub 2} annealing effect on the structural properties of ZnCoO/MoS{sub 2} hybrid. The interplay between the electron interaction at the interface and oxygen vacancies of ZnCoO can be responsible for the magnetic properties of the ZnCoO/MoS{sub 2} hybrid. The tunable magnetic properties have a promising application in multifunctional MoS{sub 2}-based semiconductor and spintronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Layer-Dependent Pressure Effect on the Electronic Structure of 2D Black Phosphorus

Through infrared spectroscopy, we systematically study the pressure effect on electronic structures of few-layer black phosphorus (BP) with layer number ranging from 2 to 13. We reveal that the pressure-induced shift of optical transitions exhibits strong layer dependence. In sharp contrast to the bulk counterpart which undergoes a semiconductor to semimetal transition under ~1.8 GPa, the band gap of 2 L increases with increasing pressure until beyond 2 GPa. Meanwhile, for a sample with a given layer number, the pressure-induced shift also differs for transitions with different indices. Through the tight-binding model in conjunction with a Morse potential for the interlayer coupling, this layer- and transition-index-dependent pressure effect can be fully accounted. Our study paves a way for versatile van der Waals engineering of two-dimensional BP.

2-dimensional systems↗

Highly Al-doped TiO{sub 2} nanoparticles produced by Ball Mill Method: structural and electronic characterization

Highlights: • Highly Al-doped TiO{sub 2} nanoparticles were synthesized using a Ball Mill Method. • Al doping delayed anatase to rutile phase transformation. • Al doping allow controlling the structural and electronic properties of nanoparticles. - Abstract: This study presents an easy method for synthesizing highly doped TiO{sub 2} nanoparticles. The Ball Mill method was used to synthesize pure and Al-doped titanium dioxide, with an atomic percentage up to 15.7 at.% Al/(Al + Ti). The samples were annealed at 773 K, 973 K and 1173 K, and characterized using ICP-AES, XRD, Raman spectroscopy, FT-IR, TG, STEM, XPS, and UV–vis spectroscopy. The effect of doping and the calcination temperature on the structure and properties of the nanoparticles were studied. The results show high levels of internal doping due to the substitution of Ti{sup 4+} ions by Al{sup 3+} in the TiO{sub 2} lattice. Furthermore, anatase to rutile transformation occurs at higher temperatures when the percentage of doping increases. Therefore, Al doping allows us to control the structural and electronic properties of the nanoparticle synthesized. So, it is possible to obtain nanoparticles with anatase as predominant phase in a higher range of temperature.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mechanism of Ball Milling Effect on Carbothermic Reduction of Industrial Magnesia by Coke

Mechanical milling always improves the chemical reaction rate in the metallurgy process. The experiment proved that ball milling treatment on raw materials, including industrial magnesia, metallurgical coke, and fluoride calcium, could increase greatly the reaction rate of magnesia. The reaction samples and residues were analyzed by particle size measurement, X-ray diffraction (XRD) analysis, Raman spectroscopy analysis, scanning electron microscope (SEM), and transmission electron microscope (TEM). The results suggested that the positive effect of ball milling on the reaction rate came from three aspects. Ball milling could decrease magnesia particle size and peel coke into graphite sheets to enlarge their contact surface. Meanwhile, ball milling could slightly destroy the crystal grain surface of magnesia and decrease the crystallization of graphite. The nanometer-scale magnesia particles and graphite sheets would stably and strongly attract together after a longer time ball milling. The possible evolution of the particles during ball milling was given, which explained the mechanism of the ball milling effect on the carbothermic reduction of industrial magnesia by coke.

36 MATERIALS SCIENCE↗

Strain-Modified Raman Responses in Monolayer MoS 2 Nanobubbles Resolved at 5 nm

The formation of nanoscale bubbles is an unavoidable consequence during the transfer of two-dimensional materials onto target substrates, driven by van der Waals interactions at the interface. While often viewed as imperfections, these nanoscale bubbles have garnered considerable scientific interest due to the substantial in-plane strain gradients they induce, which in turn give rise to a variety of intriguing optoelectronic effects, particularly in semiconducting transition metal dichalcogenides. Determining and analyzing the strain distribution within nanobubbles at the nanoscale is crucial for advancing our understanding of these underlying strain-induced effects. Here, we present a high-resolution scanning tunneling microscopy-based tip-enhanced Raman spectroscopic investigation of localized nanoscale strain distribution within the nanobubbles formed between monolayer MoS 2 and Au interface. By employing cryogenic temperature (78 K), we successfully differentiate the nanoscale Raman signatures between nanobubble edge and pristine MoS 2 . We verify a maximum tensile strain of ∽1.15–1.34% at the nanobubble edge, which gradually diminishes toward the center, yielding a cross-sectional strain profile consistent with a doughnut-shaped distribution. Furthermore, we report to achieve ∽5 nm spatial resolution in probing such edge-localized strain within the nanobubble. In addition, comparative average strain analysis of such MoS 2 nanobubbles is conducted via geometric mechanistic analysis such as membrane and nonlinear plate theories, providing key insight into the geometric nature near the bubble edge. Our work provide fundamental information about strain-induced nanoscale chemical understanding of 2D materials on the nanometer scale, paving the way for practical applications of nanobubbles in strain-engineered optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Patchy silica-coated silver nanowires as SERS substrates

We report a class of core-shell nanomaterials that can be used as efficient surface-enhancement Raman scattering (SERS) substrates. The core consists of silver nanowires, prepared through a chemical reduction process, that are used to capture 4- mercaptobenzoic acid (4-MBA), a model analyte. The shell was prepared through a modified Stöber method and consists of patchy or full silica coats. The formation of silica coats was monitored via transmission electron microscopy, UV-visible spectroscopy and phase-analysis light scattering for measuring effective surface charge. Surprisingly, the patchy silica coated silver nanowires are better SERS substrate than silver nanowires; nanomolar concentration of 4-MBA can be detected. In addition, “nano-matryoshka” configurations were used to quantitate/explore the effect of the electromagnetic field at the tips of the nanowire (“hot spots”) in the Raman scattering experiment.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Importance of Correctly Describing Charge-Transfer Excitations for Understanding the Chemical Effect in SERS

The enhancement mechanism due to the molecule-surface chemical coupling in surface-enhanced Raman scattering (SERS) is governed to a large extent by the energy difference between the highest occupied molecular orbital (HOMO) of the metal and the lowest unoccupied molecular orbital (LUMO) of the molecule. Here, we investigate the importance of correctly describing charge-transfer excitations, using time dependent density functional theory (TDDFT), when calculating the chemical coupling in SERS. It is well-known that TDDFT, using traditional functionals, underestimates the position of charge-transfer excitations. Here, we show that this leads to a significant overestimation of the chemical coupling mechanism in SERS. Significantly smaller enhancements are found using long-range corrected (LC) functionals as compared with a traditional generalized gradient approximation (GGA) and hybrid functionals. Enhancement factors are found to be smaller than 530 and typically less than 50. Our results show that it is essential to correctly describe charge-transfer excitations for predicting the chemical enhancement in SERS.

Environmental Molecular Sciences Laboratory↗

Simulations of the IR and Raman spectra of water confined in amorphous silica slit pores

Water in nano-scale confining environments is a key element in many biological, material, and geological systems. The structure and dynamics of the liquid can be dramatically modified under these conditions. Probing these changes can be challenging, but vibrational spectroscopy has emerged as a powerful tool for investigating their behavior. A critical, evolving component of this approach is a detailed understanding of the connection between spectroscopic features and molecular-level details. In this paper, this issue is addressed by using molecular dynamics simulations to simulate the linear infrared (IR) and Raman spectra for isotopically dilute HOD in D 2 O confined in hydroxylated amorphous silica slit pores. The effect of slit-pore width and hydroxyl density on the silica surface on the vibrational spectra is also investigated. The primary effect of confinement is a blueshift in the frequency of OH groups donating a hydrogen bond to the silica surface. This appears as a slight shift in the total (measurable) spectra but is clearly seen in the distance-based IR and Raman spectra. Analysis indicates that these changes upon confinement are associated with the weaker hydrogen-bond accepting properties of silica oxygens compared to water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly efficient Cu-decorated iron oxide nanocatalyst for low pressure CO2 conversion

We report a nanoparticulate iron oxide based catalyst for CO2 conversion with high efficiency at low pressures and on the effect of the presence of copper on the catalyst’s restructuring and its catalytic performance. In situ X-ray scattering reveals the restructuring of the catalyst at the nanometer scale. In situ X-ray absorption near edge structure (XANES) shows the evolution of the composition and oxidation state of the iron and copper components under reaction conditions along with the promotional effect of copper on the chemical transformation of the iron component. X-ray diffraction (XRD), XANES and Raman spectroscopy proved that the starting nanocatalyst is composed of iron oxides differing in chemical nature (α-Fe2O3, Fe3O4, FeO(OH)) and dimensionality, while the catalyst after CO2 conversion was identified as a mixture of α-Fe, Fe3C, and traces of Fe5C2. The significant increase of the rate CO2 is turned over in the presence of copper nanoparticles indicates that Cu nanoparticles activate hydrogen, which after spilling over to the neighbouring iron sites, facilitate a more efficient conversion of carbon dioxide.

Benzene↗

Overcoming diffusion-related limitations in semiconductor defect imaging with phonon-plasmon-coupled mode Raman scattering

Carrier diffusion is of paramount importance in many semiconductor devices, such as solar cells, photodetectors, and power electronics. Structural defects prevent such devices from reaching their full performance potential. Although a large carrier diffusion length indicates high material quality, it also implies increased carrier depletion by an individual extended defect (for instance, a dislocation) and obscures the spatial resolution of neighboring defects using optical techniques. For commonly utilized photoluminescence (PL) imaging, the spatial resolution is dictated by the diffusion length rather than by the laser spot size, no matter the spot is at or below the diffraction limit. We show how Raman imaging of the LO phonon-plasmon-coupled mode can be used to recover the intrinsic spatial resolution of the optical system, and we demonstrate the effectiveness of the technique by imaging defects in GaAs with diffraction-limited optics, achieving a 10-fold improvement in resolution. Furthermore, by combining Raman and PL imaging, we can independently and simultaneously determine the spatial dependence of the electron density, hole density, radiative recombination rate, and non-radiative recombination rate near a dislocation-like defect, which has not been possible using other techniques.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Dry reforming of methane over CeO 2 -supported Pt-Co catalysts with enhanced activity

Dry reforming of methane provides opportunities of using CH 4 and CO 2 to produce syngas. The PtCo/CeO 2 bimetallic catalyst shows higher activity and H 2 /CO ratio than the corresponding monometallic catalysts, mainly attributed to the synergistic effect of Pt-Co. Structural feature of the PtCo/CeO 2 catalyst was revealed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of adsorbed CO and in situ techniques like X-ray diffraction (XRD), X-ray adsorption fine structure (XAFS) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). Pt-Co alloy and separated Co particles co-existed in the bimetallic catalyst, whereas the former was determined as the dominant active structure with a Pt-Co-mixed-surface termination. During reaction, Pt and Co in the alloy structure nearly maintained their metallic state with slight oxygen decoration, yielding oxygen-metal site-pairs (O*-*). Combined kinetic investigations and DFT calculations reveal that the O*-modified catalytic surface of PtCo/CeO 2 promotes CH bond activation with higher entropy contribution (less constraints) to compensate its higher activation barrier. Thermogravimetric analysis (TGA), transmission electron microscope (TEM) and Raman spectroscopy show that the PtCo/CeO 2 catalyst is resistant to coke formation as effectively as Pt/CeO 2 and can be easily regenerated by a mild CO 2 treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interplay of Bias-Driven Charging and the Vibrational Stark Effect in Molecular Junctions

We observe large, reversible, bias driven changes in the vibrational energies of PCBM based on simultaneous transport and surface-enhanced Raman spectroscopy (SERS) measurements on PCBM-gold junctions. A combination of linear and quadratic shifts in vibrational energies with voltage is analyzed and compared with similar measurements involving C-60-gold junctions. A theoretical model based on density functional theory (DFT) calculations suggests that both a vibrational Stark effect and bias-induced charging of the junction contribute to the shifts in vibrational energies. In the PCBM case, a linear vibrational Stark effect is observed due to the permanent electric dipole moment of PCBM. The vibrational Stark shifts shown here for PCBM junctions are comparable to or larger than the charging effects that dominate in C-60 junctions.

36 MATERIALS SCIENCE↗

The Ionization Constants of DCO{sub 3}{sup -} and DPO{sub 4}{sup 2-} under Candu Reactor Primary Coolant Conditions by Raman Spectroscopy

The ionization constants of bicarbonate and hydrogen phosphate have been measured in light and heavy water up to 325 deg. C using Raman spectroscopy. Ionization constants in heavy water at temperatures above 100 deg. C have been measured for very few acids and bases. Together with other results, this work will be used to develop and verify models of the deuterium isotope effect on oxide solubilities in Candu reactor primary coolant. A custom-built titanium/sapphire flow cell was paired with a Horiba Jobin Yvon HR800 LabRAM system to collect Raman spectra of aqueous solutions under Candu primary coolant temperatures. The temperature-controlled cell is made of materials that are relatively inert under the extreme experimental conditions required for hydrothermal studies. Raman spectra were collected with detector polarizations parallel and perpendicular to the laser polarization. These were subtracted and corrected to obtain the reduced isotropic spectrum, which contains only symmetric vibrations, has a flat baseline, and has peak areas proportional to species concentration. Vibrational modes involving deuterium are shifted to lower wavenumbers in heavy water due to the increased mass of deuterium over hydrogen. The speciation between the two solvents is also measurably different. The relative concentration of the acidic species in solution increases with temperature, making its peaks easier to fit at high temperatures. The Raman band positions shift to lower wavenumbers with increasing temperature because the hydrogen bonding in bulk water begins to break down, which strengthens hydrogen bonding to the ions. The basic equilibrium constants were determined from the concentration of each species in solution combined with an activity coefficient model. A simplified form of the 'density' model was then fitted to the data. These fit results were combined with literature values of pK{sub w} in light and heavy water to determine the pK{sub a} values at saturation vapor pressure. The experimental results show excellent agreement with known literature values in light water where they exist at lower temperatures. These equilibrium constants are the first to be reported for both chemical systems in heavy water above 25 deg. C. This work extends the equilibrium constants in H{sub 2}O: - For HCO{sub 3}{sup -} from 250 deg. C to 325 deg. C; - For HPO{sub 4}{sup 2-} from 50 deg. C to 300 deg. C. These are the first ever ionization constants in D{sub 2}O for DPO{sub 4}{sup 2-} and the first values above 25 deg. C for DCO{sub 3}{sup -}. These results will be used to develop predictive models for the deuterium isotope effect on activated corrosion product transport under Candu nuclear reactor primary coolant conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

3D TiO{sub 2} submicrostructures decorated by silver nanoparticles as SERS substrate for organic pollutants detection and degradation

Graphical abstract: - Highlights: • Contrive a multifunctional SERS substrate with 3D sub-micrometer structure and multicomponent. • The blue wing of butterfly (Euploea mulciber) is used as template for Ag/TiO{sub 2} nanocomposites. • The 3D submicrostructures Ag/TiO{sub 2} presents superior SERS effect and photocatalytic activity. • Pave a facile route to prepare multifunctional material by utilizing smart structural designs in nature. - Abstract: The blue wing of butterfly Euploea mulciber is used as a template to generate Ag/TiO{sub 2} nanocomposites. Thereinto, Ag nanoparticles are deposited uniformly onto TiO{sub 2} substrate with three dimensional (3D) submicrometer structures. This unique 3D sub-micrometer structures featured with ridges, ribs and struts can provide a large number of active “hot spots” for enhanced Raman signal. Meanwhile, depositing Ag onto the TiO{sub 2} surface can greatly boost its SERS effect and photocatalytic activity by bringing additional electrons into the molecules and inhibiting electrons–holes recombination. Thus, the as-prepared 3D Ag/TiO{sub 2} submicrostructures can not only offer sensitive and reproducible SERS signals, but also present superior photocatalytic activity, which can be utilized to detect and eliminate organic pollutants.

36 MATERIALS SCIENCE↗