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At least 1,135 records · Page 63

Atomic resolution convergent beam electron diffraction analysis using convolutional neural networks

Two types of convolutional neural network (CNN) models, a discrete classification network and a continuous regression network, were trained to determine local sample thickness from convergent beam diffraction (CBED) patterns of SrTiO 3 collected in a scanning transmission electron microscope (STEM) at atomic column resolution. Acquisition of atomic resolution CBED patterns for this purpose requires careful balancing of CBED feature size in pixels, acquisition speed, and detector dynamic range. The training datasets were derived from multislice simulations, which must be convolved with incoherent source broadening. Sample thicknesses were also determined using quantitative high-angle annular dark-field (HAADF) STEM images acquired simultaneously. The regression CNN performed well on sample thinner than 35 nm, with 70% of the CNN results within 1 nm of HAADF thickness, and 1.0 nm overall root mean square error between the two measurements. The classification CNN was trained for a thicknesses up to 100 nm and yielded 66% of CNN results within one classification increment of 2 nm of HAADF thickness. Our approach depends on methods from computer vision including transfer learning and image augmentation.

36 MATERIALS SCIENCE↗

Insight into the Fast-Rechargeability of a Novel Mo 1.5 W 1.5 Nb 14 O 44 Anode Material for High-Performance Lithium-Ion Batteries

Wadsley–Roth phased niobates are promising anode materials for lithium-ion batteries, while their inherently low electrical conductivity still limits their rate-capability. Herein, a novel doped Mo 1.5 W 1.5 Nb 14 O 44 (MWNO) material is facilely prepared via an ionothermal-synthesis-assisted doping strategy. The detailed crystal structure of MWNO is characterized by neutron powder diffraction and aberration corrected scanning transmission electron microscope, unveiling the full occupation of Mo 6+ -dopant at the t1 tetrahedral site. In half-cells, MWNO exhibits enhanced fast-rechargeability. In this work, the origin of the improved performance is investigated by ultraviolet–visible diffuse reflectance spectroscopy, density functional theory (DFT) computation, and electrochemical impedance spectroscopy, revealing that bandgap narrowing improves the electrical conductivity of MWNO. Furthermore, operando X-ray diffraction elucidates that MWNO exhibits a typical solid-solution phase conversion-based lithium-ion insertion/extraction mechanism with reversible structural evolution during the electrochemical reaction. The boosted lithium-ion diffusivity of MWNO, due to the Mo 6+ /W 6+ doping effect, is confirmed by a galvanostatic intermittent titration technique and DFT. With the simultaneously enhanced electrical conductivity and lithium-ion diffusivity, MWNO successfully demonstrates its fast-rechargeability and practicality in the LiNi 0.5 Mn 1.5 O 4 -coupled full-cells. Therefore, this work illustrates the potential of ionothermal synthesis in energy storage materials and provides a mechanistic understanding of the doping effect on improving material's electrochemical performance.

25 ENERGY STORAGE↗

Facile microwave synthesis and photocatalytic activity of monodispersed BaTiO{sub 3} nanocuboids

A facile microwave hydrothermal method for preparation of monodispersed barium titanate (BaTiO{sub 3}) nanocuboids with average size of 13 nm is developed, and the effects of synthesis parameters, such as molar composition of the precursor, synthesis time and temperature, on the morphology of BaTiO{sub 3} nanocrystals are systematically evaluated. The resulting products are characterized by X-ray diffraction (XRD), Raman spectrum, infrared spectrum (IR), UV–vis diffuse reflectance spectrum, water contact angle, thermogravimetry (TG), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and selected area electron diffraction (SAED). A possible formation mechanism of BaTiO{sub 3} nanocuboids is proposed. The BaTiO{sub 3} nanocuboids show high photocatalytic activity for the degradation of Rhodamin B under UV irradiation. - Highlights: • Monodispersed BaTiO{sub 3} nanocuboids are prepared by a facile microwave process. • The BaTiO{sub 3} nanocuboids have average size of 13 nm. • Oleic acid is the key factor to control the morphology of BaTiO{sub 3} nanocuboids. • BaTiO{sub 3} nanocuboids exhibit enhanced photocatalytic properties.

36 MATERIALS SCIENCE↗

Comparative analysis of the effect of low-dimensional alumina structures on cell lines L929 and Neuro-2a

The paper presents the toxicity evaluation of nanostructures on the basis of alumina of different shape (nanofibers, nanoplates, nanosheets, nanosheet agglomerates) and with similar physical and chemical properties (particle size, specific surface area, phase composition, and zeta potential). The nanostructures were examined by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), low-temperature nitrogen adsorption, and dynamic light scattering (DLS). The cytotoxicity of nanostructures was estimated using L929 fibroblast cells and Neuro-2a tumor cells. It has been found that the L929 cells are less subject to the influence of alumina nanoparticles than the Neuro-2a tumor cells. Probably, the differences in the proliferation activity of normal and tumor cells in contact with the synthesized nanostructures are due to a change in the pH of the cell microenvironment.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis and characterization of Fe{sub 2}O{sub 3} nanoparticles by simple precipitation method

A simple and efficient synthesis of Iron-oxide nanoparticles was carried out by precipitation method using ferric chloride as precursor and ammonium hydroxide as a stabilizing agent at different calcination temperatures. The synthesized powder was characterized by powder X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscope (FE-SEM) and Transmission Electron Microscopy (TEM). X-ray diffraction indicated the formation hematite Fe{sub 2}O{sub 3} structure. FTIR showed various functional groups of particles and absorption bands related to metal oxygen vibration modes. The heating temperatures were varied at 100 °C, 200°C, and 300°C. The Fe{sub 2}O{sub 3} nanostructures with the average particle size of about 36.22 nm were prepared at 300°C for 4h. TEM study is also confirming the nanosize of Fe{sub 2}O{sub 3} particle. This aqueous precipitation method gives a large scale production of Fe{sub 2}O{sub 3} nanoparticles easily.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Cooling thermal parameters and microstructure features of directionally solidified ternary Sn–Bi–(Cu,Ag) solder alloys

Low temperature soldering technology encompasses Sn–Bi based alloys as reference materials for joints since such alloys may be molten at temperatures less than 180 °C. Despite the relatively high strength of these alloys, segregation problems and low ductility are recognized as potential disadvantages. Thus, for low-temperature applications, Bi–Sn eutectic or near-eutectic compositions with or without additions of alloying elements are considered interesting possibilities. In this context, additions of third elements such as Cu and Ag may be an alternative in order to reach sounder solder joints. The length scale of the phases and their proportions are known to be the most important factors affecting the final wear, mechanical and corrosions properties of ternary Sn–Bi–(Cu,Ag) alloys. In spite of this promising outlook, studies emphasizing interrelations of microstructure features and solidification thermal parameters regarding these multicomponent alloys are rare in the literature. In the present investigation Sn–Bi–(Cu,Ag) alloys were directionally solidified (DS) under transient heat flow conditions. A complete characterization is performed including experimental cooling thermal parameters, segregation (XRF), optical and scanning electron microscopies, X-ray diffraction (XRD) and length scale of the microstructural phases. Experimental growth laws relating dendritic spacings to solidification thermal parameters have been proposed with emphasis on the effects of Ag and Cu. The theoretical predictions of the Rappaz-Boettinger model are shown to be slightly above the experimental scatter of secondary dendritic arm spacings for both ternary Sn–Bi–Cu and Sn–Bi–Ag alloys examined. - Highlights: • Dendritic growth prevailed for the ternary Sn–Bi–Cu and Sn–Bi–Ag solder alloys. • Bi precipitates within Sn-rich dendrites were shown to be unevenly distributed. • Morphology and preferential region for the Ag{sub 3}Sn growth depend on Ag content and Ṫ{sub L}. • Rappaz-Boettinger model reasonably estimated the experimental scatter of λ{sub 2}.

36 MATERIALS SCIENCE↗

Atomic structure of different surface terminations of polycrystalline ZnPd

The intermetallic compound ZnPd has been found to have desirable characteristics as a catalyst for the steam reforming of methanol. The understanding of the surface structure of ZnPd is important to optimize its catalytic behavior. However, due to the lack of bulk single-crystal samples and the complexity of characterizing surface properties in the available polycrystalline samples using common experimental techniques, all previous surface science studies of this compound have been performed on surface alloy samples formed through thin-film deposition. In this study, we present findings on the chemical and atomic structure of the surfaces of bulk polycrystalline ZnPd studied by a variety of complementary experimental techniques, including scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), low energy electron microscopy (LEEM), photoemission electron microscopy (PEEM), and microspot low-energy electron diffraction ( μ -LEED). These experimental techniques, combined with density functional theory (DFT)-based thermodynamic calculations of surface free energy and detachment kinetics at the step edges, confirm that surfaces terminated by atomic layers composed of both Zn and Pd atoms are more stable than those terminated by only Zn or Pd layers. DFT calculations also demonstrate that the primary contribution to the tunneling current arises from Pd atoms, in agreement with the STM results. The formation of intermetallics at surfaces may contribute to the superior catalyst properties of ZnPd over Zn or Pd elemental counterparts. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Microstructural, Oxidation, and Mechanical Behavior of NbTi-Based Refractory Alloys with 5 to 10 Pct Co, Cr, and Ni Additions

NbTi-based refractory alloys with additions of Co, Cr, and Ni represent an interesting medium-entropy alloy system with potential for protective oxide film formation, high strength, and ductility. This study investigates the microstructural evolution, oxidation behavior, and mechanical properties of NbTi-based alloys containing 5 to 10 at. pct Co, Cr, and Ni. CALPHAD predictions suggest that this composition range can be heat treated to obtain a predominantly body-centered cubic matrix phase. Mechanical properties, including microhardness, yield strength, maximum strength, and specific strength are evaluated through isothermal compression tests conducted between room temperature and 800 °C. The oxidation kinetics of these alloys are assessed through discontinuous oxidation tests. Parabolic oxidation kinetics were observed for NbTi–10Ni and NbTi–5Co, while linear oxidation kinetics were found for NbTi–10Cr and NbTi–10(CoCrNi). Microstructures and oxide layers are characterized using X-ray diffraction, electron backscatter diffraction, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. All alloys exhibit significant mechanical softening between room temperature and 800 °C, with elastic-perfectly plastic flow observed at 800 °C. The addition of 10 pct Cr to NbTi resulted in two BCC phases up to 1050 °C, conflicting with CALPHAD predictions of a single-phase solid solution at this temperature, and resulting in higher flow stress at 800 °C. NbTi–10(CoCrNi) exhibited the lowest flow stress at 800 °C despite having more ‘cocktail effect’ potential and insufficient molar fractions of Co, Cr, or Ni to form a desirable protective oxide film.

36 MATERIALS SCIENCE↗

Characterization of the intermediate in formation of selenate-substituted ettringite

Precipitation of SeO{sub 4}{sup 2−}-substituted ettringite is an efficient method to immobilize SeO{sub 4}{sup 2−} under alkaline conditions. The effect of SO{sub 4}{sup 2−} on SeO{sub 4}{sup 2−} immobilization was investigated, because SO{sub 4}{sup 2−} is one of the major ions in aqueous and soil environments and it is easily incorporated in ettringite. We aimed to systemically elucidate the formation mechanisms of SeO{sub 4}{sup 2−}-substituted ettringite with and without SO{sub 4}{sup 2−}. When SO{sub 4}{sup 2−} and SeO{sub 4}{sup 2−} coexisted, both oxoanions were immediately coprecipitated with ettringite after adding a Ca source. Although SO{sub 4}{sup 2−} was partially substituted by SeO{sub 4}{sup 2−} in ettringite, no other phases were formed during the process. Without SO{sub 4}{sup 2−}, SeO{sub 4}{sup 2−}-substituted AFm phase was formed as an intermediate, confirmed by X-ray diffraction peak at d 2.878, as well as by scanning electron microscopy with energy dispersive X-ray spectroscopy and zeta potential measurements. It is clear that the incorporation mechanism of SeO{sub 4}{sup 2−} in ettringite is dependent on coexisting SO{sub 4}{sup 2−} in aqueous environments. - Highlights: • SO{sub 4}{sup 2−} is preferentially incorporated in ettringite over SeO{sub 4}{sup 2−}. • Coexisting SO{sub 4}{sup 2−} influences immobilization of SeO{sub 4}{sup 2−}. • SO{sub 4}{sup 2−}–hydrocalumite is proved as an intermediate. • The zeta potential and SEM-EDX support the XRD results.

36 MATERIALS SCIENCE↗

Two-step deformation-induced martensitic transformation in additively manufactured High-Si stainless steel

Deformation-induced phase transformation in the additively manufactured (AM) Fe–18Cr–8Ni-5.5Si (in wt.%) alloy was analyzed using the in-situ electron backscattered diffraction (EBSD) record during uniaxial tensile testing in a scanning electron microscope (SEM). Analysis of EBSD data was focused to investigate phase transformation behavior during deformation with consideration of mechanical interactions among phases and grains in the ultrafine AM microstructure. The initial EBSD phase map illustrated that the as-built microstructure was a duplex structure consisting of major austenite (γ) and minor ferrite phases, some of which showed non-traditional orientation relationship since the rapid solidification in the AM process has produced non-equilibrium state in phase formation. In the deformed as-built AM alloy, the two-step martensitic transformation (γ→ε→α´) was identified as the main deformation-induced transformation mechanism. Martensitic transformation steps were found to be associated with glides of Shockley partial dislocations on closed packed (111) planes under the influence of atomic disturbance in the γ and ε phases, respectively. Using the closed-packed plane pole figures and unit cell orientations, their evolutions and mechanisms accompanying with the transformation were analyzed. Finally, the results indicate that one variant of ε-martensite forms from their parent γ phase, while two variants of α´ form from their parent ε phase.

36 MATERIALS SCIENCE↗

Superlattice reflection signatures of the insulator–metal transition in V 3 O 5 thin films

Nanoelectronic systems that are inspired by the brain are increasingly looking to insulator–metal transition (IMT) materials as they can mimic the response characteristics of neurons to temperature changes so that these can be used in robotic and computational applications. V 3 O 5 has an insulator–metal transition at ∼430 or ∼80 K higher than VO 2 and provides a unique high-temperature opportunity for these types of applications. Here, in this work, we track the structural evolution of V 3 O 5 thin films across the IMT through conventional selected-area electron diffraction (SAED) and four-dimensional scanning TEM (4D-STEM), correlated with temperature-dependent resistance measurements. SAED patterns show reversible evidence of superlattice reflections associated with the IMT—present below T IMT and absent above it—consistent with the accompanying drop in resistance. At room temperature, nanobeam electron diffraction patterns further reveal three local configurations: (i) type I regions with clean patterns lacking superlattice reflections and spot splitting; (ii) type II regions exhibiting rows of superlattice reflections and split spots indicative of crystallographic variants; and (iii) type III regions with negligible superlattice reflections but larger spot splitting suggestive of overlapping domains of insulating and conducting phases likely driven by local lattice distortions. Upon heating, the superlattice reflections disappear between 413 and 453 K, concurrent with the resistance drop at T IMT , consistent with the emergence of a conducting phase. The overall diffraction geometry remains essentially unchanged up to 573 K, implying that relative domain orientations persist through the transition. These observations reveal nanoscale structural heterogeneity in V 3 O 5 thin films across the IMT and inform operation in regimes where mixed-phase textures are expected. A plausible indexing framework rationalizing the observed geometries is presented in the Discussion section, alongside its limitations and alternative interpretations.

25 ENERGY STORAGE↗

A Multi-Layer Composite Based on the 3Ni–Al System Produced by a Combined Deformation Treatment

Using combined deformation processing, including preliminary mechanical activation followed by consolidation via high-pressure torsion, a multi-layer nanocomposite based on nickel and aluminum is manufactured. The influence of the duration of mechanical activation on its microstructure parameters is investigated by the X-ray diffraction analysis and scanning and transmission electron microscopy. It is found out that nanostructuring of the multi-layer nanocomposite during its manufacture ensures the formation of a high density of phase and grain boundaries. It is shown that this structural transformation is accompanied by an intense strengthening effect.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis and characterization of DC magnetron sputtered nano structured molybdenum thin films

Molybdenum (Mo) thin films were deposited on corning glass (#7059) substrates using DC magnetron sputtering system. The effect of substrate temperature on the structural, morphology and topological properties have been investigated. Films were characterized by variety of techniques such as low angle x-ray diffraction (low angle XRD), field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM). The low angle XRD analysis revealed that the synthesized Mo films are nanocrystalline having cubic crystal structure with (110) preferential orientation. The microstructure of the deposited Mo thin films observed with FE-SEM images indicated that films are homogeneous and uniform with randomly oriented leaf shape morphology. The AFM analysis shows that with increase in substrate temperature the rms roughness of Mo films increases. The obtained results suggest that the synthesized nanostructured Mo thin films have potential application as a back contact material for high efficiency solar cells like CdTe, CIGS, CZTS etc.

36 MATERIALS SCIENCE↗

Optimization of BaZrO{sub 3} concentration as secondary phase in superconducting YBa{sub 2}Cu{sub 3}O{sub 7} for high current applications

We report the superconducting state properties of YBa{sub 2}Cu{sub 3}O{sub 7} (YBCO) on introduction of BaZrO{sub 3} (BZO) as a secondary phase. YBCO+xBZO (x= 0, 2, 4, 6, and 10 wt%) composite samples were prepared by solid state reaction method and characterized for structural, morphological and superconducting properties. X-ray diffraction confirms the increased crystallinity and images of scanning electron microscopy measurement show an increase in both grain size and grain connectivity on addition of BZO in YBCO. These effects are well pronounced in an applied magnetic field. Critical current density, J{sub C}, as well as the pinning force peaks at 4% of BZO concentration showed significant difference. A three-fold enhancement in J{sub C} and a six-fold enhancement in pinning force were observed at this optimum BZO concentration. This has been attributed to the pinning of flux lines in YBCO due to introduction of BZO as a secondary phase. These results show that this composite has potential application in high current applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Oxide Growth and Validation for Aluminum Research Reactor Fuel - 19422

Aluminum fuel cladding will undergo general corrosion with resulting formation of adherent oxide films during in-reactor and post-discharge exposures under various water conditions and temperatures. These oxides include chemically-bound water that can pose challenges for extended dry storage. This paper describes laboratory experiments performed to produce hydroxide (oxide) films on aluminum 1100, 6061 and 5052 series alloy substrates immersed in water at controlled temperatures. The results are compared to the oxide film present on a spent fuel assembly irradiated in research reactor. This work is part of a broad investigation to address knowledge gaps and technical data needs for dry storage of aluminum-clad spent nuclear fuel (SNF). To adequately assess the risks posed by chemically-bound water on SNF in dry storage and strategies for removing chemically bound water, it is necessary to understand the expected composition and loading of oxide films on SNF of different service histories and to investigate the response of such oxides to irradiation and potential drying methods. These efforts require both the growth of films under controlled conditions and the production of non-radioactive surrogates for testing. The current work comprises experimental investigation of oxide growth via (1) laboratory experiments to produce hydroxide films on aluminum alloy substrates immersed in water at controlled temperatures and (2) characterization and comparison of laboratory-grown oxides to oxides on service-exposed aluminum alloys. The important factors affecting oxide growth and characteristics typical of oxide films formed by aqueous corrosion under conditions similar to in-reactor are reviewed. Aluminum oxide films were grown under a variety of controlled temperature conditions and durations to serve as surrogates for oxides found on aluminum-clad spent nuclear fuel due to aqueous corrosion. The chemically-bound water found in oxides formed by aqueous corrosion poses challenges for extended dry storage, requiring investigation of how the oxide loading and characteristics vary with exposure history and to provide the initial condition for investigation of drying methods. Characteristics including chemical composition, oxide morphology, and film thickness were measured to assess whether the surrogate films were representative of in-service-produced oxides on SNF. Tests were conducted in liquid water at atmospheric pressure in the temperature range 50-100 deg. C, with and without heat flux through the corroding surface, to replicate in-service conditions, and at 185 deg. C inside pressure vessels to replicate pre-filming procedures. Three different alloys commonly used in aluminum clad research reactor fuel were considered: Al-1100, Al-6061, and Al-5052. Specimens were characterized by weighing before and after exposure to measure oxide mass loading, X-ray diffraction to identify oxide composition, and scanning electron microscopy to examine the oxide morphology and film thickness. The oxide type and the morphological characteristics of the film on a fuel element from the Uruguay RU1 research reactor were determined and compared to the laboratory surrogates. The results show some differences compared to the 50 deg. C laboratory specimen that are rationalized with the service storage history of the element. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solid-state transformation of Fe-rich intermetallic phases in Al–5.0Cu–0.6Mn squeeze cast alloy with variable Fe contents during solution heat treatment

The Al–5.0 wt.% Cu–0.6 wt.% Mn alloys with a variable Fe content were prepared by squeeze casting. Optical microscopy (OM), Deep etching technique, scanning electron microscopy(SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to examine the solid-state transformation of Fe-rich intermetallics during the solution heat treatment. The results showed that the Chinese script-like α-Fe, Al{sub 6}(FeMn) and needle-like Al{sub 3}(FeMn) phases transform to a new Cu-rich β-Fe (Al{sub 7}Cu{sub 2}(FeMn)) phase during solution heat treatment. The possible reaction and overall transformation kinetics of the solid-state phase transformation for the Fe-rich intermetallics were investigated. - Graphical abstract: Display Omitted - Highlights: • The α-Fe, Al{sub 6}(FeMn) and Al{sub 3}(FeMn) phases change to the β-Fe phases. • Possible reactions of Fe phases during solution heat treatment are discussed. • The overall fractional transformation rate follows an Avrami curve.

36 MATERIALS SCIENCE↗

Effect of low-dimensional alumina structures on viability of L 929 cells

In the study, we estimated the cytotoxicity of alumina nanoparticles differing in shape (nanofibers, nanoplates, nanosheets, agglomerates of nanosheets) and close in physicochemical properties (particle size, specific surface area, phase composition, and zeta potential). The alumina structures were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) data, low-temperature nitrogen adsorption, and dynamic light scattering (DLS). The cytotoxicity was estimated on fibroblast cells of the L929 line. It was found that a more adverse effect on the cells was exerted by alumina nanofibers and nanosheets. The action of nanosheets on the cells was inhibitory and was of about the same level, irrespective of the observation period. The effect of alumina nanosheet agglomerates and nanoplates on the cell proliferation was weak even at an exposure time of 72 h.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Embedded Ge nanocrystals in SiO{sub 2} synthesized by ion implantation

200 nm thick SiO{sub 2} layers grown on Si substrates were implanted with 150 keV Ge ions at three different fluences. As-implanted samples were characterized with time-of-flight secondary ion mass spectrometry and Rutherford backscattering spectrometry to obtain depth profiles and concentration of Ge ions. As-implanted samples were annealed at 950 °C for 30 min. Crystalline quality of pristine, as-implanted, and annealed samples was investigated using Raman scattering measurements and the results were compared. Crystalline structure of as-implanted and annealed samples of embedded Ge into SiO{sub 2} matrix was studied using x-ray diffraction. No secondary phase or alloy formation of Ge was detected with x-ray diffraction or Raman measurements. Scanning transmission electron microscope measurements were done to get the nanocrystal size and localized information. The results confirmed that fluence dependent Ge nanocrystals of different sizes are formed in the annealed samples. It is also observed that Ge is slowly diffusing deeper into the substrate with annealing.

36 MATERIALS SCIENCE↗