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At least 1,441 records · Page 80

Unsupported and carbon-supported silver catalysts for oxygen reduction reaction in alkaline media

Quick and easy Ag catalysts preparation via wet chemical synthesis method using only reducing agent (pure-Ag); reducing agent and citric acid as the capping agent (Ag-CA); and carbon support (KetjenBlack 600J), capping agent, and the reducing agent (Ag/C) is demonstrated. The Ag-based electrocatalysts are characterized by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) with energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of Ag catalysts for O 2 reduction reaction (ORR) in 1 M KOH is evaluated using the rotating (ring)-disc electrode method. SEM and HAADF-STEM results show that the unsupported pure-Ag and Ag-CA catalysts consist mainly of big agglomerates, and Ag/C has the smallest agglomerates and some sub-3 nm Ag nanoparticles. The XPS results reveal that Ag in all the catalysts is in the metallic form (Ag 0 ). Despite consisting of big agglomerates, the Ag-CA catalyst exhibits similar ORR electrocatalytic activity to that of Ag/C. Ag-CA (unsupported) shows the lowest hydrogen peroxide yield. These results are of great importance for the development of Ag-based catalysts that can be prepared in a fast, simple and easily up scalable fashion, for anion exchange membrane fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer during the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.

08 HYDROGEN↗

Relationship between nanostructure-magnetic property induced by temperature for iron oxide nanoparticles in vacuum, Ar and O 2 environments

It is known that superparamagnetic magnetite (Fe 3 O 4 ) nanoparticles (NPs) become ferromagnetic under Si 2+ ion irradiation due to particle size growth and microstructure evolution; it has been proposed that this feature could be used for in situ high temperature (up to 500 °C) radiation monitoring in the core of nuclear reactors. Herein, magnetite NPs synthesized by a nanocluster deposition system are heated to 800 °C in three different environments (argon, oxygen and vacuum), and nanostructure-magnetic property correlations are investigated by vibrating sample magnetometry, scanning electron microscopy, and X-ray diffraction. Magnetization of the NPs is increased due to the sintering and overall size growth by the agglomeration of the particles, while the morphology remains nearly unchanged up to 800 °C, with the one anomaly that zerovalent Fe appeared due to the reduction of the Fe 3 O 4 at 800 °C in vacuum. In argon and oxygen at high-temperature, antiferromagnetic hematite is created, which causes a reduction of the magnetization, and abrupt growth of particle size above 500 °C.

36 MATERIALS SCIENCE↗

What causes the variation in superconducting properties of UTe 2 ?

Reaching a consensus on the superconducting order parameter of unconventional superconductors remains a central challenge in the field of magnetically-mediated superconductivity. Though UTe 2 is largely accepted as a rare example of an odd-parity superconductor, its precise order parameter remains highly debated, even at ambient conditions. A key underlying issue is the large sample-to-sample variation in superconducting properties at zero applied pressure and magnetic field. Here, we investigate the origin of the observed variation by means of single crystal x-ray diffraction (SC-XRD) and scanning transmission electron microscopy (STEM) measurements. Our results reveal highly ordered crystalline lattices, in agreement with the expected Immm structure, and no signs of uranium vacancies. Tiny amounts of interstitial defects, however, are observed on the Te2 layers that host Te chains along the b axis. We argue that these defects give rise to slightly enhanced atomic displacement parameters observed in SC-XRD data and are enough to disrupt the unconventional superconducting state in UTe 2 . Our findings highlight the need to focus future order parameter determination efforts on single crystals of UTe 2 with minimal amounts of structural disorder.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Micro to nanostructural observations in neutron irradiated nuclear graphites PCEA and PCIB

Here, the neutron irradiation induced structural changes in nuclear grade graphites PCEA and PCIB were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS). The graphite samples were irradiated at the Advanced Test Reactor National User Facility at the Idaho National Laboratory. Received doses ranged from 1.5 dpa - 6.8 dpa and irradiation temperatures varied between 350°C - 670°C. XRD data showed crystallite sizes to reduce by 35% (for both La and Lc) for low dose, low temperature specimens and by 50% (for both La and Lc) for high dose, high temperature specimens (compared to unirradiated specimens of the same grade). Analysis of the G peak in Raman spectra of irradiated specimens provided evidence for the fragmentation of crystallites following neutron irradiation. Conventional TEM and SAED were used to observe the structure of lattice fringes and measure the spacing of planes. Image analysis software was applied to TEM images to quantify fringe length, tortuosity, and relative orientation of planes. Neutron irradiation appeared to induce basal plane fragmentation and curvature. EELS was performed to study the proportion of sp2 bonding and specimen density. The high dose high temperature specimens showed evidence of structural recovery where sp2 values are slightly higher than values associated with low dose low temperature specimens. Data from XRD, Raman, TEM, SAED and EELS showed that low dose low temperature specimens tended to exhibit higher structural damage (such as lower sp2 content, higher d-spacing, and reduced crystallite size) than high dose high temperature specimens.

36 MATERIALS SCIENCE↗

Microstructural evolution of Mo-UO 2 cermets under high temperature hydrogen environments

Ceramic-metallic (cermet) materials show promise for use in nuclear thermal propulsion applications due to attractive thermophysical properties including high temperature stability and high thermal conductivity. In this work, molybdenum-uranium dioxide (Mo-UO 2 ) cermet fuel elements were fabricated by means of spark plasma sintering (SPS) and were subsequently exposed to hydrogen at high temperatures (2500 K). Mo-UO 2 samples pre- and post-exposure were characterized by means of optical microscopy, scanning electron microscopy, and X-ray diffraction (XRD). Microscopy analyses of the as-produced material displayed microscopic cracking on the interior of the spherical UO 2 fuel particles but confirmed that the fuel particles were fully encapsulated in the Mo matrix. The results further showed mass loss, macroscopic swelling, and cracking in the cermet samples which occurred during high temperature hydrogen testing. Nanoscale swelling was evidenced by XRD in the Mo matrix and UO 2 fuel structure due to the incorporation of defects and accompanied microstrain.

36 MATERIALS SCIENCE↗

Insight into the interfacial microstructure and chemistry of hot isostatically pressed AA6061-AA6061 bonds for U-10Mo fuel cladding application

Here, in the present study, hot isostatic pressing (HIP) bonding was carried out using AA6061-AA6061 plates for U-10Mo monolithic fuel cladding application. HIP was performed at 560°C with an applied isostatic pressure of 103 MPa for 90 min. Interfacial microstructure characterizations were performed using scanning electron microscopy (SEM) combined with electron backscatter diffraction (EBSD) to quantify precipitate fractions and study recrystallization, grain growth, and orientation relationships across the interface. EBSD results confirmed that no interfacial grain growth occurred during the HIP process. Transmission electron microscopy (TEM) was also employed to quantify composition and identify phases of various precipitates and an oxide layer that formed at the interface during HIP bonding. Microstructural analyses revealed the formation of a large fraction of Mg 2 Si precipitate and a ~50 nm thick Mg-oxide layer at the interface. Further TEM analysis confirmed that the oxide layer was not continuous, and Mg 2 Al 2 O 5 oxide particles with an average size of 18 nm were present in the oxide layer. Finite element modeling analysis was performed to study the stress distribution at the interface during HIP processing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Structural transition from two-dimensional ZIF-L to three-dimensional ZIF-8 nanoparticles in aqueous room temperature synthesis with improved CO2 adsorption

Highlights: • ZIF-L and ZIF-8 were synthesised with the same molar ratio of reagents (Zn{sup + 2}/Hmim = 8). • TEA threshold loading which was responsible for the phase transition was determined. • The CO{sub 2} desorption was improved due to increase of surface basicity and porosity. - Abstract: A new micron-sized leaf- two-dimensional (2D) structured zeolitic imidazolate framework (ZIF-L) and nano-sized ZIF-8 were successfully synthesised in aqueous basic solution at room temperature with the same molar ratio of reagents (Zn{sup + 2}/Hmim = 8). Both ZIFs have attracted tremendous research interest due to their wide applications including absorption, separation, and catalysis. This phase and morphology change could be tailored by changing the concentration of base-type additive triethylamine (TEA). Also, this morphology change from 2D (ZIF-L) to three-dimensional (3D) (ZIF-8) was observed by X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), attenuated total reflectance infrared (ATR-IR) spectroscopy analysis, and surface area and pore textural properties using micromeritics gas adsorption analyser. The total amount of basic sites and carbon dioxide (CO{sub 2}) desorption capacity were also calculated using CO{sub 2} temperature-programmed desorption (CO{sub 2}-TPD) technique. Furthermore, TEA/total mole ratio of 0.0006 was proved as transition loading between two phases. Also, the particle and crystal size of samples decreased with increasing TEA/total mole ratio. The smallest ZIF-L and ZIF-8 particles obtained were 1.6 μm and 177 nm, respectively that showed excellent thermal stability. The basicity and uptakes of CO{sub 2} improved proportionally with TEA and followed this order: ZIF-8 > ZIF-L. This study provides some new insights into zeolitic imidazolate framework by controlling crystal growth and morphology.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The effect of ball-milling time and annealing temperature on fracture toughness of Ni-3 wt.% SiC using small punch testing

Highlights: • The fracture energy of Ni-SiC is strongly dependent on the grain size of Ni matrix • The ball-milling time governs the fracture behaviour of Ni-3 wt.% SiC • A higher proportion of big SiC particles at grain boundary is responsible for a lower fracture toughness - Abstract: A set of dispersion strengthened Ni-3 wt.% SiC samples have been prepared via a powder metallurgy route for an application in molten salt reactor (MSR) systems. A mixture of 97 wt.% Ni and 3 wt.% SiC powder was prepared by varying the ball-milling time (8, 24, 36 and 48 h). The ball-milling process was followed by powder consolidation using spark plasma sintering (SPS) and rapid cooling to room temperature. The samples were then annealed at different temperatures (300 °C, 700 °C and 850 °C). The fracture behaviour of the Ni-3 wt.% SiC samples was investigated using the Small Punch Test (SPT). A scanning electron microscope (SEM) with energy dispersive spectrometer (EDS) and electron back-scatter diffraction (EBSD), as well as transmission electron microscopy (TEM) were employed to examine the microstructure of the tested Ni-3 wt.% SiC samples. The obtained results show that the SPT fracture energy is strongly dependent on the grain size of Ni matrix, which is affected by ball-milling times and annealing temperature. It has been further found that the segregation of large SiC particles at grain boundaries promotes intergranular fracture and thus significantly reduces the fracture energy. The results indicate that the distribution and size of SiC particles at grain boundary is mainly affected by the ball-milling time. Hence, the ball-milling time governs the fracture toughness of Ni-3 wt.% SiC samples.

36 MATERIALS SCIENCE↗

Effects of in-process cryocooling on metallurgical and mechanical properties of friction stir processed Al7075 alloy

Highlights: • For in-process cryocooling (IPC) during FSP, an efficient cooling fixture was designed & fabricated. • FSP of Al7075 alloy with IPC setup suppressed precipitate coarsening as well as grain growth. • Nanosize η′ precipitates (20–30 nm) in IPC condition increased work hardening capacity & strength. • Simultaneous improvement in ductility & strength occurred for sample FSPed with IPC. - Abstract: Friction stir processing (FSP) of heat treatable aluminum alloys is reported to deteriorate strength and hardness properties in spite of huge grain size refinement. The improvement in strength due to the grain size refinement after FSP could not be able to offset the reduction in strength due to coarsening or dissolution of the strengthening precipitate(s). To overcome this, the present work investigates an effective way of heat rejection from the FSP zone to control the precipitate evolution besides the grain size refinement during FSP of Al7075 alloy. The FSP was carried out with standardized process parameters (i.e. 720 rpm, 65 mm/min traverse speed) under two different cooling environments: (i) at normal air cooling and (ii) by rushing a chilled mixture (−30 °C) of liquid nitrogen and methanol through the bottom of the backing plate. Microstructural evolution was examined through optical, scanning and transmission electron microscopy and electron backscatter diffraction to confirm the grain size and morphology of precipitate(s) formed. The in-process cryocooling during the FSP led to 65 and 72% improvement in the Vickers hardness and tensile strength, respectively, in comparison to the solutionized base metal. The results have been analyzed in terms of precipitate interface characteristics and its strengthening effect, Hall–Petch strengthening due to grain size reduction and tradeoff between them.

36 MATERIALS SCIENCE↗

Biosynthesis of the palladium/sodium borosilicate nanocomposite using Euphorbia milii extract and evaluation of its catalytic activity in the reduction of chromium(VI), nitro compounds and organic dyes

Highlights: • Green synthesis of Pd/sodium borosilicate nanocomposite using Euphorbia milii aqueous extract. • Characterization of catalyst by FT-IR, XRD, FESEM, EDS, TEM and elemental mapping. • Catalytic reduction of Cr(VI), 2,4-DNPH, 4-NP, CR, MO and MB by Pd/sodium borosilicate nanocomposite. - Abstract: For the first time, a green method is developed to prepare palladium/sodium borosilicate nanocomposite by using aqueous extract of the leaves of Euphorbia milii as bioreducing and stabilizing agent. The immobilization of Pd NPs on the surface of the sodium borosilicate glass was established by several instrumental analysis including X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), EDS elemental dot maps and transmission electron microscopy (TEM). The green synthesized nanocatalyst exhibited excellent performance in the reduction of the chromium (VI) (Cr(VI)), nitro compounds such as 2,4-dinitrophenylhydrazine (2,4-DNPH) and 4-nitrophenol (4-NP) and some organic dyes containing Congo red (CR), Methyl orange (MO), and Methylene blue (MB). The biosynthesized heterogeneous catalyst was easily recovered and reused at least in 5 consecutive reactions with no losing of its performance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Surface grain refinement of casting A380 aluminum alloy by ultrasonic-assisted surface mechanical grinding treatment

A novel surface processing technique, ultrasonic-assisted surface mechnical grinding treatment (U-SMGT), was proposed and applied to modify the surface micriostructure of the casting aluminum alloy (A380). Comprehensive post-process chracterization techniques including 3D profilometry, optical microscope, scanning electric microscopy (SEM), and electron backscatter diffraction (EBSD) were carried out to investigate the surface morphology and microstructure of the processed region (PR). It was found that a surface layer of grain refinement with a thickness of about 50 µm was formed. In the as-received base material (BM), large clusters of dendritic eutectic phase with a size of approximately 20 µm were isolated by α-Al matrix. Nano-indentation tests showed that hardness of the eutectic and α-Al in the as-received BM was 2.15 GPa and 1.2 GPa respectively. After U-SMGT, the large dendritic eutectic phase was broken down into much fine particles with an average size of 0.57 µm. These fine particles were uniformly distributed into the α-Al matrix. Nano-indentation measurement exhibited a hardness of 2.27 GPa within the processed region. The overall high hardness in the processed region is a result of the pinning effect of uniformly distributed fine dendrites and grain refinement of Al-matrix.

36 MATERIALS SCIENCE↗

Investigation of deformation mechanisms in an advanced FeCrAl alloy using in-situ SEM-EBSD testing

The deformation mechanisms associated with uniaxial tensile testing are observed by conducting tensile experiments of an FeCrAl alloy using scanning electron microscopy (SEM) coupled with electron backscattered diffraction (EBSD). Prior to the deformation, investigated alloy was consisting grain and precipitate size of ~63.0 μm and ~6.7 μm, respectively. The recorded SEM micrographs and EBSD data at increasing levels of strains revealed the complex phenomena of slip bands’ formation in the presence of surface grain morphology evolution and their (001), (110) and (111) crystallographic planes distortions. The grains with orientation (110)||tensile direction (TD) shows higher shape change; however, (001)||TD and (111)||TD oriented grains show higher lattice gradient formation. Extracted information from the EBSD indicates that the crystallographic rotations drive towards specific, fiber-like texture in relation to the loading direction. Postmortem analysis of the recorded microstructure during the tensile deformation explains the phenomena of crack formation in the hard-intermetallic particles before the ultimate tensile strength (UTS). However, after the UTS, pores were identified in the neck that resulted from extensive plastic deformation. In-depth analysis was carried out to identify the cause of cracks and pores formation phenomena during the tensile test.

36 MATERIALS SCIENCE↗

Quasi-static and dynamic response of a Cu/Nb composite following equal channel angular extrusion

The article presents a study of the plastic properties of a Cu–18%Nb composite following equal channel angular extrusion under both low- and high-strain rate loadings. The microstructures are characterized by optical and scanning electron microscopy as well as electron backscatter diffraction. Comparisons are also made with a Cu–50%Nb laminate made by accumulative roll bonding. Textures obtained within the respective phases in the extruded composite closely mimic those previously reported for the pure components alone (Cu, Nb). Grain sizes of the major phase (Cu) exhibit broad distributions, due largely to partial recrystallization during the extrusion process. Further re-crystallization is obtained within localized deformation bands produced at high strain rates (3 × 10 3 s –1 ). While the degree of anisotropy and the strain rate sensitivity of the composite response are similar to those of pure Cu after extrusion, the strength levels of the composite are somewhat greater, falling broadly between those obtained in the pure components after extrusion to comparable plastic strains. Furthermore, the implications for selection of composite composition and processing for achieving higher strengths are briefly discussed.

36 MATERIALS SCIENCE↗

Terrace site hydroxylation upon water dimer formation on monolayer NiO/Ag(100)

The interaction of water vapor with monolayer NiO/Ag(100) was examined using both experimental and computational techniques. Initial film growth was characterized by scanning tunneling microscopy and low energy electron diffraction showing the formation of NiO(1×1). X-ray photoelectron spectroscopy (XPS) reveals that the initial film was mainly composed of NiO oxide with a small amount of hydroxyl groups (OH) attributed to the dissociation of background water vapor at highly reactive edge sites. Density functional theory (DFT) reveals that the adsorption of a water monomer on NiO/Ag(100) terrace sites prefers to be in the molecular rather than the dissociate state. XPS results indicate that upon exposing the oxide film to high water vapor pressures (maximum 333.3 Pa), extensive hydroxylation occurs which is attributed to water dissociation at terrace sites. DFT reveals that upon aggregation of water monomers to dimers at the oxide interface the dissociated dimer is energetically stable. The results herein are consistent with previous MgO/Ag(100) studies, further revealing that for certain metal oxides the formation of water dimers at the metal oxide-vapor interface is a key mechanism leading to extensive terrace site hydroxylation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mesoporous Crystalline Niobium Oxide with a High Surface Area: A Solid Acid Catalyst for Alkyne Hydration

A mesoporous crystalline niobium oxide with tunable pore sizes was synthesized via the sol–gel-based inverse micelle method. The material shows a surface area of 127 m 2 /g, which is the highest surface area reported so far for crystalline niobium oxide synthesized by soft template methods. The material also has a monomodal pore size distribution with an average pore diameter of 5.6 nm. A comprehensive characterization of niobium oxide was performed using powder X-ray diffraction, Brunauer–Emmett–Teller, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, UV–vis, and X-ray photoelectron spectroscopy. The material acts as an environmentally friendly, solid acid catalyst toward hydration of alkynes under with excellent catalytic activity (99% conversion, 99% selectivity, and 4.39 h –1 TOF). Brønsted acid sites present in the catalyst were found to be responsible for the high catalytic activity. Lastly, the catalyst was reusable up to five cycles without a significant loss of the activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Vapor Deposition-Grown Hexagonal Boron Nitride and Graphene for Tandem Dielectric Capacitive Polymer Devices

To address the low energy density of polymeric capacitors, this work explores how tandem combinations of antagonistic properties can enhance energy storage. We introduce multilayer architecture integrating chemical vapor deposition (CVD)-grown ≈2 nm hexagonal boron nitride (hBN) and graphene with ferroelectric polyvinylidene fluoride (PVDF) and linear polyetherimide (PEI) layers to suppress leakage paths, reduce loss, and promote Maxwell–Wagner–Sillars polarization. Raman spectroscopy, X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and plasma focused ion beam (PFIB) analyses confirm robust material integration. In conclusion, for the tandem device, E BD ≈600 V/μm, while individual layers show lower values (PVDF|Graphene (Gr)|PVDF ≈ 50 V/μm and PEI|hBN|PEI ≈ 275 V/μm), yielding an overall ≈6000% enhancement and demonstrating the effectiveness of the 2D multilayer design.

Chemical vapor deposition (CVD)↗

Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe 2 Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy

PdSe 2 has a layered structure with an unusual, puckered Cairo pentagonal tiling. Its atomic bond configuration features planar 4-fold-coordinated Pd atoms and intralayer Se–Se bonds that enable polymorphic phases with distinct electronic and quantum properties, especially when atomically thin. PdSe 2 is conventionally orthorhombic, and direct synthesis of its metastable polymorphic phases is still a challenge. Here, we report an ambient-pressure chemical vapor deposition approach to synthesize metastable monoclinic PdSe 2 . Monoclinic PdSe 2 is shown to be synthesized selectively under Se-deficient conditions that induce Se vacancies. These defects are shown by first-principles density functional theory calculations to reduce the free energy of the metastable monoclinic phase, thereby stabilizing it during synthesis. Further, the structure and composition of the monoclinic PdSe 2 crystals are identified and characterized by scanning transmission electron microscopy imaging, convergent beam electron diffraction, and electron energy loss spectroscopy. Polarized Raman spectroscopy of the monoclinic PdSe 2 flakes reveals their strong in-plane optical anisotropy. Electrical transport measurements show that the monoclinic PdSe 2 exhibits n-type charge carrier conduction with electron mobilities up to ~298 cm 2 V –1 s –1 and a strong in-plane electron mobility anisotropy of ~1.9. The defect-mediated growth pathway identified in this work is promising for phase-selective direct synthesis of other 2D transition metal dichalcogenides.

2D material↗