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At least 505 records · Page 28

Layer-dependent topological phase in a two-dimensional quasicrystal and approximant

The electronic and topological properties of materials are derived from the interplay between crystalline symmetry and dimensionality. Simultaneously introducing “forbidden” symmetries via quasiperiodic ordering with low dimensionality into a material system promises the emergence of new physical phenomena. Here, we isolate a two-dimensional (2D) chalcogenide quasicrystal and approximant, and investigate their electronic and topological properties. The 2D layers of the materials with a composition close to Ta 1.6 Te, derived from a layered transition metal dichalcogenide, are isolated with standard exfoliation techniques, and investigated with electron diffraction and atomic resolution scanning transmission electron microscopy. Density functional theory calculations and symmetry analysis of the large unit cell crystalline approximant of the quasicrystal, Ta 21 Te 13 , reveal the presence of symmetry-protected nodal crossings in the quasicrystalline and approximant phases, whose presence is tunable by layer number. Our study provides a platform for the exploration of physics in quasicrystalline, low-dimensional materials and the interconnected nature of topology, dimensionality, and symmetry in electronic systems.

36 MATERIALS SCIENCE↗

Abrupt orthorhombic relaxation in compressively strained ultrathin SrRuO 3 films

Lattice structure can dictate electronic and magnetic properties of a material. Especially, reconstruction at a surface or heterointerface can create properties that are fundamentally different from those of the corresponding bulk material. In this work, we have investigated the lattice structure on the surface and in the thin films of epitaxial SrRuO 3 with the film thickness up to 22 pseudo-cubic unit cells (u.c.), using the combination of surface sensitive low energy electron diffraction and bulk sensitive scanning transmission electron microscopy. Our analysis indicates that, in contrast to many perovskite oxides, the RuO6 tilt and rotational distortions appear even in single unit cell SrRuO 3 thin films on cubic SrTiO 3 , while the full relaxation to the bulk-like orthorhombic structures takes 3-4 u.c. from the interface for thicker films. Yet the TiO 6 octahedra of the substrate near the interface with SrRuO 3 films show no sign of distortion, unlike those near the interface with CaRuO 3 films. Two orthogonal in-plane rotated structural domains are identified. These octahedral distortions are essential for the understanding of the thickness dependent transport and magnetism in ultrathin films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NEUTRON-IRRADIATION–INDUCED DAMAGE ASSESSMENT IN CONCRETE USING COMBINED PHASE CHARACTERIZATION AND NONLINEAR FAST FOURIER TRANSFORM SIMULATION

Understanding irradiation effects in concrete cavities of light water reactors is critical to the long-term operation (60+ years) of US nuclear power plants. Susceptibility of concrete to neutron irradiation greatly varies as a function of its constituents: coarse aggregates, sand, and hardened cement paste (hcp). In particular, higher irradiation–susceptibility of aggregates was found to be a direct function of radiation-induced volumetric expansion (RIVE), or the propensity of aggregates to swell as a function of mineral contents, structures and textures. Irradiation-induced amorphization is accompanied by significant swelling, especially in silicates. For example, the maximum volumetric expansions of quartz and feldspars have been shown to be as large as ≈ 18% and ≈ 8%, respectively, while the change of density in calcite remains rather low (≈ 0.3–0.5%). High swelling is associated with a high number of covalent bonds (Si–O) and a high degree of polymerization of [SiO4] tetrahedrons. Differential RIVEs between rock-forming minerals cause high stresses and may potentially develop cracking within the aggregates at the interface between aggregates and the hcp and within the hcp. Modeling neutron-irradiation effects in concrete requires addressing the problem at a scale that captures both the details of the aggregates’ mineralogy and texture, which is <~ 100 μm, and the representative size of concrete, which is ~ 10 cm. This requires high-resolution, large mapping capabilities. To this end, the US Department of Energy (DOE) Light Water Reactor Sustainability (LWRS) Program developed an original tool suite called Microstructure Oriented Scientific Analysis of Irradiated Concrete (MOSAIC) in which Nonlinear 2D-fast Fourier transform (FFT) techniques are employed to model mechanical or irradiation-induced cracking of high-resolution complex microstructures derived from combined mapping techniques, including micro x-ray fluorescence (m-XRF), energy-dispersive x-ray spectroscopy (EDS), electron backscatter diffraction (EBSD), ellipsometry, and scanning electron microscopy (SEM). Irradiated mineral properties are derived from the Irradiated Minerals, Aggregate and Concrete (IMAC) database, which includes available relevant literature data. Rigorous coupled damage-creep simulations are obtained through sequential linear analysis. Illustrations of actual accelerated irradiation-damage propagation in a complex microstructures are presented herein.

Le Pape, Yann↗

Influence of Multidirectional Forging on Microstructural, Mechanical, and Corrosion Behavior of Mg-Zn Alloy

Multidirectional forging (MDF) was applied to Mg-6%Zn alloy up to 5 passes successfully at 280 °C. MDF-processed materials were characterized using optical microscope, scanning electron microscope, electron backscatter diffraction, transmission electron microscope, and x-ray diffraction. Obtained results showed a significant reduction in grain size (up to 3.8 μm) having a large fraction of high-angle grain boundaries after 5 passes of MDF process. Maximum tensile strength of 230 MPa was achieved for 5-pass MDF-processed Mg-6%Zn alloy which is about ~ 2.0 times higher in comparison with that of homogenized alloy (117 MPa) and was attributed to higher dislocations density and grain refinement. Corrosion behavior of the alloy was investigated in 0.1 M NaCl solution using potentiodynamic polarization test, electrochemical impedance spectra analysis, and immersion tests. It was found that the corrosion rate of 5-pass MDF sample improved (0.34 mm/year) ~2.5 times in comparison with that of homogenized Mg-6%Zn alloy (0.86 mm/year) due to fine grain structure, which creates more grain boundaries that act as a corrosion barrier.

36 MATERIALS SCIENCE↗

Interrogating the Effects of Hydrogen on the Behavior of Planar Deformation Bands in Austenitic Stainless Steel

The effects of internal hydrogen on the deformation microstructures of 304L austenitic stainless steel have been characterized using electron backscattered diffraction (EBSD), transmission Kikuchi diffraction (TKD), high-resolution scanning transmission electron microscopy (HRSTEM), and nanoprobe diffraction. Samples, both thermally precharged with hydrogen and without thermal precharging, were subjected to tensile deformation of 5 and 20 pct true strain followed by multiple microscopic interrogations. Internal hydrogen produced widespread stacking faults within the as-forged initially unstrained material. While planar deformation bands developed with tensile strain in both the hydrogen-precharged and non-precharged material, the character of these bands changed with the presence of internal hydrogen. As shown by nanobeam diffraction and HRSTEM observations, in the absence of internal hydrogen, the bands were predominantly composed of twins, whereas for samples deformed in the presence of internal hydrogen, ε -martensite became more pronounced and the density of deformation bands increased. For the 20 pct strain condition, α '-martensite was observed at the intersection of ε -martensite bands in hydrogen-precharged samples, whereas in non-precharged samples α '-martensite was only observed along grain boundaries. We hypothesize that the increased prevalence of α '-martensite is a secondary effect of increased ε -martensite and deformation band density due to internal hydrogen and is not a signature of internal hydrogen itself.

36 MATERIALS SCIENCE↗

MICRO/NANO-STRUCTURAL EXAMINATION AND FISSION PRODUCT IDENTIFICATION IN NEUTRON IRRADIATED AGR-1 TRISO FUEL

Advanced microscopic and microanalysis techniques were developed and applied to study irradiation effects and fission product behavior in selected low-enriched uranium oxide/uranium carbide TRISO-coated particles from fuel compacts in six capsules irradiated to burnups of 11.2 to 19.6% FIMA. Although no TRISO coating failures were detected during the irradiation, the fraction of Ag-110m retained in individual particles often varied considerably within a single compact and at the capsule level. At the capsule level Ag-110m release fractions ranged from 1.2 to 38% and within a single compact, silver release from individual particles often spanned a range that extended from 100% retention to nearly 100% release. In this paper, selected irradiated particles from Baseline, Variant 1 and Variant 3 type fueled TRISO coated particles were examined using Scanning Electron Microscopy, Atom Probe Tomography; Electron Energy Loss Spectroscopy; Precession Electron Diffraction, Transmission Electron Microscopy, Scanning Transmission Electron Microscopy (STEM), High Resolution Electron Microscopy (HRTEM) examinations and Electron Probe Micro-Analyzer. Particle selection in this study allowed for comparison of the fission product distribution with Ag retention, fuel type and irradiation level. Nano sized Ag-containing features were predominantly identified in SiC grain boundaries and/or triple points in contrast with only two sitings of Ag inside a SiC grain in two different compacts (Baseline and Variant 3 fueled compacts). STEM and HRTEM analysis showed evidence of Ag and Pd co-existence in some cases and it was found that fission product precipitates can consist of multiple or single phases. STEM analysis also showed differences in precipitate compositions between Baseline and Variant 3 fuels. A higher density of fission product precipitate clusters were identified in the SiC layer in particles from the Variant 3 compact compared with the Variant 1 compact. Trend analysis shows precipitates were randomly distributed along the perimeter of the IPyC-SiC interlayer but only weakly associated with kernel protrusion and buffer fractures. There has been no evidence that the general release of silver is related to cracks or significant degradation of the microstructure. The results presented in this paper provide new insights to Ag transport mechanism(s) in intact SiC layer of TRISO coated particles.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Influence of surface morphology and UFG on damping and mechanical properties of composite reinforced with spinel MgAl{sub 2}O{sub 4}-SiC core-shell microcomposites

Interface between ceramic particulate and matrix is known to control the response of the materials and functionality of the composite. Among numerous physical properties, grain structure of the materials has also played a significant role in defining the behaviour of metal matrix composites. Usually, silicon carbide (SiC) particles show poor interfacial wettability in aluminium melt. Herein, we were successfully synthesized magnesium oxide (MgO) and nanocrystalline magnesium aluminate (MgAl{sub 2}O{sub 4}) spinel coated silicon carbide (SiC) core-shell micro-composites through sol-gel technique to improve the wettability of dispersoids. Core-shell structures of submicron size were thoroughly investigated by various characterization techniques. Further, aluminium matrix composites incorporated with pristine SiC, MgO grafted SiC and MgAl{sub 2}O{sub 4} grafted SiC particles were fabricated by stir casting technique, respectively. Additionally, as-cast composites were processed via friction stir processing (FSP) technique to observe the influence of grain refinement on mechanical and damping properties. Electron back scattered diffraction (EBSD), Field emission scanning electron microscopy (FE-SEM) and X-ray energy dispersion spectroscopy (EDX) analysis were conducted for investigating grain size refinement, adequate dispersion, stability and de-agglomeration of encapsulated SiC particles in aluminium matrix. The mechanical as well as thermal cyclic (from − 100 to 400 °C) damping performance of the as-cast and friction stir processed composites were studied, respectively. Finally, the enhanced properties were attributable to reduced agglomeration, stabilization and proper dispersion of the tailored SiC particles Al matrix. - Highlights: •Synthesizing a novel coating layer of MgO and MgAl{sub 2}O{sub 4} spinel onto SiC particles •Significant improvement in UTS and hardness by reinforcing tailored SiC in Al •Significant grain refinements were obtained through FSP •SiC/MgAl{sub 2}O{sub 4}/Al exhibits ~ 61% higher storage modulus as compare to pure Al after FSP.

36 MATERIALS SCIENCE↗

Effect of Rolling Temperature on Fracture Properties of INRAFMS at Different Temperatures

Two heats of Indian reduced activation ferritic / martensitic steel have been produced with similar chemical composition and identical process parameters except the start and final rolling temperature referred as P950 and P1050, respectively. Fracture behaviours of both the heats have been evaluated, and it was found that quasistatic fracture properties are better for P1050 than P950. An attempt is made to establish the reasons for the observed behaviour through optical, scanning electron microscopic, electron backscatter diffraction and transmission electron microscopic studies. These variations are attributed to the difference in rolling temperature of both heats. P1050 meets the acceptance criteria as per Indian specifications, and it compares favourably with the international grades of equivalent RAFM steels.

36 MATERIALS SCIENCE↗

Specific physical and chemical properties of two modifications of poly(N-vinylcaprolcatam)

Two modifications of poly(N-vinylcaprolactam)—PVCL25 and PVCL40 (drying of a PVCL solution at 25 and 40°C, respectively)—as powdered films and their solutions were systematically investigated for the first time. Powders were studied by X-ray diffraction, IR spectroscopy, scanning electron microscopy, low-temperature krypton adsorption, and differential scanning calorimetry. Solutions were studied by smallangle X-ray scattering and dynamic light scattering. It was demonstrated that powders of PVCL25 and PVCL40 differ in the characteristics of the sub- and microstructure and in the water content and the solutions differ in the particle size. The relationships between the characteristics of the systems in the solid and liquid state and between the hydrodynamic diameter of PVCL particles in solution and their coagulation time were found.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cost-Effective Thermomechanical Processing of Nanostructured Ferritic Alloys: Microstructure and Mechanical Properties Investigation

Nanostructured ferritic alloys (NFAs), such as oxide-dispersion strengthened (ODS) alloys, play a vital role in advanced fission and fusion reactors, offering superior properties when incorporating nanoparticles under irradiation. Despite their importance, the high cost of mass-producing NFAs through mechanical milling presents a challenge. This study delves into the microstructure-mechanical property correlations of three NFAs produced using a novel, cost-effective approach combining severe plastic deformation (SPD) with the continuous thermomechanical processing (CTMP) method. Analysis using scanning electron microscopy (SEM)-electron backscatter diffraction (EBSD) revealed nano-grain structures and phases, while scanning transmission electron microscopy (STEM)-energy dispersive X-ray spectroscopy (EDS) quantified the size and density of Ti-N, Y-O, and Cr-O fine particles. Atom probe tomography (APT) further confirmed the absence of finer Y-O particles and characterized the chemical composition of the particles, suggesting possible nitride dispersion strengthening. Correlation of microstructure and mechanical testing results revealed that CTMP alloys, despite having lower nanoparticle densities, exhibit strength and ductility comparable to mechanically milled ODS alloys, likely due to their fine grain structure. However, higher nanoparticle densities may be necessary to prevent cavity swelling under high-temperature irradiation and helium gas production. Further enhancements in uniform nanoparticle distribution and increased sink strength are recommended to mitigate cavity swelling, advancing their suitability for nuclear applications.

36 MATERIALS SCIENCE↗

Characterization of intermetallics in aluminum to zinc coated interstitial free steel joining by pulsed MIG brazing for automotive application

In order to meet the demand for lighter and more fuel efficient vehicles, a significant attempt is currently being focused toward the substitution of aluminum for steel in the car body structure. It generates vital challenge with respect to the methods of joining to be used for fabrication. However, the conventional fusion joining has its own difficulty owing to formation of the brittle intermetallic phases. In this present study AA6061-T6 of 2 mm and HIF-GA steel sheet of 1 mm thick are metal inert gas (MIG) brazed with 0.8 mm Al–5Si filler wire under three different heat inputs. The effect of the heat inputs on bead geometry, microstructure and joint properties of MIG brazed Al-steel joints were exclusively studied and characterized by X-ray diffraction, field emission scanning electron microscopy (FESEM), electron probe micro analyzer (EPMA) and high resolution transmission electron microscopy (HRTEM) assisted X-ray spectroscopy (EDS) and selective area diffraction pattern. Finally microstructures were correlated with the performance of the joint. Diffusion induced intermetallic thickness measured by FESEM image and concentration profile agreed well with the numerically calculated one. HRTEM assisted EDS study was used to identify the large size FeAl{sub 3} and small size Fe{sub 2}Al{sub 5} type intermetallic compounds at the interface. The growth of these two phases in A2 (heat input: 182 J mm{sup −1}) is attributed to the slower cooling rate with higher diffusion time (~ 61 s) along the interface in comparison to the same for A1 (heat input: 155 J mm{sup −1}) with faster cooling rate and shorter diffusion time (~ 24 s). The joint efficiency as high as 65% of steel base metal is achieved for A2 which is the optimized parameter in the present study. - Highlights: • AA 6061 and HIF-GA could be successfully joined by MIG brazing. • Intermetallics are exclusively studied and characterized by XRD, FESEM and EPMA. • Intermetallic formation by diffusion is worth considering or not. • HRTEM-EDS, SAD pattern identifies the morphologies and size of intermetallics. • A compromise concerning formation of IMC is necessary.

36 MATERIALS SCIENCE↗

A facile recovery process for cathodes from spent lithium iron phosphate batteries by using oxalic acid

A simplistic and novel leaching process is developed to dispose spent lithium iron phosphate (LiFePO 4 ) batteries. In this paper, oxalic acid is selected as a leaching reagent to recover lithium as a resource and remove phosphorus from LiFePO 4 batteries, benefiting from its low natural effects. The physical properties of spent cathode materials (before leaching) and residues (after leaching) are identified by X-ray diffraction (XRD) and scanning electronic microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS). The total amounts of Li and Fe are analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The process occurs under conditions of a 0.3 mol·L -1 oxalic acid concentration, a temperature of 80°C, a reaction time of 60 min and a solid/liquid ratio of 60 g· L -1 . It can effectively precipitate ~92% ferrum in terms of FeC 2 O 4 ·2H 2 O from LiFePO 4 , with the leaching efficiency of Li achieving up to 98%. This method demonstrates a new strategy for dealing with spent lithium iron phosphate batteries with a low cost and low environmental impact.

25 ENERGY STORAGE↗

Toward accurate measurement of electromagnetic field by retrieving and refining the center position of non-uniform diffraction disks in Lorentz 4D-STEM

Recent advancement in scanning transmission electron microscopy (STEM) allows the use of 4D-STEM, a technique that captures an electron diffraction pattern at each scan point in STEM, to measure electrostatic and magnetic potential and field in materials. However, accurate measurement, separation of the magnetic and electric signals, and removal of artifacts remain challenging, especially in the presence of complex non-uniform diffraction contrast within the disks. In this work, based on dynamic simulations of 4D-STEM patterns built upon superstructures consisting of millions of atoms to account for different sample thickness and edge geometries, we show how the shape and intensity distribution of the central disk are affected by multiple scattering. We propose a robust refinement procedure through iteration of the spin-sensitive peak position of the disk-center in the circular Hough transform filtered images from experimental Lorentz 4D-STEM dataset after minimizing the possible artifacts, such as those due to the change of thickness, dynamic scattering, and scanning process. We verify that caution must be taken as in practice the rigid-disk-shift model used to reconstruct induction maps can easily break down due to disk-protrusion when there exists a nonconstant phase gradient or thickness within the width of the probe. Through quantitative analysis and comparing experiment with calculation the effect of the non-spin-related intensity distribution inside the disk as well as that causes the disk shift due to the intensity-protrusion can be removed, and high-quality magnetic field mapping is possible.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗

Tuning piezoelectric properties through epitaxy of La 2 Ti 2 O 7 and related thin films

Current piezoelectric sensors and actuators are limited to operating temperatures less than ~200ºC due to the low Curie temperature of the piezoelectric material. The strengthening the piezoelectric coupling of high-temperature piezoelectric materials, such as La 2 Ti 2 O 7 (LTO), would allow sensors to operate across a broad temperature range. The crystalline orientation and piezoelectric coupling direction of LTO thin films can be controlled by epitaxial matching to SrTiO 3 (001), SrTiO 3 (110), and rutile TiO 2 (110) substrates via pulsed laser deposition. The structure and phase purity of the films are investigated by x-ray diffraction and scanning transmission electron microscopy. Piezoresponse force microscopy is used to measure the in-plane and out-of-plane piezoelectric coupling in the films. The strength of the out-of-plane piezoelectric coupling can be increased when the piezoelectric direction is rotated partially out-of-plane via epitaxy. The strongest out-of-plane coupling is observed for LTO/STO(001). Deposition on TiO 2 (110) results in epitaxial La 2/3 TiO 3 , an orthorhombic perovskite of interest as a microwave dielectric material and an ion conductor. La 2/3 TiO 3 can be difficult to stabilize in bulk form, and epitaxial stabilization on TiO 2 (110) is a promising route to realize La 2/3 TiO 3 for both fundamental studies and device applications. Overall, these results confirm that control of the crystalline orientation of epitaxial LTO-based materials can govern the resulting functional properties.

36 MATERIALS SCIENCE↗

Effective decolorization and adsorption of contaminant from industrial dye effluents using spherical surfaced magnetic (Fe{sub 3}O{sub 4}) nanoparticles

Treatment of highly concentrated Industrial dye stuff effluents released in the environment is the major issue faced in the era of waste management as well as in water pollution. Though there is availability of conventional techniques in large numbers, there is a need of efficient and effective advance technologies. In account of that, Nanotechnology plays a prominent role to treat the heavy metals, organic and inorganic contaminants using smart materials in nano regime (1 -100 nm). Among these nanomaterials like Iron Oxide (Fe{sub 3}O{sub 4}, magnetic nanoparticle) is one of the most promising candidates to remove the heavy metals from the industrial effluent. Fe{sub 3}O{sub 4} is the widely used smart material with magnetic property having high surface area; high surface to volume ratio provides more surface for the chemical reaction for the surface adsorption. Fe{sub 3}O{sub 4} nanoparticles have been synthesized using sonochemical method using ultra frequency in aqueous solution under optimized conditions. The as-synthesized nanoparticle was analyzed using different characterization tool. The Transmission Electron microscope (TEM) images revealed 10-12 nm spherical shape nanoparticles; crystal phase and surface morphology was confirmed by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM), respectively. The functional group were identified by Fourier Transform-Infra Red Spectroscopy (FT-IR), revealed the bending and stretching vibrations associated with Iron Oxide nanoparticle. In present study, for the efficient removal of contaminants, different concentration (10-50 ppm) of dye stuff effluent has been prepared and subjected to adsorption and decolourization at definite time intervals with Fe{sub 3}O{sub 4} nanoparticles. The concentration of Iron oxide and the time (45 mins) was kept fixed for the reaction whereas the concentration of dye stuff effluent was kept varying. It was found that the spherical shaped Fe{sub 3}O{sub 4} proved to be the potential material for the adsorption of corresponding contaminants due to its highly active adsorbing surfaces. The result concluded that the effective adsorption and decolourization of contaminants is observed in different concentration with the maximum time period of 45 mins with the optimized concentration of Fe{sub 3}O{sub 4}.

54 ENVIRONMENTAL SCIENCES↗

Reactivity of Redox Cycled Fe-bearing Subsurface Sediments Towards Hexavalent Chromium Reduction

Structural Fe(II) in clay minerals and natural sediments is known to reduce Cr(VI) to Cr(III), but the effect of redox-cycled Febearing natural sediments on Cr(VI) reduction kinetics is poorly understood. The objective of this study was to understand the kinetics and mechanisms of Cr(VI) reduction by Fe(II) in redox cycled natural sediment. Fe-bearing sediment was collected from the Ringold formation in the 300 area of Hanford, Washington, United States. Fe redox cycling of the sediment was accomplished via four cycles of bioreduction of structural Fe(III) in Hanford sediment and air oxidation of the resulting Fe(II). Bio-produced Fe(II) in Hanford sediment from each redox cycle was utilized to reduce Cr(VI) at three temperatures (10, 20 and 30° C). The initial rate of Cr(VI) reduction generally increased with each redox cycle, which was more pronounced at high temperatures. The amount of Fe(II) oxidized to the amount of Cr(VI) reduced was close to the expected stoichiometric ratio of 3. Aqueous concentrations of Si, Al, and Fe revealed some dissolution of the sediment after reaction with Cr(VI). Xray diffraction (XRD) and scanning electron microscopy (SEM) detected secondary mineral formation. Mössbauer data showed that the oxidation of Fe(II) was coupled with the reduction of Cr(VI) but no Feoxides/ oxyhydroxides formed. Transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), XANES, and EXAFS were performed for representative reduced Cr solids that formed from reduction of Cr(VI) by sediment-associated Fe(II) at 30oC. TEM revealed that the d-spacing of Cr-reacted montmorillonite at 30° C, a dominant Fe-bearing mineral in Hanford sediment, expanded from 10 Å to 13 Å. This layer expansion was likely due to intercalation of reduced Cr(III) into the interlayer space of the montmorillonite structure. EELS exhibited an L2 absorption peak at 586.0 eV and an L3 absorption peak at 577.0 eV, suggestive of Cr(III) in a hydroxide mineral phase. Similarly, XANES and EXAFS analyses confirmed Cr(VI) reduction to Cr(OH)3 at 30° C and indicated an edge-sharing coordination of the Cr(III) octahedra to 2-3 other Cr or metal ions. This study has important implications for understanding the reactivity of clay-rich sediment towards Cr(VI) reduction at contaminated sites and the stability of the reduced Cr(III).

Bishop, Michael E.↗

Continuous-flow synthesis of thermochromic M-phase VO2 particles via rapid one-step hydrothermal reaction – effect of mixers

VO2 particles are promising materials for thermochromic smart windows that reduce building energy loss. Continuous-flow hydrothermal processes showcase advantages for synthesizing VO2 particles compared with traditional batch reaction systems. Mixers play a crucial role in particle fabrication in continuous-flow systems. In this study, a Center T-Mixer and a Collision Cross-Mixer are developed and implemented in a hot water fluidized suspension reaction (HWFSR) system. The influence of the resident time on the particle phase and size was evaluated, and properties of particles derived from systems equipped with differing mixers were compared. The resulting particles were characterized using techniques of X-ray powder diffraction (XRD) analysis, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). When compared with the Center T-Mixer, results indicate that the Collision Cross-Mixer has better control regarding the morphology and size distribution of resulting particles while improving the transition temperatures of the as-synthesized materials. HWFSR systems containing novel mixer designs are capable of producing pure M-phase VO2 particles in a single step contrary to the current reactor design that use a second postheat treatment step, and they are capable of synthesizing many other nanoparticle species, especially those requiring high temperature and pressure reaction conditions.

continuous-flow process↗