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At least 739 records · Page 41

Radiation-Induced Interfacial Hydroxyl Transformation on Boehmite and Gibbsite Basal Surfaces

Understanding the radiolytic reactivity of aluminum oxyhydroxide phases widely present in stored nuclear wastes is essential to develop reliable processing approaches. Recent experiments using vibrational sum frequency generation (VSFG), a surface sensitive technique, have shown that rehydration of γ-irradiated boehmite (010) and gibbsite (001) surfaces does not recover the initial hydroxyl density prior to irradiation. In this study, using density functional theory and nudged elastic band calculations, we examine dehydration and rehydration of these surfaces and attendant proton transfer mechanisms. While dehydration of both surfaces is predicted to be energetically unfavorable, rehydration of boehmite (010) is favorable after overcoming an energy barrier of 0.52 eV that relates to the orientation of surface hydroxyls controlling the hydrogen bonding network of adsorbed water. In the case of gibbsite (001), for which the experimental results suggest that rehydration mainly involves the reformation of interlayer hydroxyls, we found that a two-proton transfer mechanism is more likely than a one-proton transfer mechanism, and that it prevents the reorientation of interlayer hydroxyls into intralayer hydroxyls consistent with experimental VSFG findings. A detailed analysis of the effect of surface hydrogen vacancy on the strength of hydrogen bond interactions was performed, which indicates that H 2 and H 2 O are the energetically most favorable product species to form from radiation-induced surface H and/or OH defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Construction of Lattice Strain in Bimetallic Nanostructures and Its Effectiveness in Electrochemical Applications

Bimetallic nanocrystals (NCs), associated with various surface functions such as ligand effect, ensemble effect, and strain effect, exhibit superior electrocatalytic properties. The stress-induced surface strain effect can alter binding strength between the surface active sites and reactants as well as their intermediates, and the electrochemical performance of bimetallic NCs can be significantly facilitated by the lattice-strain modification via their morphologies, sizes, shell-thickness, surface defectiveness as well as compositions. Here in this review, an overview of fundamental principles, characterization techniques, and quantitative determination of the surface lattice strain is provided. Various strategies and synthesis efforts on creating lattice-strain-engineered bimetallic NCs, including the de-alloying process, atomic layer-by-layer deposition, thermal treatment evolution, one-pot synthesis, and other efforts are also discussed. It is further outlined how the lattice strain effect promotes electrochemical catalysis through the selected case studies. The reactions on oxygen reduction reaction, small molecular oxidation, water splitting reaction, and electrochemical carbon dioxide reduction reactions are focused. In particular, studies of lattice strain arisen from core–shell nanostructure and defectiveness are highlighted. Lastly, the potential challenges are summarized and the prospects of lattice-strain-based engineering on bimetallic nanocatalysts with suggestion and guidance of the future electrocatalyst design are envisioned.

36 MATERIALS SCIENCE↗

Modeling Climate Change Impacts on an Arctic Polygonal Tundra: 1. Rates of Permafrost Thaw Depend on Changes in Vegetation and Drainage

Model projections of permafrost thaw during the next century diverge widely. Here we used ecosys to examine how climate change will affect permafrost thaw in a polygonal tundra at Barrow AK. The model was tested against diurnal and seasonal variation in energy exchange, soil heat flux, soil temperature ( T s ), and active layer depth (ALD) measured during 2014 and 2015, and interannual variation in ALD measured from 1991 to 2015. During RCP 8.5 climate change from 2015 to 2085, increases in T a and precipitation ( P ) to 6.2 °C and 27% above current values, and in atmospheric CO 2 concentrations ( C a ) to 763 μmol mol -1 , altered energy exchange by increasing leaf area index of dominant sedge relative to that of moss. Increased Ca and sedge leaf area index imposed greater stomatal control of transpiration and reduced soil heat fluxes, slowing soil warming, limiting increases in evapotranspiration, and thereby causing gradual soil wetting. Consequently, increases in surface T s and ALD of 2.4–4.7 °C and 21–24 cm above current values were modeled after 70 years. ALD increase was slowed if model boundary conditions were altered to improve landscape drainage. These rates were smaller than those of earlier modeling studies, some of which did not account for changes in vegetation, but are closer to those derived from current studies of warming impacts in the region. Therefore, accounting for climate change effects on vegetation density and composition, and consequent effects on surface energy budgets, will cause slower increases in T s and ALD to be modeled during climate change simulations.

54 ENVIRONMENTAL SCIENCES↗

Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers

In this paper, the preparation and characterization of modified LiMn 2 O 4 (LMO) cathodes utilizing chemisorbed alkylphosphonic acids to chemically modify their surfaces are reported. Electrochemical methods to study ionic and molecular mobility through the alkylphosphonate self-assembled monolayers (SAMs) for different alkyl chain compositions, in order to better understand their impact on the lithium-ion electrochemistry, are utilized. Electrochemical trends for different chains correlate to trends observed in contact angle measurements and solvation energies obtained from computational methods, indicating that attributes of the microscopic wettability of these interfaces with the battery electrolyte have an important impact on ionic mobility. The effects of surface modification on Mn dissolution are also reported. The alkylphosphonate layer provides an important mode of chemical stabilization to the LMO, suppressing Mn dissolution by 90% during extended immersion in electrolytes. A more modest reduction in dissolution is found upon galvanostatic cycling, in comparison to pristine LMO cathodes. Finally, taken together, the data suggest that alkylphosphonates provide a versatile means for the surface modification of lithium-ion battery cathode materials allowing the design of specific interfaces through modification of organic chain functionalities.

25 ENERGY STORAGE↗

Surface energy of fayalite and its effect on Fe-Si-O oxygen buffers and the olivine-spinel transition

The surface energy (hydrated surfaces) of fayalite ($α$-Fe 2 SiO 4 ) was determined to be 2.47 ± 0.25 J/m 2 using high-temperature oxide melt solution calorimetry. This is larger than the surface energy of magnetite (Fe 3 O 4 ), but lower than that of forsterite ($α$-Mg 2 SiO 4 ). The changes in the positions of the quartz-fayalite-magnetite (QFM) and quartz-iron-fayalite (QIF) buffers with particle size reduction were calculated. QFM is lowered in $f_{O_2}$ by 3–7 log units as a function of temperature for 30 nm particles while QIF is raised by 1–2 log units. The estimated surface energy difference between olivine and spinel polymorphs decreases the pressure of the olivine-spinel transition in Fe 2 SiO 4 by about 1 GPa.

quartz-iron-fayalite (QIF) buffers↗

Removable, Sequestration Coatings for Mitigating Hazardous Contaminants Related to Deactivation and Decommissioning Activities

This project is a collaborative effort between InnoSense LLC (ISL) and Oak Ridge National Laboratory (ORNL) aimed at mitigating the mercury (Hg) contamination problem at the Y-12 National Security Complex (NSC). The report summarizes the research and technology development work of the Phase IIB Project, led by Dr. Uma Sampathkumaran at ISL for the period of July 31, 2017–October 31, 2021. The Y-12 site cleanup includes technologies for safe and cost-effective facility demolition, soil remediation, and on-site treatment and disposal of mercury bearing wastes. One of the technology demonstration goals was a reactive strippable coating for targeted pre-demolition and de-contamination to limit Hg mobilization and the volume of debris requiring treatment for disposal. Toward this, ISL has developed a water-based reactive strippable coating (Trap & See-Hg™) to sequester elemental Hg(0) and mercuric Hg(II) species in the coating. The coating provides multiple benefits including (1) Hg vapor suppression, (2) sealing in the hazardous contaminants, (3) visually locating the contaminant through color changes, and (4) remediating the contaminated surfaces upon coating removal. Through collaboration between ORNL and ISL in Phase II work, the team successfully demonstrated the Trap & See-Hg technology to (1) visually locate the presence of Hg on concrete, soil and drywall surfaces, (2) effectively sequester all mercury species (elemental, soluble and insoluble Hg) from lab-generated and ex-situ soil and brick/rubble samples collected from the Y 12 site with 80 to 95% efficiency to capture/reduce Hg vapor concentration, (3) be applied by manual and robotic spray applicators and cure at room ambient, (4) remain a cohesive and peelable coating upon drying, and (5) sequester Hg0 from walls in the alpha-2 building basement at Y-12 during a small scale in-situ field trial. In Phase IIB, ISL’s effort was focused on refining the coating formulations with additives containing passive and reactive sorbents, colorimetric indicator, and thixotropic agents to achieve the desired performance. The paints were then evaluated at ORNL for applicability to metal and concrete surfaces of different sizes and shapes, and soil rubble, Hg-sorption capacity and achieving sag-free coating on surfaces when applied by a manual spray applicator. Ambient cure of the coating resulted in a dry thickness of 16–20 mil. The coatings were removed from smooth or rough surfaces with low to moderate force. Both lab-generated Hg-contaminated samples and soil and brick/rubble samples containing a range of Hg concentrations (collected from the Y-12 site by UCOR) were used in this project. Optimized formulations were applied to these samples and evaluated for ability to suppress Hg vapors, sequester Hg 0 and Hg(II) species and color mapping of mercury species on the test surface. The ORNL team initially identified three to four potential sites at Y-12 and ORNL for potential demonstration. However, the pandemic closed any possible avenues for on-site demonstration of the robotic spray applicator. The metal and concrete samples with low to high Hg content provided by UCOR from an ongoing demolition were subsequently used for ex-situ sample characterization and analysis at ORNL over a period of 25 days. The coatings suppressed Hg vapors with an efficiency of 95–99% from heavily contaminated metal and 60% from concrete substrate. Analysis of total Hg in the peeled paints indicates sorption capacities ranging from 12 µg Hg/g of paint from concrete to 1.2 mg Hg/g of paint from the metal substrates while peeled paints from soil samples could capture a total Hg from 2.3 mg Hg/g to 66 mg/g paint. Toxicity characteristic leaching procedure (TCLP) tests recovered total mercury leached at 0.15±0.0008 µg/L for concrete to 126.81±0.67 µg/L and 377.25±5.67 µg/L for the two metal substrates, to allow for informed decisions on downstream disposal considerations. Together, this Phase IIB demonstrated the potential value of the Trap & See-Hg for Hg uptake, vapor suppression, and color mapping, and may thus be used to enhance worker safety during site cleanup, facility demolition, and downstream waste disposal at Y-12 NSC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Low thermal budget dopant activation in shallow junctions of implanted Si via Tunable plasma enhanced annealing

Low thermal budget (LTB) annealing has become increasingly critical for shallow junctions as semiconductor devices are scaled down. Plasma Enhanced Annealing (PEA) has emerged as a promising LTB annealing process, however its mechanisms remain unclear. In this study, arsenic and boron implanted silicon wafers were subjected to helium or argon ion bombardment generated by annealing plasmas under controlled ion energies and doses in a home-built annealing reactor. The structural and electrical changes were characterized by four-point probe measurements, secondary ion mass spectrometry, Raman spectroscopy and spectroscopic ellipsometry. A pronounced reduction in sheet resistance, accompanied by a decrease in the damage layer thickness demonstrates the surface selective annealing capability of PEA process. Comparative studies using He and Ar plasmas and related ion bombardment reveal a dependence of activation efficacy on both ion species and the dopant implantation profile. Furthermore, a multi-step annealing mechanism is proposed, consisting of an initial (low dose) structural recovery stage followed by the generation of “extended” defects and concluded at large doses by an enhanced dopant activation. The proposed annealing kinetics are thought to be controlled by ion flux, dose and energy. Finally, these results highlight PEA as an effective, surface-selective, LTB approach for shallow-dopant activation and near surface annealing, and provide mechanistic insights into PEA processes.

dopant activation↗

Two-Dimensional Crystallization of Poly( N -isopropylacrylamide)-Capped Gold Nanoparticles

Surface-sensitive X-ray reflectivity and grazing incidence small-angle X-ray scattering reveal the structure of polymer-capped-gold nanoparticles (AuNPs that are grafted with poly(N-isopropylacrylamide); PNIPAM–AuNPs) as they self-assemble and crystallize at the aqueous suspension/vapor interface. Citrate-stabilized AuNPs (5 and 10 nm in nominal diameter) are ligand-exchanged by 6 kDa PNIPAM-thiol to form corona brushes around the AuNPs that are highly stable and dispersed in aqueous suspensions. Surprisingly, no clear evidence of thermosensitive effect on surface enrichment or self-assembly of the PNIPAM–AuNPs is observed in the 10–35 °C temperature range. However, addition of simple salts (in this case, NaCl) to the suspension induces migration of the PNIPAM–AuNPs to the aqueous surface, and above a threshold salt concentration, two-dimensional crystals are formed. In conclusion, the 10 nm PNIPAM–AuNPs form a highly ordered single layer with in-plane triangular structure, whereas the 5 nm capped NPs form short-range triangular structure that gradually becomes denser as salt concentration increases.

36 MATERIALS SCIENCE↗

Low temperature aging in a molecular glass: the case of cis -methyl formate

Glassy films of cis-methyl formate show spontaneous dipole orientation on deposition from the vacuum, the so-called ‘spontelectric effect’, creating surface potentials and electric fields within the films. We follow the decay of these fields, and their accompanying dipole orientation, on the hours timescale at deposition temperatures between 40 K and 55 K. Our data trace the low temperature ‘secondary decay’ mechanism, at tens of degrees below the glass transition temperature of 90 K. We show that secondary decay is due to molecular rotation, with associated activation energies lying between 0.1 and 0.2 eV. Diffusion is absent, as established from published neutron reflectivity data. Using an analytical model for the spontelectric effect, data are placed on a quantitative footing, showing that angular motion in excess of 50° reproduces the observed values of activation energies. Exploitation of the spontelectric effect is new in the study of glass aging and is shown here to give insight into the elusive processes which take place far from the molecular glass transition temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of dislocation configurations in SiC crystals through X-ray topography aided by ray tracing simulations

Silicon carbide as a wide bandgap semiconductor is of great research interest for its widespread deployment in a range of electronic and optoelectronic devices, particularly in power electronics. However, defects in silicon carbide crystals are still major concerns that is hampering the development of high-performance devices. X-ray topography, particularly using the synchrotron beam has been instrumental in characterizing and analyzing defect configurations in silicon carbide crystals to optimize crystal growth as well as understand the effect of defects on device performance. Here, in recent years, the use of ray-tracing simulation technique based on the orientation contrast mechanism to simulate contrast of defects observed on actual X-ray topographs has proven to be an effective approach to investigate the nature of crystallographic defects in various semiconductors. This review discusses the principle of ray-tracing simulation and its application and modifications to incorporate the effects of surface relaxation and photoelectric absorption to better simulate different dislocations observed in 4H–SiC as well as 6H–SiC crystals of various orientations. The adaptation to weak beam topography and plane wave topography is also discussed. The application of ray-tracing simulation in dislocation characterization of silicon carbide of different polytypes is systematically reviewed including different types of dislocations observed in both off-axis wafers and axial-sliced samples through synchrotron X-ray topography under various beam conditions, recording geometries and reflections. The result of ray-tracing simulation is further utilized in other studies including the investigation of effective penetration depth of all types of dislocations lying on the basal plane on grazing-incidence X-ray topography.

Engineering↗

Stress localization investigation of additively manufactured GRCop-42 thin-wall structure

A full-field crystal plasticity (CP) framework is presented for the GRCop-42 alloy to study microscopic mechanical behavior and local stress heterogeneities. The microstructures of additively manufactured (AM) materials are often unique relative to conventionally processed materials, and the local thermal histories drive these differences during the build process. These thermal histories depend on the process parameters (laser power, scan speed, and scan strategy) and the part geometry. Prior research has shown that the mechanical properties of thin-walled structures can vary significantly with wall thickness due to changes in the thermal boundary conditions during manufacturing. It is, therefore, desirable to perform CP simulations based on the phenomenological constitutive model to predict the local mechanical responses induced by microstructural heterogeneities. This work generates representative microstructures based on experimentally collected grain information (i.e., texture) for grain scale stress analysis, and the material constitutive parameters are calibrated using the experimental mechanical testing data. Here, we specifically investigated the effect of crystallographic texture and grain morphologies on the size-dependent mechanical properties of AM GRCop-42. The selection of appropriate material properties for implementing an effective free surface boundary condition and the influence of adjacent buffer layers are also discussed. Analysis of local field results reveals a strong correlation between stress localization and the initial grain orientation. However, no significant relationship between the misorientation of the individual adjacent grains and the average misorientation is observed.

36 MATERIALS SCIENCE↗

A Novel Surface Restoration Method for Hydropower Steel Components: Plasma Gouging and Inconel Cold Spray Coating for Material Repair

A novel surface restoration approach combining plasma gouging with subsequent cold spray deposition is demonstrated in this study. Plasma gouging effectively removes the damaged steel surface, leaving grooves and forming a plasma gouging affected zone up to ~300?µm thick. Within this zone, a hardened martensitic layer with a peak hardness of ~370?HV—almost twice that of the base substrate (~200?HV)—is produced. Following plasma gouging, cold spray deposition is applied to rebuild the surface. Experimental results reveal that cold spray coatings deposited at low energy suffer from delamination, whereas high energy cold spray deposits yield a well-bonded coating. Microstructural analysis further shows that the martensitic layer formed by plasma gouging undergoes dynamic recrystallization during cold spray, reducing the hardness to 317?HV. These findings demonstrate the feasibility of this hybrid method for effective surface restoration of damaged steel components.

Wang, Tianhao↗

Study of the crystal device for deflecting high-energy proton beams using synchrotron radiation diffraction

Currently, bent silicon single crystals are used at large accelerators to extract and collimate proton beams. A device for multiple deflection of a proton beam based on several bent silicon strips operating in the volume reflection mode has recently been developed. In this device, the bending of silicon strips successively located on the surface of a thick plate is implemented due to the internal stress induced by grooves mechanically formed on the crystal surface (Twyman effect). Topography based on angular scanning and synchrotron radiation was applied to measure the bending of individual deflector strips and the crystal as a whole. The measurement results are compared with the data obtained with a proton beam.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Non-equilibrium molecular dynamics simulation to evaluate the effect of confinement on fluid flow in silica nanopores

The flow of fluids in nano-confinement has applications in separations, water purification, medical systems and in the recovery of fluids in petroleum systems. It is believed that fluids do not obey continuum laws when flowing in nanopores (or in confinement). This paper attempts to shed light on various nano confinement effects such as fluid-wall interactions, pore size and molecular geometry, using molecular dynamic simulation. Here, water, hexane, and methanol flow behaviors were simulated for pore diameters ranging from 1 to 8 nm. In addition to the density analysis of the confined fluids, the fluid flows in saturated nanopores were simulated by the sectional flow method. Water and methanol molecules were completely stabilized in the 1 nm pore. Hexane molecules could not enter the 1 nm pore, due to geometric considerations. For the 2 – 8 nm pores, all fluids showed reduced flow rate compared to the Hagen–Poiseuille flow, due to an interfacial molecular layer stabilized at the pore surface. Flow reduction observed in these studies is contrary to significant flow enhancements observed for fluid flow in carbon nanotubes of similar dimensions. Water flow showed almost constant stick length for all the pore sizes. Methanol flow had the largest stick length. Hexane flow was reduced because of overcrowding of molecules at the pore surface. The effect of confinement diminished with an increase in pore diameter.

42 ENGINEERING↗

Investigating Spillover Energy as a Descriptor for Single-Atom Alloy Catalyst Design

The identification of thermodynamic descriptors of catalytic performance is essential for the rational design of heterogeneous catalysts. Here, we investigate how spillover energy, a descriptor quantifying whether intermediates are more stable at the dopant or host metal sites, can be used to design single-atom alloys (SAAs) for formic acid dehydrogenation. Further, using theoretical calculations, we identify NiCu as a SAA with favorable spillover energy and demonstrate that formate intermediates produced after the initial O–H activation are more stable at Ni sites where rate-determining C–H activation occurs. Surface science experiments demonstrated that NiCu(111) SAAs are more reactive than Cu(111) while they still follow the formate reaction pathway. However, reactor studies of silica-supported NiCu SAA nanoparticles showed only a modest improvement over Cu resulting from surface coverage effects. Overall, this study demonstrates the potential of engineering SAAs using spillover energy as a design parameter and highlights the importance of adsorbate–adsorbate interactions under steady-state operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrodeposited nickel coatings for exceptional corrosion mitigation in industrial grade molten chloride salts for concentrating solar power

Molten chloride salt eutectics are attractive candidates for use as thermal energy storage media and heat transfer fluids in generation-three concentrating solar thermal power (Gen3 CSP) plants. However, corrosion of alloys in molten chloride salts, especially at high temperatures, is an extremely challenging problem that studies focus on lower temperatures, shorter durations, or analytical grade, and high-purity, salts. To date, there has been no study on corrosion or corrosion mitigation in an industrial-grade salt at a high temperature such as 750 °C. To alleviate this knowledge gap, the study presents new multiscale fractal-textured Ni coatings on various alloy surfaces for effective corrosion mitigation at 750 °C in molten chloride salts. Using the electrodeposition method, durable double-layer textured coatings were formed on stainless steel alloys (SS316, SS310, and SS347) and In800H. The corrosion performance of the coatings is investigated in both analytical-grade purity and, for the first time, practically relevant industrial-grade chloride salts. Ni-coated ferrous alloys showed an exceptionally reduced corrosion rate in the range of 350–480 μm/y in analytical-grade salts, and between 450 and 490 μm/y in purified industrial-grade salts at 750 °C. Ni coatings on ferrous alloys reduced corrosion rates by as much as 70% compared to uncoated surfaces and were comparable to the expensive Ha230 alloy with a high Ni content. As a result, by the use of innovative fractal corrosion mitigation coatings, for the first time, low-cost structural alloys are rendered viable for use with industrial-grade chloride salts, which is profoundly beneficial in practical systems.

14 SOLAR ENERGY↗

Calibrating Bond-Based Peridynamic Parameters Using a Novel Least Squares Approach

Here, we present a novel procedure to calibrate bond micromoduli in a discrete bond-based peridynamics setting. Conventionally, an analytical expression has been used based on strain energy equivalence. In the present work, the micromoduli for individual bonds in a neighborhood are calibrated by equating the effective peridynamic stiffness to the reference material stiffness and posed as a set of linear system of equations. The solution to this is found by a least squares approach which aims to reduce the error in the components of the stiffness matrix. Finally, results for an isotropic case in a local neighborhood of particles are shown to demonstrate the feasibility of this approach.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Pseudoplasticity and Dynamic Interfacial Tension Relaxation Effects on Nucleate Pool Boiling in Aqueous Polymeric Liquids

Nucleate pool boiling heat transfer and its ebullient dynamics in polymeric solutions at atmospheric pressure saturated conditions are experimentally investigated. Three grades of hydroxyethyl cellulose (HEC) are used, which have intrinsic viscosity in the range 5.29 ≤ [ η ] ≤ 10.31 [dl/g]. Their aqueous solutions in different concentrations, with zero-shear viscosity in the range 0.0021 ≤ η 0 ≤ 0.0118 [N∙s/m 2 ], exhibit shear-thinning rheology in varying degrees, as well as gas–liquid interfacial tension relaxation and wetting. Boiling heat transfer in solutions with constant molar concentrations of each additive, which are greater than their respective critical polymer concentration C * , is seen to have anomalous characteristics. There is degradation in the heat transfer at low heat fluxes, relative to that in the solvent, where the postnucleation bubble dynamics in the partial boiling regime is dominated by viscous resistance of the polymeric solutions. At higher heat fluxes, however, there is enhancement of boiling heat transfer due to a complex interplay of pseudoplasticity and dynamic surface tension effects. The higher frequency vapor bubbling train with high interfacial shear rates in this fully developed boiling regime tends to be influenced by increasing shear-thinning and time-dependent differential interfacial tension relaxation at the dynamic gas–liquid interfaces.

Engineering↗