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At least 667 records · Page 37

Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalyst for enhanced CO 2 -methanol conversion at low temperature and pressure

Cu-ZnO-Al 2 O 3 is the most widely applied catalyst for CO 2 hydrogenation to methanol. However, it is still a challenge to produce methanol using this catalyst under low-temperature (<250 °C) and low-pressure (<10 bar) conditions with desirable yield and selectivity. In this work, by tuning the experimental processing parameters such as solvent, loading amount, and annealing temperature, highly improved ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalysts have been successfully demonstrated. Here, by using organic solvent (N,N-dimethylformamide (DMF), acetone, or isopropanol) for dip-coating loading process instead of deionized (DI) water, Cu-ZnO-Al 2 O 3 nanocatalysts was comparatively better dispersed on the nanorod array support with populated and abundant active sites, thus enhancing the methanol yield. With the control of the loading amount and annealing temperature, finely distributed Cu nanoparticles were obtained on the ZnO nanorod surfaces to enhance the interactions between Cu and ZnO nanorod surfaces. Further improvement of the catalyst performance is demonstrated by tuning the reaction space velocity. At 200 °C and 10 bar conditions, the optimized catalyst achieved a methanol yield of 6.46 mol h –1 kg –1 with 100 % selectivity. The good stability after prolonged testing of the catalysts demonstrates the potential practical implementation. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements under the 1 bar reveal that the CO 2 hydrogenation to methanol on the ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalyst follows the CO reaction pathway, due to the surface oxygen vacancies on ZnO nanorods which facilitate CO 2 dissociation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Coupled nonlinear elasticity, plastic slip, twinning, and phase transformation in single crystal titanium for plate impact loading

High purity single crystal titanium (Ti) under shockwave loading in plate impact experiment is modelled and simulated, with help of the finite element. A thermodynamically consistent system of equations is formulated in the frame of large deformation to consider material anisotropy, rate dependence, and multi-physics including nonlinear elasticity, dislocation based plastic slip, deformation twinning, and phase transformation. A novel kinematics is proposed to consider phase transformation in the α twin variants and also to consider the dislocation based slip in all of components of parent material, primary twins and the ω phase. The thermodynamically consistent driving forces for plastic slip, twinning, and phase transformation are developed based upon the second law of thermodynamics. For nonlinear elasticity, the stiffness matrix is dependent on the volume fractions of all components, and the volumetric part of Cauchy stress is obtained from the nonlinear equation of state. Dislocation based plastic slip in multi-variant and multiphase heterogeneous materials is developed and interactions of dislocations among all slip modes are taken into account. A mechanism for dislocation density evolution during twinning and phase transformation is proposed. The shock loading along the [0001] and [10$\bar{1}1$ directions of single crystal high purity Ti is investigated computationally. Very good correspondence between simulation and experiment is obtained, which includes pole figures, volume fractions of components, free surface velocity, peak pressure, and phase transformation pressure. Multiple experimental phenomena are interpreted based upon the progression of dislocation slip, deformation twinning, and phase transformation. In compression with the [10$\bar{1}1$ crystal, a higher volume fraction in the primary twins but a lower secondary twin volume fraction in the [0001] crystal in experiment was observed. Finally, the higher propensity for phase transformation occurs in the [0001] crystal is reproduced. In addition to material texture, distributions of temperature, stresses, and plastic strains dependent on the impact loading directions are revealed.

36 MATERIALS SCIENCE↗

Dry in-pile fracture test (DRIFT) for separate-effects validation of ceramic fuel fracture models

Fracture is an important component of nuclear fuel behavior, and significant efforts have been invested into developing fuel performance models that are capable of accurately representing fracture. Usable data on the process of fracture propagation in nuclear fuel under realistic service conditions are very limited. To address this need, a series of separate-effects experiments were developed and performed at Idaho National Laboratory's Transient Reactor Test (TREAT) facility. These experiments employ a heat sink to radially remove heat from the fuel in a manner that approximates the effect of coolant in an operating light-water reactor (LWR). The test holder for these experiments is known as the Dry In-pile Fracture Test (DRIFT). A series of experiments employing DRIFT and TREAT were performed to provide data on the extent and nature of fracture in fresh fuel at various points during a ramp to full power. Novel aspects of these experiments include the way they employ a heat sink to replicate steady-state LWR conditions, as well as the use of fiber optic sensors for in-reactor thermal instrumentation. Details on the development of this experiment, experimental conditions, and resulting data (including in situ thermal measurements and post-irradiation imaging of fracture) are provided in this work. LWR-equivalent powers ranging from 10 to 25 kW/m were tested using this apparatus. Cracking was visible at all power levels, with increasing cracking extent as the power level increased, although there was little difference in the cracking between the two highest-power tests, which had LWR-equivalent powers of 20 and 25 kW/m.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Gas tungsten arc welding and post weld heat treatment effects on microstructure and mechanical property of castable nanostructured alloy steel

Here, this paper details the first study of castable nanostructured alloy (CNA) steel gas tungsten arc weldability and the post-weld heat treatment (PWHT) effects. Effects of welding heat input, thermal cycles, and PWHT on microstructures, microhardness distributions, room temperature tensile properties, and fracture characteristics are discussed. Results show that CNA steel exhibits excellent weldability (i.e., no indication of welding defects and reasonable tensile properties). The welded joint exhibited heterogeneous microstructures with δ-ferrite as well as large microhardness variation and fluctuation. The welded joint yield and ultimate tensile strengths were similar to those of the base metal, but the elongations decreased by 30 %. However, with normalization and tempering PWHT, the δ-ferrite was eliminated, microstructure was modified, hardness was unified, and joint ductility was restored. The study indicated that the CNA reduced-activation ferritic-martensitic steel owns excellent weldability, and PWHT is needed for the industrial application of welded structures.

36 MATERIALS SCIENCE↗

Molecular-level insights into CO 2 activation on Ni(111) from in situ infrared spectroscopy

The activation of CO 2 on nickel surfaces is the first step of various CO 2 conversion processes. Consequently, understanding the surface intermediates formed during this step and their adsorption sites is crucial for elucidating reaction mechanisms. In this study, we employ in situ infrared spectroscopy to investigate the interaction of 1 mbar CO 2 with a model Ni(111) catalyst between 25°C and 300°C. Under these conditions, CO 2 is activated via a direct dissociation into CO and atomic oxygen, while the oxidation state of the Ni(111) surface is primarily determined by residual H 2 and O 2 . The high surface coverage of CO and oxygen at ambient CO 2 pressure induces a competitive adsorption mechanism on the energetically favored hollow sites. This mechanism leads to a temperature-dependent distribution of CO between top and hollow sites, potentially explaining the effect of reaction conditions on the adsorption site of CO intermediates in CO 2 conversion reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical Study of Coupled Water and Vapor Flow, Heat Transfer, and Solute Transport in Variably-Saturated Deformable Soil During Freeze-Thaw Cycles

As climate change intensifies, soil water flow, heat transfer, and solute transport in the active, unfrozen zones within permafrost and seasonally frozen ground exhibit progressively more complex interactions that are difficult to elucidate with measurements alone. For example, frozen conditions impede water flow and solute transport in soil, while heat and mass transfer are significantly affected by high thermal inertia generated from water-ice phase change during the freeze-thaw cycle. To assist in understanding these subsurface processes, the current study presents a coupled two-dimensional model, which examines heat conduction-convection with water-ice phase change, soil water (liquid water and vapor) and groundwater flow, advective-dispersive solute transport with sorption, and soil deformation (frost heave and thaw settlement) in variably saturated soils subjected to freeze-thaw actions. This coupled multiphysics problem is numerically solved using the finite element method. The model's performance is first verified by comparison to a well-documented freezing test on unsaturated soil in a laboratory environment obtained from the literature. Then based on the proposed model, we quantify the impacts of freeze-thaw cycles on the distribution of temperature, water content, displacement history, and solute concentration in three distinct soil types, including sand, silt and clay textures. The influence of fluctuations in the air temperature, groundwater level, hydraulic conductivity, and solute transport parameters was also comparatively studied. The results show that (a) there is a significant bidirectional exchange between groundwater in the saturated zone and soil water in the vadose zone during freeze-thaw periods, and its magnitude increases with the combined influence of higher hydraulic conductivity and higher capillarity; (b) the rapid dewatering ahead of the freezing front causes local volume shrinkage within the non-frozen region when the freezing front propagates downward during the freezing stage and this volume shrinkage reduces the impact of frost heave due to ice formation. This gradually recovers when the thawed water replenishes the water loss zone during the thawing stage; and (c) the profiles of soil moisture, temperature, displacement, and solute concentration during freeze-thaw cycles are sensitive to the changes in amplitude and freeze-thaw period of the sinusoidal varying air temperature near the ground surface, hydraulic conductivity of soil texture, and the initial groundwater levels. Our modeling framework and simulation results highlight the need to account for coupled thermal-hydraulic-mechanical-chemical behaviors to better understand soil water and groundwater dynamics during freeze-thaw cycles and further help explain the observed changes in water cycles and landscape evolution in cold regions.

54 ENVIRONMENTAL SCIENCES↗

Response of Atmospheric River Width and Intensity to Aquaplanet Warming: A Detection Algorithm‐ and Background Moisture‐Independent Approach

The width of an atmospheric river (AR) is an important parameter when evaluating its impact. Although previous research suggests ARs will widen with global warming, a precise response has been muddled by the large sensitivity of width to a diverse set of AR detection techniques (ARDTs). Here, we propose a methodology that removes the influence of the ARDT by modeling AR‐integrated vapor transport (IVT) profiles as idealized exponential curves with free parameters given by background IVT, intensity above background IVT, and profile width. Notably, our definition for AR profile width does not include any explicit numerical thresholds, relative or absolute, for IVT. We apply our approach to a series of idealized aquaplanet experiments, first with a baseline sea surface temperature (SST) distribution, and then with +2K, +4K, and +6K uniform warming, so as to determine the contributions of each free parameter to AR width. We also apply our approach to high‐resolution atmosphere‐only models forced with SSTs modified to preserve historical variability but following projected warming over 2016–2050. Our results show that contributions to impacts‐relevant AR widening comes primarily from enhancements in background IVT and AR intensity, as opposed to from dynamic width changes.

54 ENVIRONMENTAL SCIENCES↗

Q-dependent collective relaxation dynamics of glass-forming liquid Ca0.4K0.6(NO3)1.4 investigated by wide-angle neutron spin-echo

Abstract The relaxation behavior of glass formers exhibits spatial heterogeneity and dramatically changes upon cooling towards the glass transition. However, the underlying mechanisms of the dynamics at different microscopic length scales are not fully understood. Employing the recently developed wide-angle neutron spin-echo spectroscopy technique, we measured the Q -dependent coherent intermediate scattering function of a prototypical ionic glass former Ca 0.4 K 0.6 (NO 3 ) 1.4 , in the highly viscous liquid state. In contrast to the structure modulated dynamics for Q < 2.4 Å −1 , i.e., at and below the structure factor main peak, for Q > 2.4 Å −1 , beyond the first minimum above the structure factor main peak, the stretching exponent exhibits no temperature dependence and concomitantly the relaxation time shows smaller deviations from Arrhenius behavior. This finding indicates a change in the dominant relaxation mechanisms around a characteristic length of 2π/(2.4 Å −1 ) ≈ 2.6 Å, below which the relaxation process exhibits a temperature independent distribution and more Arrhenius-like behavior.

42 ENGINEERING↗

Molecular insight into the lower critical solution temperature transition of aqueous alkyl phosphonium benzene sulfonates

Abstract Ionic liquid (IL)-water mixtures can exhibit a lower critical solution temperature (LCST) transition, but changes in long-range order and local molecular environment during this transition are not comprehensively understood. Here we show that in IL-H 2 O LCST mixtures, the IL forms loosely held aggregate structures that grow in size leading up to a critical temperature, whereas the aggregation of a fully miscible aqueous mixture, obtained by minor chemical modification of the anion, decreases with increasing temperature. Radial distribution functions from molecular dynamics simulations support the observation of aggregation phenomena in the IL-H 2 O mixtures. A local molecular structure of the ions is derived from multi-dimensional NMR experiments in conjunction with reported molecular dynamics simulations. In addition to considerable shifts of water’s hydrogen bonding network in the fully miscible phase, by NMR we observe the anion’s protons response to the intermolecular thermal environment and the intramolecular environment and find that the responses are determined by the sulfonate ionic functional group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of the energy distribution of electrons escaping confinement from an electron cyclotron resonance ion source

Production of high charge state ions in electron cyclotron resonance ion sources (ECRISs) is dependent on the electron energy distribution (EED) within the source plasma. In order to better understand the EED, a measurement of electrons escaping axially from an ECRIS device has been performed at the National Superconducting Cyclotron Laboratory. Electrons were measured escaping from the Superconducting Source for Ions, driven at 18 GHz. Dependencies of the observed EED on the confining magnetic field strength and injected microwave power are reported. This paper focuses on large peaks of electrons in the 400–1200 keV energy range. Measurements of the axial bremsstrahlung spectrum have been simultaneously carried out to provide a direct comparison between both techniques. A comparison between the energy associated with the peak of the electron distribution and the spectral temperature of the bremsstrahlung distribution is shown.

47 OTHER INSTRUMENTATION↗

Radiative transfer in stars by feebly interacting bosons

Starting from first principles, we study radiative transfer by new feebly-interacting bosons (FIBs) such as axions, axion-like particles (ALPs), dark photons, and others. Our key simplification is to include only boson emission or absorption (including decay), but not scattering between different modes of the radiation field. Based on a given distribution of temperature and FIB absorption rate in a star, we derive explicit volume-integral expressions for the boson luminosity, reaching from the free-streaming to the strong-trapping limit. The latter is seen explicitly to correspond to quasi-thermal emission from a “FIB sphere” according to the Stefan-Boltzmann law. Our results supersede expressions and approximations found in the recent literature on FIB emission from a supernova core and, for radiatively unstable FIBs, provide explicit expressions for the nonlocal (“ballistic”) transfer of energy recently discussed in horizontal-branch stars.

79 ASTRONOMY AND ASTROPHYSICS↗

Flexosensitive polarization vortices in thin ferroelectric films

In this work, we present a theoretical study on the influence of the flexoelectric coupling on the spatial distribution and temperature behavior of the spontaneous polarization for several types of stable domain structure in thin ferroelectric films, such as stripe domains and vortices. Finite-element modeling (FEM) for BaTiO 3 films and analytical calculations within the Landau-Ginzburg-Devonshire approach reveals that an out-of-plane polarization component can be very sensitive to the flexoelectric coupling for periodic quasi-2D stripe domains and 3D vortex-antivortex structures. However, the influence is rather different for these structures. The flexoelectric coupling increases significantly the amplitude of a small out-of-plane polarization component in the stripe domains, and the “up” or “down” direction of the component is defined by the sign of the flexoelectric coefficients. Concerning the vortex-antivortex pairs, their antivortices with in-plane antiсirculation have smooth wide dipolar cores through the entire film, whose shape and other features are almost insensitive to the coupling. The vortices with in-plane vorticity have spikelike cores with an out-of-plane quadrupolar moment induced by the flexoelectric coupling. The cores are located near the film–dead-layer interfaces. FEM results corroborated by analytical calculations prove that a change of the flexoelectric coefficient sign leads to a reorientation of the core axial polarization, making the flexosensitive 3D vortices similar to the recently introduced “flexons” in cylindrical nanoparticles. The relatively wide temperature range (from 200 to 400 K) of the flexosensitive vortices' existence gives us confidence that they can be observed experimentally in thin ferroelectric films by scanning-probe and nonlinear optical microscopy methods.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mirror at the edge of the universe: Reflections on an accelerated boundary correspondence with de Sitter cosmology

An accelerated boundary correspondence (ABC) is solved for the de Sitter moving mirror cosmology. The beta Bogoliubov coefficients reveal the particle spectrum is a Planck distribution with temperature inversely proportional to horizon radius. The quantum stress tensor indicates a constant emission of energy flux consistent with eternal equilibrium, while the total energy carried by the particles remains finite. In conclusion, the curved spacetime transformation to flat spacetime with an accelerated boundary is illustrated, and also shown for anti-de Sitter (AdS) spacetime.

79 ASTRONOMY AND ASTROPHYSICS↗

Conjugate Heat Transfer Analysis of the Supercritical CO2 Based Counter Flow Compact 3D Heat Exchangers

Compact heat exchangers using supercritical fluids such as CO2 are preferred due to their high heat transfer capacity and smaller footprint. Three-dimensional conjugate forced convection heat transfer analysis was performed on several shell-and-tube counter-flow microchannel heat exchangers. Numerical simulations were conducted to test effect of change in mass flow rate, hydraulic diameter and various cross sections on the heat transfer. Increasing mass flow rate improved heat transfer up to a maximum value and then decreased downstream with increasing turbulence. Maximum heat transfer was obtained for the micro channel with the smallest hydraulic diameter. Amongst the cross sections analyzed (circular, square, circular with radial ribs, and square with radial ribs), the most uniform distribution of temperature and maximum heat transfer were obtained for circular cross section with radial ribs. An optimally efficient operation of such a heat exchanger can be attained by considering these factors during multi-objective constrained optimization of geometric parameters and requirements for additive manufacturing of such compact heat exchangers.

Chitale, Janhavi↗

Recent Progress in Developing Nb 3 Sn Conductors With Increased Specific Heat

A possible approach to reducing Nb 3 Sn magnet training is to increase the energy margin of Nb 3 Sn conductors by enhancing their specific heat (C p ). For this study, we have been developing Nb 3 Sn conductors with increased C p by incorporating substances with high C p at 2-10 K based on a conductor design that is compatible with standard Nb 3 Sn strand production. In the past couple of years our efforts have been mainly focused on improving strand design (e.g., position of high- C p filaments, thickness of the Cu tube for the high-C p filaments, ratio of the Cu powder to the high-C p substance, filament spacing, etc.) in order to obtain good strand drawability and to reduce degradation after rolling, which is needed for production of Rutherford cables. We also tried a new high-C p substance, Gd 2 O 2 S, and verified that it has much higher C p over the whole magnetic field range than the Gd 2 O 3 we used before. With that development work we can now produce high-C p strands with good drawability and low levels of degradation after rolling. This paper reports our findings and the current status of the development of high-C p Nb 3 Sn conductors.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Effect of material properties on batch‐to‐glass conversion kinetics

Abstract A recently developed model of the cold cap—the reacting glass batch (melter feeds) floating on molten glass in an electric glass melter—couples heat transfer with the feed‐to‐glass conversion kinetics. The model allows for determining the distributions of temperature and various properties within the cold cap. In the present study, this model is applied to four melter feeds designed for high‐level and low‐activity nuclear wastes. Profiles of temperature, conversion degree, cold cap porosity and density, condensed matter velocity, and heating rate were determined using the material properties of the cold cap. Effects of vigorous foaming at the cold cap bottom were considered. Density, thermal conductivity, and glass production rate strongly affect the cold cap thickness and the fraction of undissolved silica entering the melt under the cold cap. The heating rate profile in the cold cap is highly nonlinear, with high heating rates observed in the foam layer.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗