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At least 721 records · Page 40

Validation of Thermal Scattering Laws for Light Water at Elevated Temperatures with Diffusion Experiments

Light water is the most important neutron moderator in many reactor applications. Thermal neutron scattering kernels for H bound in H 2 O are represented by ENDF-format thermal scattering laws (TSLs) evaluated at discrete temperatures T . Nuclear data evaluations are conventionally validated utilizing a combination of critical benchmarks and experimental cross section data. Existing public critical benchmarks may be inadequate for testing water TSLs over the full range of T of interest in reactor applications, and experimental thermal scattering cross section data for water is sparse at elevated T . In this work, MC21 is used to simulate the decay of the equilibrium thermal neutron flux in light-water spheres of several radii. The fundamental-mode time eigenvalue $\mathcal{a}$ is calculated at 22 °C and 227 °C (at saturation pressure) for each sphere using three different H-H 2 O TSLs. Fitting $\mathcal{a}$ to a polynomial function of geometric buckling allows calculation of the thermal neutron diffusion length L . Extrapolation lengths are treated as a function of the transport mean free path and geometry. Experimental L data from 25 publications at 49 temperatures (from 10 °C to 295 °C), computed by several different time-dependent and space-dependent decay methods, is used to develop an empirical fit of L vs. T . The MC21-calculated L for the TSLs tested are within ±1% of the predicted values at 22 °C and 227 °C. This validation approach, which may be repeated at arbitrary T , constitutes an integral benchmark specific to and characterizing the detailed physics of the thermal scattering kernel applied.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Elevated temperature, nano-mechanical testing in situ in the scanning electron microscope

A general nano-mechanical test platform capable of performing variable temperature and variable strain rate testing in situ in the scanning electron microscope is described. A variety of test geometries are possible in combination with focused ion beam machining or other fabrication techniques: indentation, micro-compression, cantilever bending, and scratch testing. The system is intrinsically displacement-controlled, which allows it to function directly as a micro-scale thermomechanical test frame. Stable, elevated temperature indentation/micro-compression requires the indenter tip and the sample to be in thermal equilibrium to prevent thermal displacement drift due to thermal expansion. This is achieved through independent heating and temperature monitoring of both the indenter tip and sample. Furthermore, the apex temperature of the indenter tip is calibrated, which allows it to act as a referenced surface temperature probe during contact. A full description of the system is provided, and the effects of indenter geometry and of radiation on imaging conditions are discussed. The stabilization time and temperature distribution throughout the system as a function of temperature is characterized. The advantages of temperature monitoring and thermal calibration of the indenter tip are illustrated, which include the possibility of local thermal conductivity measurement. Finally, validation results using nanoindentation on fused silica and micro-compression of <100> silicon micro-pillars as a function of temperature up to 500 Degree-Sign C are presented, and procedures and considerations taken for these measurements are discussed. A brittle to ductile transition from fracture to splitting then plastic deformation is directly observed in the SEM for silicon as a function of temperature.

36 MATERIALS SCIENCE↗

Note: Operation of gamma-ray microcalorimeters at elevated count rates using filters with constraints

Microcalorimeter sensors operated near 0.1 K can measure the energy of individual x- and gamma-ray photons with significantly more precision than conventional semiconductor technologies. Both microcalorimeter arrays and higher per pixel count rates are desirable to increase the total throughput of spectrometers based on these devices. The millisecond recovery time of gamma-ray microcalorimeters and the resulting pulse pileup are significant obstacles to high per pixel count rates. Here, we demonstrate operation of a microcalorimeter detector at elevated count rates by use of convolution filters designed to be orthogonal to the exponential tail of a preceding pulse. These filters allow operation at 50% higher count rates than conventional filters while largely preserving sensor energy resolution.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Shape of isolated domains in lithium tantalate single crystals at elevated temperatures

The shape of isolated domains has been investigated in congruent lithium tantalate (CLT) single crystals at elevated temperatures and analyzed in terms of kinetic approach. The obtained temperature dependence of the growing domain shape in CLT including circular shape at temperatures above 190 °C has been attributed to increase of relative input of isotropic ionic conductivity. The observed nonstop wall motion and independent domain growth after merging in CLT as opposed to stoichiometric lithium tantalate have been attributed to difference in wall orientation. The computer simulation has confirmed applicability of the kinetic approach to the domain shape explanation.

36 MATERIALS SCIENCE↗

Tantalum and vanadium response to shock-wave loading at normal and elevated temperatures. Non-monotonous decay of the elastic wave in vanadium

The evolution of the elastic precursor waves in pure tantalum and vanadium is presented at normal and elevated temperatures over propagation distances that ranged from 0.125 to 3 mm. Measurements were performed in order to obtain experimental data about the temperature-rate dependence of the yield stress of the two metals. With increasing propagation distance, the rate of the decay of elastic precursor decreases, as the shear stress in the elastic precursor wave approaches the Peierls stresses. It has been found that the decay, with propagation distance, of the post-spike minimum of the spike-like elastic precursor wave in vanadium is essentially non-monotonous. The experiments also revealed that annealing of tantalum and vanadium increases their Hugoniot elastic limit. The anomalous increase of the high strain rate yield stress with temperature, as observed earlier for some FCC and HCP metals, has not been detected in these measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Note: A method for minimizing oxide formation during elevated temperature nanoindentation

A standardized method to protect metallic samples and minimize oxide formation during elevated-temperature nanoindentation was adapted to a commercial instrument. Nanoindentation was performed on Al (100), Cu (100), and W (100) single crystals submerged in vacuum oil at 200 °C, while the surface morphology and oxidation was carefully monitored using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The results were compared to room temperature and 200 °C nanoindentation tests performed without oil, in order to evaluate the feasibility of using the oil as a protective medium. Extensive surface characterization demonstrated that this methodology is effective for nanoscale testing.

36 MATERIALS SCIENCE↗

Dirac point and transconductance of top-gated graphene field-effect transistors operating at elevated temperature

Top-gated graphene field-effect transistors (GFETs) have been fabricated using bilayer epitaxial graphene grown on the Si-face of 4H-SiC substrates by thermal decomposition of silicon carbide in high vacuum. Graphene films were characterized by Raman spectroscopy, Atomic Force Microscopy, Scanning Tunnelling Microscopy, and Hall measurements to estimate graphene thickness, morphology, and charge transport properties. A 27 nm thick Al₂O₃ gate dielectric was grown by atomic layer deposition with an e-beam evaporated Al seed layer. Electrical characterization of the GFETs has been performed at operating temperatures up to 100 °C limited by deterioration of the gate dielectric performance at higher temperatures. Devices displayed stable operation with the gate oxide dielectric strength exceeding 4.5 MV/cm at 100 °C. Significant shifting of the charge neutrality point and an increase of the peak transconductance were observed in the GFETs as the operating temperature was elevated from room temperature to 100 °C.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Communication: Estimating the initial biasing potential for λ-local-elevation umbrella-sampling (λ-LEUS) simulations via slow growth

In a recent article [Bieler et al., J. Chem. Theory Comput. 10, 3006–3022 (2014)], we introduced a combination of the λ-dynamics (λD) approach for calculating alchemical free-energy differences and of the local-elevation umbrella-sampling (LEUS) memory-based biasing method to enhance the sampling along the alchemical coordinate. The combined scheme, referred to as λ-LEUS, was applied to the perturbation of hydroquinone to benzene in water as a test system, and found to represent an improvement over thermodynamic integration (TI) in terms of sampling efficiency at equivalent accuracy. However, the preoptimization of the biasing potential required in the λ-LEUS method requires “filling up” all the basins in the potential of mean force. This introduces a non-productive pre-sampling time that is system-dependent, and generally exceeds the corresponding equilibration time in a TI calculation. In this letter, a remedy is proposed to this problem, termed the slow growth memory guessing (SGMG) approach. Instead of initializing the biasing potential to zero at the start of the preoptimization, an approximate potential of mean force is estimated from a short slow growth calculation, and its negative used to construct the initial memory. Considering the same test system as in the preceding article, it is shown that of the application of SGMG in λ-LEUS permits to reduce the preoptimization time by about a factor of four.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward accurate thermochemistry of the {sup 24}MgH, {sup 25}MgH, and {sup 26}MgH molecules at elevated temperatures: Corrections due to unbound states

The total partition functions Q(T) and their first two moments Q{sup ′}(T) and Q{sup ″}(T), together with the isobaric heat capacities C{sub p}(T), are computed a priori for three major MgH isotopologues on the temperature range of T = 100–3000 K using the recent highly accurate potential energy curve, spin-rotation, and non-adiabatic correction functions of Henderson et al. [J. Phys. Chem. A 117, 13373 (2013)]. Nuclear motion computations are carried out on the ground electronic state to determine the (ro)vibrational energy levels and the scattering phase shifts. The effect of resonance states is found to be significant above about 1000 K and it increases with temperature. Even very short-lived states, due to their relatively large number, have significant contributions to Q(T) at elevated temperatures. The contribution of scattering states is around one fourth of that of resonance states but opposite in sign. Uncertainty estimates are given for the possible error sources, suggesting that all computed thermochemical properties have an accuracy better than 0.005% up to 1200 K. Between 1200 and 2500 K, the uncertainties can rise to around 0.1%, while between 2500 K and 3000 K, a further increase to 0.5% might be observed for Q{sup ″}(T) and C{sub p}(T), principally due to the neglect of excited electronic states. The accurate thermochemical data determined are presented in the supplementary material for the three isotopologues of {sup 24}MgH, {sup 25}MgH, and {sup 26}MgH at 1 K increments. These data, which differ significantly from older standard data, should prove useful for astronomical models incorporating thermodynamic properties of these species.

74 ATOMIC AND MOLECULAR PHYSICS↗

Intrinsic evolutions of dielectric function and electronic transition in tungsten doping Ge{sub 2}Sb{sub 2}Te{sub 5} phase change films discovered by ellipsometry at elevated temperatures

Tungsten (W) doping effects on Ge{sub 2}Sb{sub 2}Te{sub 5} (GSTW) phase change films with different concentrations (3.2, 7.1, and 10.8%) have been investigated by variable-temperature spectroscopic ellipsometry. The dielectric functions from 210 K to 660 K have been evaluated with the aid of Tauc-Lorentz and Drude dispersion models. The analysis of Tauc gap energy (E{sub g}) and partial spectral weight integral reveal the correlation between optical properties and local structural change. The order degree increment and chemical bond change from covalent to resonant should be responsible for band gap narrowing and electronic transition enhancement during the phase change process. It is found that the elevated crystalline temperature for GSTW can be related to improved disorder degree. Furthermore, the shrinkage of E{sub g} for GSTW should be attributed to the enhanced metallicity compared with undoped GST.

36 MATERIALS SCIENCE↗

Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allows an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rotating disk electrode system for elevated pressures and temperatures

We describe the development and test of an elevated pressure and temperature rotating disk electrode (RDE) system that allows measurements under well-defined mass transport conditions. As demonstrated for the oxygen reduction reaction on polycrystalline platinum (Pt) in 0.5M H{sub 2}SO{sub 4}, the setup can easily be operated in a pressure range of 1–101 bar oxygen, and temperature of 140 °C. Under such conditions, diffusion limited current densities increase by almost two orders of magnitude as compared to conventional RDE setups allowing, for example, fuel cell catalyst studies under more realistic conditions. Levich plots demonstrate that the mass transport is indeed well-defined, i.e., at low electrode potentials, the measured current densities are fully diffusion controlled, while at higher potentials, a mixed kinetic-diffusion controlled regime is observed. Therefore, the setup opens up a new field for RDE investigations under temperature and current density conditions relevant for low and high temperature proton exchange membrane fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Damage buildup in Ar-ion-irradiated 3 C -SiC at elevated temperatures

Above room temperature, the accumulation of radiation damage in 3 C -SiC is strongly influenced by dynamic defect interaction processes and remains poorly understood. Here, we use a combination of ion channeling and transmission electron microscopy to study lattice disorder in 3 C -SiC irradiated with 500 keV Ar ions in the temperature range of 25–250 °C. Results reveal sigmoidal damage buildup for all the temperatures studied. For 150 °C and below, the damage level monotonically increases with ion dose up to amorphization. Starting at 200 °C, the shape of damage–depth profiles becomes anomalous, with the damage peak narrowing and moving to larger depths and an additional shoulder forming close to the ion end of range. As a result, damage buildup curves for 200 and 250 °C exhibit an anomalous two-step shape, with a damage saturation stage followed by rapid amorphization above a critical ion dose, suggesting a nucleation-limited amorphization behavior. Despite their complexity, all damage buildup curves are well described by a phenomenological model based on an assumption of a linear dependence of the effective amorphization cross section on ion dose. Here, in contrast to the results of previous studies, 3 C -SiC can be amorphized by bombardment with 500 keV Ar ions even at 250 °C with a relatively large dose rate of ~2×10 13 cm -2 s -1 , revealing a dominant role of defect interaction dynamics at elevated temperatures.

36 MATERIALS SCIENCE↗

Optical and electronic properties of sub-surface conducting layers in diamond created by MeV B-implantation at elevated temperatures

Boron implantation with in-situ dynamic annealing is used to produce highly conductive sub-surface layers in type IIa (100) diamond plates for the search of a superconducting phase transition. Here, we demonstrate that high-fluence MeV ion-implantation, at elevated temperatures avoids graphitization and can be used to achieve doping densities of 6 at. %. In order to quantify the diamond crystal damage associated with implantation Raman spectroscopy was performed, demonstrating high temperature annealing recovers the lattice. Additionally, low-temperature electronic transport measurements show evidence of charge carrier densities close to the metal-insulator-transition. After electronic characterization, secondary ion mass spectrometry was performed to map out the ion profile of the implanted plates. The analysis shows close agreement with the simulated ion-profile assuming scaling factors that take into account an average change in diamond density due to device fabrication. Finally, the data show that boron diffusion is negligible during the high temperature annealing process.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Stand-alone polarization-modulation infrared reflection absorption spectroscopy instrument optimized for the study of catalytic processes at elevated pressures

This article describes the design and construction of a compact, “user-friendly” polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS) instrument at the Center for Functional Nanomaterials (CFN) of Brookhaven National Laboratory, which allows studying surfaces at pressures ranging from ultra-high vacuum to 100 Torr. Surface infrared spectroscopy is ideally suited for studying these processes as the vibrational frequencies of the IR chromophores are sensitive to the nature of the bonding environment on the surface. Relying on the surface selection rules, by modulating the polarization of incident light, it is possible to separate the contributions from the isotropic gas or solution phase, from the surface bound species. A spectral frequency range between 1000 cm -1 and 4000 cm -1 can be acquired. While typical spectra with a good signal to noise ratio can be obtained at elevated pressures of gases in ~2 min at 4 cm -1 resolution, we have also acquired higher resolution spectra at 0.25 cm -1 with longer acquisition times. By way of verification, CO uptake on a heavily oxidized Ru(0001) sample was studied. As part of this test study, the presence of CO adsorbed on Ru bridge sites was confirmed, in agreement with previous ambient pressure X ray photoelectron spectroscopy studies. In terms of instrument performance, it was also determined that the gas phase contribution from CO could be completely removed even up to pressures close to 100 Torr. A second test study demonstrated the use of the technique for studying morphological properties of a spin coated polymer on a conductive surface. Note that this is a novel application of this technique. In this experiment, the polarization of incident light was modulated manually (vs. through a photoelastic modulator). It was demonstrated, in good agreement with the literature, that the polymer chains preferentially lie parallel with the surface. This PM-IRRAS system is small, modular, and easily reconfigurable. It also features a “vacuum suitcase” that allows for the integration of the PM-IRRAS system with the rest of the suite of instrumentation at our laboratory available to external users through the CFN user proposal system.

36 MATERIALS SCIENCE↗

The behavior of methane–water mixtures under elevated pressures from simulations using many-body potentials

Non-polarizable empirical potentials have been proven to be incapable of capturing the mixing of methane–water mixtures at elevated pressures. Although density functional theory-based ab initio simulations may circumvent this discrepancy, they are limited in terms of the relevant time and length scales associated with mixing phenomena. Here, we show that the many-body MB-nrg potential, designed to reproduce methane–water interactions with coupled cluster accuracy, successfully captures this phenomenon up to 3 GPa and 500 K with varying methane concentrations. Two-phase simulations and long time scales that are required to fully capture the mixing, affordable due to the speed and accuracy of the MBX software, are assessed. Constructing the methane–water equation of state across the phase diagram shows that the stable mixtures are denser than the sum of their parts at a given pressure and temperature. As a result, we find that many-body polarization plays a central role, enhancing the induced dipole moments of methane by 0.20 D during mixing under pressure. Overall, the mixed system adopts a denser state, which involves a significant enthalpic driving force as elucidated by a systematic many-body energy decomposition analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amino acid modified Ni catalyst exhibits reversible H 2 oxidation/production over a broad pH range at elevated temperatures

Hydrogenases interconvert H 2 and protons at high rates and with high energy efficiencies, providing inspiration for the development of molecular catalysts. Studies designed to determine how the protein scaffold can influence a catalytically active site has led to the synthesis of amino acid derivatives, [Ni(P Cy 2 N Amino acid 2) 2 ] 2+ (CyAA), of [Ni(P R 2 N R' 2 ) 2 ] 2+ complexes. It is shown that these CyAA derivatives can catalyze fully reversible H 2 production/oxidation, a feature reminiscent of enzymes. The reversibility is achieved in acidic aqueous solutions, 0.25% H 2 /Ar, and elevated temperatures (tested up to 348 K) for the glycine (CyGly), arginine (CyArg), and arginine methyl ester (CyArgOMe) derivatives. As expected for a reversible process, the activity is dependent upon H 2 and proton concentration. CyArg is significantly faster in both directions than the other two derivatives (~300 s -1 H 2 production and 20 s -1 H 2 oxidation; pH = 1, 348 K). The significantly slower rates for CyArgOMe (35 s -1 production and 7 s -1 oxidation) compared to CyArg suggests an important role for the COOH group during catalysis. That CyArg is faster than CyGly (3 s -1 production and 4 s -1 oxidation under the same conditions) suggests that the additional structural features imparted by the guanidinium groups facilitate fast and reversible H 2 addition/release. Furthermore, these observations demonstrate that appended, outer coordination sphere amino acids work in synergy with the active site and can play an equally important role for synthetic molecular electrocatalysts as the protein scaffold does for redox active enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Asynchronous nitrogen supply and demand produce nonlinear plant allocation responses to warming and elevated CO 2

Terrestrial ecosystem responses to climate change are mediated by complex plant–soil feedbacks that are poorly understood, but often driven by the balance of nutrient supply and demand. We actively increased aboveground plant-surface temperature, belowground soil temperature, and atmospheric CO 2 in a brackish marsh and found nonlinear and nonadditive feedbacks in plant responses. Changes in root-to-shoot allocation by sedges were nonlinear, with peak belowground allocation occurring at +1.7 °C in both years. Above 1.7 °C, allocation to root versus shoot production decreased with increasing warming such that there were no differences in root biomass between ambient and +5.1 °C plots in either year. Elevated CO 2 altered this response when crossed with +5.1 °C, increasing root-to-shoot allocation due to increased plant nitrogen demand and, consequently, root production. We suggest these nonlinear responses to warming are caused by asynchrony between the thresholds that trigger increased plant nitrogen (N) demand versus increased N mineralization rates. The resulting shifts in biomass allocation between roots and shoots have important consequences for forecasting terrestrial ecosystem responses to climate change and understanding global trends.

54 ENVIRONMENTAL SCIENCES↗