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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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A multiphysics model is presented to study potential losses in Cu-MEAs and how various physical phenomena impact the product distribution of CO 2 reduction.
The rapid transient method records time stamps of individual ion arrival for accurate identification and quantification of nanoparticles.
An unexpected blue shift in the characteristic uranyl ν1 stretching frequency is observed upon engagement of the uranyl oxo with isothiocyanate group stemming from coupling between UO and U-NCS modes.
Phosphinodiboranates (H 3 BPR 2 BH 3 – ) are a class of borohydrides that have merited a reputation as weakly coordinating anions, which is attributed in part to the dearth of coordination complexes known with transition metals, lanthanides, and actinides. We recently reported how K(H 3 BP t Bu 2 BH 3 ) exhibits sluggish salt elimination reactivity with f-metal halides in organic solvents such as Et 2 O and THF. Here we report how this reactivity appears to be further attenuated in solution when the t Bu groups attached to phosphorus are exchanged for R = Ph or H, and we describe how mechanochemistry was used to overcome limited solution reactivity with K(H 3 BPPh 2 BH 3 ). Grinding three equivalents of K(H 3 BPPh 2 BH 3 ) with UI 3 (THF) 4 or LnI 3 (Ln = Ce, Pr, Nd) allowed homoleptic complexes with the empirical formulas U(H 3 BPPh 2 BH 3 ) 3 (1), Ce(H 3 BPPh 2 BH 3 ) 3 (2), Pr(H 3 BPPh 2 BH 3 ) 3 (3), and Nd(H 3 BPPh 2 BH 3 ) 3 (4) to be prepared and subsequently crystallized in good yields (50–80%). Single-crystal XRD studies revealed that all four complexes exist as dimers or coordination polymers in the solid-state, whereas 1 H and 11 B NMR spectra showed that they exist as a mixture of monomers and dimers in solution. Treating 4 with THF breaks up the dimer to yield the monomeric complex Nd(H 3 BPPh 2 BH 3 ) 3 (THF) 3 (4-THF). XRD studies revealed that 4-THF has one chelating and two dangling H 3 BPPh 2 BH 3 – ligands bound to the metal to accommodate binding of THF. In contrast to the results with K(H 3 BPPh 2 BH 3 ), attempting the same mechanochemical reactions with Na(H 3 BPH 2 BH 3 ) containing the simplest phosphinodiboranate were unsuccessful; only the partial metathesis product U(H 3 BPH 2 BH 3 )I 2 (THF) 3 (5) was isolated in poor yields. Here, despite these limitations, our results offer new examples showing how mechanochemistry can be used to rapidly synthesize molecular coordination complexes that are otherwise difficult to prepare using more traditional solution methods.
Celeritas is a new computational transport code designed for high-performance simulation of high-energy physics detectors. This work describes some of its current capabilities and the design choices that enable the rapid development of efficient on-device physics. The abstractions that underpin the code design facilitate low-level performance tweaks that require no changes to the higher-level physics code. We evaluate a set of independent changes that together yield an almost 40% speedup over the original GPU code for a net performance increase of 220× for a single GPU over a single CPU running 8.4M tracks on a small demonstration physics app.
Standard forms of density-functional theory (DFT) have good suggestive power for many materials, but are not yet fully satisfactory for cluster, solid, and liquid forms of water. Current work has stressed the importance of DFT errors in describing dispersion, but we note that errors in other parts of the energy may also contribute. We obtain information about the nature of DFT errors by using a many-body separation of the total energy into its 1-body, 2-body, and beyond-2-body components to analyze the deficiencies of the popular PBE and BLYP approximations for the energetics of water clusters and ice structures. The errors of these approximations are computed by using accurate benchmark energies from the coupled-cluster technique of molecular quantum chemistry and from quantum Monte Carlo calculations. The systems studied are isomers of the water hexamer cluster, the crystal structures Ih, II, XV, and VIII of ice, and two clusters extracted from ice VIII. For the binding energies of these systems, we use the machine-learning technique of Gaussian Approximation Potentials to correct successively for 1-body and 2-body errors of the DFT approximations. We find that even after correction for these errors, substantial beyond-2-body errors remain. The characteristics of the 2-body and beyond-2-body errors of PBE are completely different from those of BLYP, but the errors of both approximations disfavor the close approach of non-hydrogen-bonded monomers. We note the possible relevance of our findings to the understanding of liquid water.
We present a general methodology to determine the diagnostic sensitivity that is directly applicable to neutron-activation diagnostics fielded on a wide variety of neutron-producing experiments, which include inertial-confinement fusion (ICF), dense plasma focus, and ion beam-driven concepts. This approach includes a combination of several effects: (1) non-isotropic neutron emission; (2) the 1/r{sup 2} decrease in neutron fluence in the activation material; (3) the spatially distributed neutron scattering, attenuation, and energy losses due to the fielding environment and activation material itself; and (4) temporally varying neutron emission. As an example, we describe the copper-activation diagnostic used to measure secondary deuterium-tritium fusion-neutron yields on ICF experiments conducted on the pulsed-power Z Accelerator at Sandia National Laboratories. Using this methodology along with results from absolute calibrations and Monte Carlo simulations, we find that for the diagnostic configuration on Z, the diagnostic sensitivity is 0.037% ± 17% counts/neutron per cm{sup 2} and is ∼ 40% less sensitive than it would be in an ideal geometry due to neutron attenuation, scattering, and energy-loss effects.
The dynamics of texture formation, changes in crystal structure, and stress accommodation mechanisms have been studied in perovskite-type R3⁻c rhombohedral LaCoO₃ during uniaxial compression using in-situ neutron diffraction. The in-situ neutron diffraction revealed the complex crystallographic changes causing the texture formation and significant straining along certain crystallographic directions during compression, which are responsible for the appearance of hysteresis and non-linear ferroelastic deformation in the LaCoO₃ perovskite. The irreversible strain after the first loading was connected with the appearance of non-recoverable changes in the intensity ratio of certain crystallographic peaks, causing non-reversible texture formation. However, in the second loading/unloading cycle, the hysteresis loop was closed and no further irrecoverable strain appeared after deformation. The significant texture formation is responsible for an increase in the Young's modulus of LaCoO₃ at high compressive stresses, ranging from 76 GPa at the very beginning of the loading to 194 GPa at 900 MPa at the beginning of the unloading curve.
A universal procedure was developed to calibrate image plate scanners using radioisotope sources. Techniques to calibrate scanners and sources, as well as cross-calibrate scanner models, are described to convert image plate dosage into physical units. This allows for the direct comparison of quantitative data between any facility and scanner. An empirical relation was also derived to establish sensitivity response settings for arbitrary gain settings. In practice, these methods may be extended to any image plate scanning system.
We report on the anisotropic optical properties of single-crystal tin monosulfide (SnS). The components ε{sub a}, ε{sub b}, and ε{sub c} of the pseudodielectric-function tensor (ε)=(ε₁)+i(ε₂) spectra are taken from 0.73 to 6.45 eV by spectroscopic ellipsometry. The measured (ε) spectra are in a good agreement with the results of the calculated dielectric response from hybrid density functional theory. The (ε) spectra show the direct band-gap onset and a total of eight above-band-gap optical structures that are associated with the interband-transition critical points (CPs). We obtain accurate CP energies by fitting analytic CP expressions to second-energy-derivatives of the (ε) data. Their probable electronic origins and implications for photovoltaic applications are discussed.
A detailed understanding of the inherently multiscale proton transport process raises a number of scientifically challenging questions. For example, there remain many (partially addressed) questions on the molecular mechanism for long-range proton migration and the potential for the formation of long-lived traps giving rise to burst-and-rest proton dynamics. Using results from a sizeable collection of ab initio molecular dynamics (AIMD) simulations (totaling ∼2.7 ns) with various density functional approximations (Becke-Lee-Yang-Parr (BLYP), BLYP–D3, Hamprecht-Cohen-Tozer-Handy, B3LYP) and temperatures (300–330 K), equilibrium and dynamical properties of one excess proton and 128 water molecules are studied. Two features in particular (concerted hops and weak hydrogen-bond donors) are investigated to identify modes in the system that are strongly correlated with the onset of periods of burst-and-rest dynamics. The question of concerted hops seeks to identify those time scales over which long-range proton transport can be classified as a series of sequential water hopping events or as a near-simultaneous concerted process along compressed water wires. The coupling of the observed burst-and-rest dynamics with motions of a fourth neighboring water molecule (a weak hydrogen-bond donor) solvating the protonated water molecule is also investigated. The presence (absence) of hydrogen bonds involving this fourth water molecule before and after successful proton hopping events is found to be strongly correlated with periods of burst (rest) dynamics (and consistent with pre-solvation concepts). By analyzing several realizations of the AIMD trajectories on the 100-ps time scale, convergence of statistics can be assessed. For instance, it was observed that the probability for a fourth water molecule to approach the hydronium, if not already proximal at the beginning of the lifetime of the hydronium, is very low, indicative of the formation of stable void regions. Furthermore, the correlations of the neighboring water atoms are identified as the fourth water approaches the hydronium. Finally, the temperature effects on structural and dynamical properties are studied.
The dynamics of ions in ultrafast laser ablation of metals is studied over fluences ranging from the ablation threshold up to ≈75 J/cm{sup 2} by means of three well-established diagnostic techniques. Langmuir probe, Faraday cup, and spectrally resolved intensified charge coupled device imaging simultaneously monitored the ions produced during ultrafast laser ablation of a pure copper target with 800 nm, ≈50 fs, Ti: Sapphire laser pulses. The fluence dependence of ion yield is analyzed, resulting in the observance of three different regimes. The specific ion yield shows a maximum at about 4–5 J/cm{sup 2}, followed by a gradual reduction and a transition to a high-fluence regime above ≈50 J/cm{sup 2}. The fluence dependence of the copper ions angular distribution is also analyzed, observing a gradual increase in forward-peaking of Cu ions for fluences up to ≈10 J/cm{sup 2}. A broader ion component is observed at larger angles for fluences larger than ≈10 J/cm{sup 2}. Finally, an experimental characterization of the ionic angular distribution for several metallic targets (Mg, Al, Cr, Fe, Cu, and W) is carried out at a relatively high fluence of ≈66 J/cm{sup 2}. Interestingly, the ion emission from the volatile metals shows a narrow, forward-peaked distribution, and a high peak ion yield compared to the refractory metals. Moreover, the width of ionic angular distributions presents a striking correlation with the peak ion yield.
In this work, we examine how deuterium becomes trapped in plasma-exposed tungsten and forms near-surface platelet-shaped precipitates. How these bubbles nucleate and grow, as well as the amount of deuterium trapped within, is crucial for interpreting the experimental database. Here, we use a combined experimental/theoretical approach to provide further insight into the underlying physics. With the Tritium Plasma Experiment, we exposed a series of ITER-grade tungsten samples to high flux D plasmas (up to 1.5 × 10{sup 22 }m{sup −2} s{sup −1}) at temperatures ranging between 103 and 554 °C. Retention of deuterium trapped in the bulk, assessed through thermal desorption spectrometry, reached a maximum at 230 °C and diminished rapidly thereafter for T > 300 °C. Post-mortem examination of the surfaces revealed non-uniform growth of bubbles ranging in diameter between 1 and 10 μm over the surface with a clear correlation with grain boundaries. Electron back-scattering diffraction maps over a large area of the surface confirmed this dependence; grains containing bubbles were aligned with a preferred slip vector along the <111> directions. Focused ion beam profiles suggest that these bubbles nucleated as platelets at depths of 200 nm–1 μm beneath the surface and grew as a result of expansion of sub-surface cracks. To estimate the amount of deuterium trapped in these defects relative to other sites within the material, we applied a continuum-scale treatment of hydrogen isotope precipitation. In addition, we propose a straightforward model of near-surface platelet expansion that reproduces bubble sizes consistent with our measurements. For the tungsten microstructure considered here, we find that bubbles would only weakly affect migration of D into the material, perhaps explaining why deep trapping was observed in prior studies with plasma-exposed neutron-irradiated specimens. We foresee no insurmountable issues that would prevent the theoretical framework developed here from being extended to a broader range of systems where precipitation of insoluble gases in ion beam or plasma-exposed metals is of interest.
The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI){sub x}M{sup +} (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.
Neutron time-of-flight diagnostics have long been used to characterize the neutron spectrum produced by inertial confinement fusion experiments. The primary diagnostic goals are to extract the d + t → n + α (DT) and d + d → n + {sup 3}He (DD) neutron yields and peak widths, and the amount DT scattering relative to its unscattered yield, also known as the down-scatter ratio (DSR). These quantities are used to infer yield weighted plasma conditions, such as ion temperature (T{sub ion}) and cold fuel areal density. We report on novel methodologies used to determine neutron yield, apparent T{sub ion}, and DSR. These methods invoke a single temperature, static fluid model to describe the neutron peaks from DD and DT reactions and a spline description of the DT spectrum to determine the DSR. Both measurements are performed using a forward modeling technique that includes corrections for line-of-sight attenuation and impulse response of the detection system. These methods produce typical uncertainties for DT T{sub ion} of 250 eV, 7% for DSR, and 9% for the DT neutron yield. For the DD values, the uncertainties are 290 eV for T{sub ion} and 10% for the neutron yield.
Here, we present a new experimental protocol to investigate the relationship between texture, plastic strain, and the mechanisms of plastic deformation at high pressure and temperature. The method utilizes synchrotron X-ray radiation as the probing tool, coupled with a large-volume high pressure deformation device (D-DIA). The intensity of X-ray diffraction peaks within the spectrum of the sample is used for sampling texture development in situ. The unique feature of this study is given by the sinusoidal variation of the intensity when a sinusoidal strain is applied to the sample. For a sample of magnesium oxide at elevated pressure and temperature, we demonstrate observations that are consistent with elasto-plastic models for texture development and for diffraction-peak measurements of apparent stress. The sinusoidal strain magnitude was 3%.
Single phase of nanocrystalline Ba{sub x}Sr{sub 1-x}Fe{sub 12}O{sub 19} (x = 1.0; 0.6; and 0.4) was successfully synthesized by mechanical milling method and thermal process. Stoichiometric quantities of analytical-grade SrCO{sub 3}, BaCO{sub 3}, and Fe{sub 2}O{sub 3}, were mixed and milled using a high-energy milling. The mixture of all precursors was sintered at a temperature of 1000 °C for 10 hours. The refinement of x-ray diffraction trace for all samples confirmed a single phase material with a hexagonal structure. The increase of the amount of strontium content in the barium atoms in the Ba{sub x}Sr{sub 1-x}Fe{sub 12}O{sub 19} system can decrease the lattice parameter which have been successfully substituted into the barium atoms. The calculation result of cationic distribution showed that the Ba{sub x}Sr{sub 1-x}Fe{sub 12}O{sub 19} (x = 0.6) and (x = 0.4) samples have nominal composition of Ba{sub 0,61}Sr{sub 0,39}Fe{sub 12}O{sub 19} and Ba{sub 0,37}Sr{sub 0,63}Fe{sub 12}O{sub 19}, respectively. Results of the mean of crystallite size evaluation for respective powder materials showed that the Ba{sub x}Sr{sub 1-x}Fe{sub 12}O{sub 19} (x = 1.0; 0.6; and 0.4) samples have the crystallite size of 22 nm, 25 nm and 34 nm, respectively. We concluded that the cationic distribution of barium atoms was successfully substituted by strontium atoms approaching the nominal stoichiometric composition.
With the aim of gaining a better physical insight into linear regimes in gyrotrons, a new linear model was developed. This model is based on a spectral approach for solving the self-consistent system of equations describing the wave-particle interaction in the cavity of a gyrotron oscillator. Taking into account the wall-losses self-consistently and including the main system inhomogeneities in the cavity geometry and in the magnetic field, the model is appropriate to consider real system parameters. The main advantage of the spectral approach, compared with a time-dependent approach, is the possibility to describe all of the stable and unstable modes, respectively, with negative and positive growth rates. This permits to reveal the existence of a new set of eigenmodes, in addition to the usual eigenmodes issued from cold-cavity modes. The proposed model can be used for studying other instabilities such as, for instance, backward waves potentially excited in gyrotron beam tunnels.