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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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At least 595 records · Page 33

MO-F-CAMPUS-J-01: Acoustic Range Verification of Proton Beams: Simulation of Heterogeneity and Clinical Proton Pulses

Purpose: Through simulation, to assess acoustic-based range verification of proton beams (protoacoustics) under clinical conditions. Methods: Pressure waves generated by the energy deposition of a 150 MeV, 8 mm FWHM pulsed pencil proton beam were numerically simulated through two Methods: 1) For a homogeneous water medium, an analytical wave-equation solution was used to calculate the time-dependent pressure measured at detector points surrounding the proton Bragg peak. 2) For heterogeneity studies, a CT tissue image was used to calculate the proton dose deposition and define the acoustic properties of the voxels through which numerical pressure wave propagation was simulated with the k-Wave matlab toolbox. The simulations were used to assess the dependence of the acoustic amplitude and range-verification accuracy on proton pulse rise time and tissue heterogeneity. Results: As the proton pulse rise time is increased from 1 to 40 µs, the amplitude of the expected acoustic emission decreases (a 60% drop distal to the Bragg peak), the central frequency of the expected signal decreases (from 45 to 6 kHz), and the accuracy of the range-verification decreases (from <1 mm to 16 mm at 5 cm distal to the Bragg peak). For a 300 nA pulse, the expected pressure range is on the order of 0.1 Pa, which is observable with commercial detectors. For the heterogeneous medium, our test case shows that pressure waves emitted by an anterior pencil beam directed into the abdomen and detected posteriorly can determine the Bragg peak range to an accuracy of <2mm for a 1 µs proton pulse. Conclusion: For proton pulses with fast rise-times, protoacoustics is a promising potential method for monitoring penetration depth through heterogeneous tissue. The loss of range-verification accuracy with increasing rise-times, however, suggests the need for comparisons to modeling to improve accuracy for slower cyclotron proton sources.

07 ISOTOPE AND RADIATION SOURCES↗

Hydrogen shift isomerizations in the kinetics of the second oxidation mechanism of alkane combustion. Reactions of the hydroperoxypentylperoxy OOQOOH radical

Hydroperoxyalkylperoxy species are important intermediates that are generated during the autoignition of transport fuels. In combustion, the fate of hydroperoxyalkylperoxy is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the hydroperoxyalkylperoxy is a 1,5 H-shift, for which kinetics data are experimentally unavailable. In the present work, we study 1-hydroperoxypentan-3-yl)dioxidanyl (CH 3 CH 2 CH(OO)CH 2 CH 2 OOH) as a model compound to clarify the kinetics of 1,5 H-shift of hydroperoxyalkylperoxy species, in particular α-H isomerization and alternative competitive pathways. With a combination of electronic structure calculations, we determine previously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunneling (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity, we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for these competitive reactions are computed using system-specific quantum RRK theory. The calculated temperature range is 298–1500 K, and the pressure range is 0.01–100 atm. The accurate thermodynamic and kinetics data determined in this work are indispensable in the detailed understanding and prediction of ignition properties of hydrocarbons and alternative fuels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optically detected magnetic resonance of nitrogen vacancies in a diamond anvil cell using designer diamond anvils

Optically detected magnetic resonance of nitrogen vacancy centers in diamond offers a route to both DC and AC magnetometry in diamond anvil cells under high pressures (>3 GPa). However, a serious challenge to realizing experiments has been the insertion of microwave radiation into the sample space without screening by the gasket material. We utilize designer anvils with lithographically deposited metallic microchannels on the diamond culet as a microwave antenna. We detected the spin resonance of an ensemble of microdiamonds under pressure and measured the pressure dependence of the zero field splitting parameters. Furthermore, these experiments enable the possibility for all-optical magnetic resonance experiments on nanoliter sample volumes at high pressures.

36 MATERIALS SCIENCE↗

Laboratory studies of heavy ozone

Dissociation of ozone in the Chappuis bands has been used as an O atom source to study isotope effects occurring in the O(3P) + O2(3 Sigma g) recombination reaction. The ozone produced was found to be enriched in both of its heavy isotopes. The pressure dependence (5-1000 torr) and temperature dependence (127-360 K) of this isotope effect have been investigated. The enrichment is approximately constant from 5 torr to 100 torr and decreases at higher pressures. It increases with temperature, with O3-50 showing a slightly faster rate of increase than O3-45. The results of this experiment have clearly isolated the source of the isotope effect to the gas phase O(3P) + O2(3 Sigma g) recombination reaction.

Morton, J.↗

Evidence for charge delocalization crossover in the quantum critical superconductor CeRhIn5

Abstract The nature of charge degrees-of-freedom distinguishes scenarios for interpreting the character of a second order magnetic transition at zero temperature, that is, a magnetic quantum critical point (QCP). Heavy-fermion systems are prototypes of this paradigm, and in those, the relevant question is where, relative to a magnetic QCP, does the Kondo effect delocalize their f -electron degrees-of-freedom. Herein, we use pressure-dependent Hall measurements to identify a finite-temperature scale E loc that signals a crossover from f -localized to f -delocalized character. As a function of pressure, E loc ( P ) extrapolates smoothly to zero temperature at the antiferromagnetic QCP of CeRhIn 5 where its Fermi surface reconstructs, hallmarks of Kondo-breakdown criticality that generates critical magnetic and charge fluctuations. In 4.4% Sn-doped CeRhIn 5 , however, E loc ( P ) extrapolates into its magnetically ordered phase and is decoupled from the pressure-induced magnetic QCP, which implies a spin-density-wave (SDW) type of criticality that produces only critical fluctuations of the SDW order parameter. Our results demonstrate the importance of experimentally determining E loc to characterize quantum criticality and the associated consequences for understanding the pairing mechanism of superconductivity that reaches a maximum T c in both materials at their respective magnetic QCP.

36 MATERIALS SCIENCE↗

Equation of state for Hf, Ta, W, Re, Os, Ir, Pt, and Au to multi-terapascal pressures from density-functional theory

We present the zero-temperature equation of state (pressure dependence of compression) and phase stability predictions for the 5d-transition metals obtained from all-electron density-functional theory (DFT) calculations. The results compare favorably with experiments but extend beyond current experimental capabilities to 10 TPa. Our study reveals phase changes that are explained from the calculated electronic structure. The cubic face-centered and body-centered structures (fcc and bcc), together with two-, three-, and four-layered hexagonal structures, play major roles under compression. The results’ dependence on the electron exchange and correlation in the DFT approach is investigated, and it is shown that the impact of the choice, while significant at lower pressures, diminishes in the terapascal regime. We further illustrate that the normal parabolic trends in atomic volume and bulk modulus with atomic number, due to the occupation of bonding and anti-bonding 5d states, break down at TPa pressures, suggesting drastically different chemical bonding at these extreme conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Bandwidth controlled insulator-metal transition in BaFe 2 S 3 : A Mössbauer study under pressure

BaFe 2 S 3 is a quasi one-dimensional Mott insulator that orders antiferromagnetically below 125 K. The application of pressure induces a transition to a metallic state, and superconductivity emerges.The evolution of the magnetic behavior on increasing pressure has up to now been either studied indirectly by means of transport measurements, or by using local magnetic probes only in the low pressure region. Here, we investigate the magnetic properties of BaFe 2 S 3 up to 9.9GPa by means of synchrotron 57 Fe Mossbauer spectroscopy experiments, providing the First local magnetic phase diagram. The magnetic ordering temperature increases up to 185(5) K at 7.5GPa, and is fully suppressed at 9.9GPa. The low-temperature magnetic hyperne field is continuously reduced from 12.9 to 10.3T between 1.4 and 9.1GPa, followed by a sudden drop to zero at 9.9GPa indicating a First-order phase transition. The pressure dependence of the magnetic order in BaFe2S3 can be qualitatively explained by a combination of a bandwidth-controlled insulator-metal transition as well as a pressure enhanced exchange interaction between Fe-atoms and Fe 3d-S 3p hybridization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Novel Valence Transition in Elemental Metal Europium around 80 GPa

We report valence transition could induce structural, insulator-metal, nonmagnetic-magnetic and superconducting transitions in rare-earth metals and compounds, while the underlying physics remains unclear due to the complex interaction of localized 4f electrons as well as their coupling with itinerant electrons. The valence transition in the elemental metal europium (Eu) still has remained as a matter of debate. Using resonant x-ray emission scattering and x-ray diffraction, we pressurize the states of 4f electrons in Eu and study its valence and structure transitions up to 160 GPa. We provide compelling evidence for a valence transition around 80 GPa, which coincides with a structural transition from a monoclinic (C2/c) to an orthorhombic phase ($Pnma$). We show that the valence transition occurs when the pressure-dependent energy gap between 4f and 5d electrons approaches the Coulomb interaction. Our discovery is critical for understanding the electrodynamics of Eu, including magnetism and high-pressure superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Gradual enhancement of stripe-type antiferromagnetism in the spin-ladder material BaFe 2 S 3 under pressure

We report the recent discovery of pressure-induced superconductivity in BaFe 2 S 3 and BaFe 2 Se 3 has generated considerable interest in the 123-type iron chalcogenides. The structure of these materials features iron atoms arranged in quasi-one-dimensional ladders with either stripe-type or block-type antiferromagnetism at ambient pressure, constituting a new parent state for iron-based superconductivity in need of detailed study. Here, we report pressure-dependent neutron diffraction and muon spin relaxation/rotation measurements combined with first-principles calculations to investigate the structural, magnetic, and electronic properties of BaFe 2 S 3 under pressure. The experimental results reveal a gradual enhancement of the stripe-type ordering temperature with increasing pressure up to 2.6 GPa and no observable change in the size of the ordered moment. The ab initio calculations suggest that the magnetism is highly sensitive to the Fe-S bond lengths and angles, clarifying discrepancies with previously published results. In contrast to our experimental observations, the calculations predict a reduction of the ordered moment with pressure. In conclusion, we suggest that the robustness of the stripe-type antiferromagnetism is due to strong electron correlations not fully considered in the calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On the contribution of intramolecular zero point energy to the equation of state of solid H2

Experimental evidence shows that the internal zero-point energy of the H2 molecule exhibits a relatively strong pressure dependence in the solid as well as changing considerably upon condensation. It is shown that these effects contribute about 6% to the total sublimation energy and to the pressure in the solid state. Methods to modify the ab initio isolated pair potential to account for these environmental effects are discussed.

Chandrasekharan, V.↗

The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.

Holzheid, Astrid↗

VALVE TIMING AND AREA PROFILE SELECTION FOR HYDRAULIC PUMPS AND MOTORS

A significant amount of research has been conducted to select valve timing and area profiles that create efficient and quiet hydraulic pumps and motors. Numerous active valve architectures have been modeled and optimized, but the rationale for the final solution is often unclear. The solution is usually highly dependent on the modeled valve geometry constraints and the duty cycle of the pump or motor for which the valve was optimized. This paper first presents an ideal valve area profile and what compromises are made to design for a working pressure and speed range. The ideal valve area profile is resolved using a piston-cylinder model with a pressure dependent bulk modulus and variable valve openings. The piston-cylinder is first modeled as a pump with passive (check) valves and a specified pressure drop across the valves to determine the ideal area profile. A generalization of the ideal timing is demonstrated for positive pressure differential and positive rotation direction, also known as the first quadrant. The effects on valve timing when varying pressure are shown for the first quadrant, but the trends can be extrapolated for all quadrants of operation. The ideal valve profile is implemented as fixed valve timing, meaning the valve area is only a function of the timing angle, in a pump-motor. The pump-motor is simulated in one rotation direction through a pressure range. Performance is high in pumping operation, but when the pressure differential is reversed, cylinder pressure spikes ensue. Two strategies to modify an ideal valve area profile are presented: timing grooves and a pressure shifted valve timing. Timing grooves reduce pressure spikes and cavitation in the cylinder but generally increase throttling losses. A pressure shifted valve timing has lower throttling energy losses, making it the favored solution.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Giant Barocaloric Effect at the Spin Crossover Transition of a Molecular Crystal

Here, the first experimental evidence for a giant, conventional barocaloric effect (BCE) associated with a pressure-driven spin crossover transition near room temperature is provided. Magnetometry, neutron scattering, and calorimetry are used to explore the pressure dependence of the SCO phase transition in polycrystalline samples of protonated and partially deuterated [FeL 2 ][BF 4 ] 2 [L = 2,6-di(pyrazol-1-yl)pyridine] at applied pressures of up to 120 MPa (1200 bar). The data indicate that, for a pressure change of only 0–300 bar (0–30 MPa), an adiabatic temperature change of 3 K is observed at 262 K or 257 K in the protonated and deuterated materials, respectively. This BCE is equivalent to the magnetocaloric effect (MCE) observed in gadolinium in a magnetic field change of 0–1 Tesla. The work confirms recent predictions that giant, conventional BCEs will be found in a wide range of SCO compounds.

36 MATERIALS SCIENCE↗

Extrinsic Green Photoluminescence from the Edges of 2D Cesium Lead Halides

Abstract Since the first report of the green emission of 2D all‐inorganic CsPb 2 Br 5 , its bandgap and photoluminescence (PL) origin have generated intense debate and remained controversial. After the discovery that PL centers occupy only specific morphological structures in CsPb 2 Br 5 , a two‐step highly sensitive and noninvasive optical technique is employed to resolve the controversy. Same‐spot Raman‐PL as a static property–structure probe reveals that CsPbBr 3 nanocrystals are contributing to the green emission of CsPb 2 Br 5 ; pressure‐dependent Raman‐PL with a diamond anvil cell as a dynamic probe further rules out point defects such as Br vacancies as an alternative mechanism. Optical absorption under hydrostatic pressure shows that the bandgap of CsPb 2 Br 5 is 0.3–0.4 eV higher than previously reported values and remains nearly constant with pressure up to 2 GPa in good agreement with full‐fledged density functional theory (DFT) calculations. Using ion exchange of Br with Cl and I, it is further proved that CsPbBr 3− x X x (X = Cl or I) is responsible for the strong visible PL in CsPb 2 Br 5− x X x . This experimental approach is applicable to all PL‐active materials to distinguish intrinsic defects from extrinsic nanocrystals, and the findings pave the way for new design and development of highly efficient optoelectronic devices based on all‐inorganic lead halides.

Wang, Chong↗

Elastic properties of single crystal hydrogen sulfide: A Brillouin scattering study under high pressure-temperature

We have performed high pressure-temperature Brillouin scattering measurements on single crystal hydrogen sulfide using externally heated diamond anvil cell techniques. The pressure dependences of the acoustic velocities, isothermal elastic constants, and moduli of single crystal hydrogen sulfide have been determined along four isotherms. Both elastic constants and moduli increase monotonously with pressure along each isotherm, while they show a decreased tendency with temperature elevated under the same pressure points. The experimental equation of state of single crystal hydrogen sulfide is obtained by fitting with a third-order Birch-Murnaghan and Tait equation. It is proposed that the effect of hydrogen bonds contributes to the unique tendency of elastic anisotropy in single crystal hydrogen sulfide. Through our work, we have extended the melting curve and phase diagram of hydrogen sulfide up to 12 GPa and 580 K.

36 MATERIALS SCIENCE↗

Characterization of Carbon Nanotubes Grown by Chemical Vapor Deposition

Since the superior properties of multi-wall carbon nanotubes (MWCNT) could improve numerous devices such as electronics and sensors, many efforts have been made in investigating the growth mechanism of MWCNT to synthesize high quality MWCNT. Chemical vapor deposition (CVD) is widely used for MWCNT synthesis, and scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) are useful methods for analyzing the structure, morphology and composition of MWCNT. Temperature and pressure are two important growth parameters for fabricating carbon nanotubes. In MWCNT growth by CVD, the plasma assisted method is normally used for low temperature growth. However a high temperature environment is required for thermal CVD. A systematic study of temperature and pressure-dependence is very helpful to understanding MWCNT growth. Transition metal particles are commonly used as catalysis in carbon nanotube growth. It is also interesting to know how temperature and pressure affect the interface of carbon species and catalyst particles

Cochrane, J. C.↗