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At least 631 records · Page 35

Pnictogen-Bonding Catalysis: Copolymerization of CO 2 and Epoxides on Antimony(V) Platforms

The copolymerization of CO 2 and epoxides to access polycarbonates represents a promising strategy for CO 2 utilization and for the production of useful polymers. Aiming to explore alternative transition-metal-free approaches that support this chemistry, we have investigated a series of triaryl-catecholatostiboranes as pnictogen-bonding platforms for the copolymerization of CO 2 and cyclohexene oxide (CHO). Our survey of these antimony species has identified motifs that promote this polymerization reaction efficiently, provided that bis(triphenylphosphine)iminium chloride is administered as an activator. By coupling these polymerization studies with a careful assessment of the structure, electronic attributes and Lewis acidity of the catecholatostiboranes, this work shows that high activity is generally observed with the weakest pnictogen-bond donors or Lewis acids investigated. Mechanistic studies, which indicate that the polymerization reaction is first order in stiborane, reveal a nonlinear dependence on the CO 2 pressure. This nonlinear dependence could be satisfactorily modeled based on a pre-equilibrium process involving the reversible insertion of the gaseous monomer into the growing chain. Altogether these findings greatly expand the reach of pnictogen bond catalysis while also providing an entry for the use of heavy group 15 elements as competent platforms for CO 2 utilization.

antimony↗

The structure of pressure fluctuations in turbulent shear flows

Pressure fluctuations in a turbulent channel and a homogeneous shear flows are investigated by analyzing databases obtained from direct numerical simulations. Detailed statistics associated with the pressure fluctuations in both flows are discussed. Characteristics associated with the rapid (linear) and slow (nonlinear) pressure are examined. The global dependence of the pressure fluctuations and pressure-strain correlations are also examined by evaluating the integral associated with Green's function representations of them.

Kim, John↗

First-order structural phase transition at low temperature in GaPt 5 P and its rapid enhancement with pressure

Single crystals of X Pt 5 ⁢P (X = Al, Ga, and In), belonging to the 1-5-1 family of compounds, were grown from a Pt-P solution at high temperatures, and measurements of the ambient pressure, temperature-dependent magnetization, resistivity, and x-ray diffraction were made. Additionally, the ambient-pressure Hall resistivity and temperature-dependent resistance under pressure were measured on GaPt 5 ⁢P. All three compounds have a tetragonal P4/mmm crystal structure at room temperature with metallic transport and weak diamagnetism over the 2–300 K temperature range. Surprisingly, at ambient pressure, both the transport and magnetization measurements on GaPt 5 ⁢P show a steplike feature in the 70–90 K region, suggesting a possible structural phase transition. Neither AlPt 5 ⁢P nor InPt 5 ⁢P have any signatures of a phase transition in their temperature-dependent electrical resistance and magnetization data. Both the hysteretic nature and sharpness of the features in the GaPt 5 ⁢P data suggest that the transition is first-order. Further, single-crystal x-ray diffraction measurements provided further details of the structural transition with a possibility of a crystal symmetry different from P⁢4/mmm below the transition temperature. The transition is characterized by anisotropic changes in the lattice parameters and a volume collapse with respect to the high-temperature tetragonal crystal structure. Furthermore, satellite peaks are observed at two distinct and nonequivalent wave vectors (0, 0, 0.5) and (0.5, 0.5, 0.5), and density functional theory calculations present phonon softening, especially at (0.5, 0.5, 0.5), as a possible driving mechanism. Additionally, we find that the structural transition temperature increases rapidly with increasing pressure, reaching room temperature by ~2.2 GPa, highlighting the high degree of pressure sensitivity of GaPt 5 ⁢P and fragile nature of its room-temperature structure. Even though the volume collapse and extreme pressure sensitivity suggest chemical pressure should drive a similar structural change in AlPt 5⁢ P, where both unit-cell dimensions and volume are smaller, its structure is found to be the same as that of the room-temperature GaPt 5 ⁢P. Overall, GaPt 5 ⁢P stands out as a sole member of the 1-5-1 family of compounds for which a temperature-driven structural change has been observed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ultimate Temperature of Pulse Tube Cryocoolers

An ideal pulse tube cryocooler using an ideal gas can operate at any temperature. This is not true for real gases. The enthalpy flow resulting from the real gas effects of He-3, He-4, and their mixtures in ideal pulse tube cryocoolers puts limits on the operating temperature of pulse tube cryocoolers. The discussion of these effects follows a previous description of the real gas effects in ideal pulse tube cryocoolers and makes use of models of the thermophysical properties of He-3 and He-4. Published data is used to extend the analysis to mixtures of He-3 and He-4. The analysis was done for pressures below 2 MPa and temperatures below 2.5 K. Both gases and their mixtures show low temperature limits for pulse tube cryocoolers. These limits are in the 0.5-2.2 K range and depend on pressure and mixture. In some circumstances, even lower temperatures may be possible. Pulse tube cryocoolers using the two-fluid properties of dilute 3He in superfluid He-4 appear to have no limit.

Kittel, Peter↗

Ultimate Temperature of Pulse Tube Cryocoolers

An ideal pulse tube cryocooler using an ideal gas can operate at any temperature. This is not true for real gases. The enthalpy flow resulting from the real gas effects of 3He, 4He, and their mixtures in ideal pulse tube cryocoolers puts limits on the operating temperature of pulse tube cryocoolers. The discussion of these effects follows a previous description of the real gas effects in ideal pulse tube cryocoolers and makes use of models of the thermophysical properties of 3He and 4He. Published data is used to extend the analysis to mixtures of 3He and 4He. The analysis was done for pressures below 2 MPa and temperatures below 2.5 K. Both gases and their mixtures show low temperature limits for pulse tube cryocoolers. These limits are in the 0.5-2.2 K range and depend on pressure and mixture. In some circumstances, even lower temperatures may be possible. Pulse tube cryocoolers using the ha-fluid properties of dilute 3He in superfluid 4He appear to have no limit.

Kittel, Peter↗

Gas-Liquid Flows Through Porous Media in Microgravity: The International Space Station Packed Bed Reactor Experiment

Experimental results on pressure drop and flow patterns for gas-liquid flow through packed beds obtained in the International Space Station with two types of packing are presented and analyzed. It is found that the pressure drop depends on the packing wettability in the viscous-capillary (V-C) regime and this dependence is compared with previously published results developed using short duration low-gravity aircraft tests. Within the V-C regime, the capillary contribution is the dominant force contributing to the pressure drop for the wetting case (glass) versus the viscous contribution dominating for the non-wetting case (Teflon). Outside of the V-C regime, it is also found that hysteresis effects that are often strong in normal gravity gas-liquid flows are greatly diminished in microgravity and pressure drop is nearly independent of packing wettability. A flow pattern transition map from bubble to pulse flow is also compared with the earlier aircraft data.

Viscous-capiliary regime↗

Characteristics of Five Ejector Configurations at Free-Stream Mach Numbers from 0 to 2.0

Thrust, air-handling, and base-pressure characteristics of five ejector configurations were investigated in the Lewis 8-by 6-foot wind tunnel at free-stream Mach numbers from 0 to 2.0 over ranges of primary-jet pressure ratio up to 24 and corrected secondary weight-flow ratio up to 13 percent. The ejector-shroud geometries varied from convergent to divergent. Base pressure ratio and ejector performance were interrelated by means of an exit-momentum parameter. Correlations, to at least a first approximation, with base pressure ratio, of both internal-ejector-flow separation and external-flow separation over the model boattail were shown. Furthermore, it was shown that magnitudes and exact trends in base pressure ratio depended largely, and in a complicated fashion, on ejector geometry and amount of secondary flow. External-stream effects on ejector jet thrust were determined for a typical schedule of jet-engine pressure ratios. With the exception of the ejector having the largest (1.81) shroud-exit-to primary-diameter ratio, there were no stream effects at Mach numbers from 1.5 to 2.0 and variations from quiescent-air thrust data were less than 2.5 percent at the subsonic speed investigated.

Klann, John L.↗

The calculation of pressure on slender airplanes in subsonic and supersonic flow

Under the assumption that a wing, body, or wing-body combination is slender or flying at near sonic velocity, expressions are given which permit the calculation of pressure in the immediate vicinity of the configuration. The disturbance field, in both subsonic and supersonic flight, is shown to consist of two-dimensional disturbance fields extending laterally and a longitudinal field that depends on the streamwise growth of cross-sectional area. A discussion is also given of couplings, between lifting and thickness effects, that necessarily arise as a result of the quadratic dependence of pressure on the induced velocity components. (author)

Heaslet, Max A↗

An experimental study and prediction of a two-phase pressure drop in microgravity

Experimental two-phase pressure drop results obtained in normal gravity and in nearly zero-gravity aboard a NASA-JSC reduced-gravity KC-135 aircraft are used to evaluate several empirically based correlations and flow-regime dependent models. Pressure drops in reduced gravity and those in normal gravity are shown to be related to flow pattern models for each. Two annular flow models are developed which are found to accurately predict the reduced-gravity data.

Chen, I. Y.↗

A RELAP5-3D Model of the Lobo Lead Loop

The goal of our research is to build upon the capability of RELAP5-3D to model molten lead systems. Molten lead has several potential uses in future advanced reactors like the lead fast reactor or fusion reactors that utilize dual-coolant lead lithium blankets. This potential for use in future generations of reactors highlights the necessity to develop molten lead models to ensure that they can accurately predict the thermohydraulic behavior. We have developed a RELAP5-3D model of the Lobo Lead Loop facility, located at the University of New Mexico, to verify the accuracy of RELAP5-3D via comparison to existing computational fluid dynamics results and analytical calculations. It was found that RELAP5-3D accurately calculated radiative heat transfer (within < 1%) when compared to theoretical calculations. In addition, pressure drop calculations done in RELAP5-3D demonstrated reasonable agreement within 20 kPa, mostly within ~7-15%, when compared to the computational fluid dynamics model of the facility developed by the University of New Mexico, and captured the dependence of pressure drop on flow velocity accurately. Finally, a hypothetical loss of flow transient was imposed on the RELAP5-3D model to determine the feasibility of performing a similar experiment with the Lobo Lead Loop. It was found that such an experiment could be possible as the RELAP5-3D model indicated that the temperatures of the fluid would not exceed limiting temperatures of the structure (1658 K) nor the maximum temperature of the electromagnetic pump inlet (823 K). Although there is not experimental data to begin validation, the model will be readily available for future validation studies when the experimental data is generated, especially as the model continues to evolve over time. Furthermore, the results so far demonstrate a promising first step in the verification/validation of the RELAP5-3D model of the Lobo Lead Loop.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Nonhomologous contraction and equilibria of self-gravitating, magnetic interstellar clouds embedded in an intercloud medium: Star formation. II - Results

The paper studies the equilibrium of self-gravitating isothermal models of interstellar clouds with a frozen-in magnetic field linked smoothly to the field of a hot tenuous intercloud medium. Equilibrium states are determined which can be reached by clouds contracting nonhomologously from a spherical uniform initial state. Three free parameters characterize the problem: a dimensionless initial radius related to the Jeans length of the cloud, the initial ratio of the magnetic and gas pressures in the cloud, and the initial ratio of the intercloud and cloud pressures. The dependence of the solutions on each of these parameters is investigated. It is found that: (1) the frozen-in field causes the cloud to become oblate with its major axis normal to the field lines; (2) the flattening increases as the magnetic-field strength, gravitational forces, or intercloud pressure increases; (3) increasing intercloud pressure eventually leads to gravitational collapse; and (4) the cloud can reach equilibrium only if its radius does not exceed some critical value. The observed inefficiency of the star-formation process within massive clouds is examined and explained in terms of magnetic phenomena in a collapsing cloud.

Mouschovias, T. C.↗

Water vapor absorption in the atmospheric window at 239 GHz

Absolute absorption rates of pure water vapor and mixtures of water vapor and nitrogen have been measured in the atmospheric window at 239 GHz. The dependence on pressure as well as temperature has been obtained. The experimental data are compared with several theoretical or empirical models, and satisfactory agreement is obtained with the models involving a continuum; in the case of pure water vapor, the continuum contribution based upon recent theoretical developments gives good results. The temperature dependence is stronger than that proposed in a commonly used atmospheric transmission model.

Bauer, A.↗

Electrical Conductivity and Sound Velocities of Talc Under High Pressure and High Temperature Conditions and Application to the Subducting Cocos Plate

Talc is expected to be an important water carrier in Earth's upper mantle, and understanding its electrical and seismic properties under high pressure and temperature conditions is required to detect possible talc-rich regions in subduction zones imaged using geophysical observations. Here, we conducted acoustic and electrical experiments on natural talc aggregates at relevant pressure-temperature conditions. Compressional wave velocity (V p ) was measured using ultrasonic interferometry in a Paris-Edinburgh press at pressures up to 3.4 GPa and temperatures up to 873 K. Similar Vp values are obtained regardless of the initial crystallographic preferred orientation of the samples, which can be explained by talc grain reorientation during the experiment, with the (001) plane becoming perpendicular to the uniaxial compression axis. Electrical conductivity of the same starting material was determined using impedance spectroscopy in a multi-anvil press up to 6 GPa and 1263 K. Two conductivity jumps are observed, at ∼860–1025 K and ∼940–1080 K, depending on pressure, and interpreted as talc dehydroxylation and decomposition, respectively. Electrical anisotropy is observed at low temperature and decreases with increasing pressure (∼10 at 1.5 GPa and ∼2 at 3.5 GPa). Comparison of acoustic and electrical results with geophysical observations in central Mexico supports the presence of a talc-bearing layer atop the subducted Cocos plate.

Cocos plate↗

Unconventional Pressure-Driven Metamagnetic Transitions in Topological van der Waals Magnets

Activating metamagnetic transitions between ordered states in van der Waals magnets and devices bring great opportunities in spintronics. Here we show that external pressure, which enhances the inter-layer hopping without introducing chemical disorders, triggers multiple metamagnetic transitions upon cooling in the topological van der Waals magnets Mn(Bi 1–x Sb x ) 4 Te 7 , where the antiferro magnetic interlayer superexchange coupling competes with the ferromagnetic interlayer coupling mediated by the antisite Mn spins. The temperature-pressure phase diagrams reveal that while the ordering temperature from the paramagnetic to ordered states is almost pressure-independent, the metamagnetic transitions show non-trivial pressure and temperature dependence, even re-entrance. For these highly anisotropic magnets, we attribute the former to the ordering temperature being only weakly dependent on the intralayer parameters, the latter to the parametrically different pressure and temperature dependence of the two interlayer couplings. Our independent probing of these disparate magnetic interactions paves an avenue for efficient magnetic manipulations in van der Waals magnets.

36 MATERIALS SCIENCE↗

A model for the interaction between stars and gas in the interstellar medium

A model for the ISM is considered in which stars lose mass and heat the gas while the gas can form into stars. Three scale-free models are calculated, and in each case the star formation instability leads to a network of dense filaments that surround hotter, more rarefied gas, all of which are close to pressure equilibrium. Depending upon the star formation and cooling laws adopted, the stars are located either in the middle of a bubble or along the inside edge of a dense filament. When a model for the ISM with a cooling curve appropriate for gas of cosmic abundance and a star formation rate proportional to the local gas density is used, the star formation instability is found to grow at temperatures below about 10,000 K. A network structure develops in which most of the mass is in neutral filaments. Newly formed stars lie adjacent to the filaments and create pressure forces that lead to filament motion.

Chiang, Wei-Hwan↗

Measurement of Transverse Resistance for Stacks of Non-insulated REBCO Tapes

Transverse resistance among adjacent conductors is a key parameter to calculate AC losses in superconducting cables with non-insulated conductors. The transverse pressure insert (TPI) previously developed and used at Fermilab was modified to measure transverse resistance of stacks made of non-insulated REBCO tapes as a function of transverse pressure at liquid nitrogen temperature. Pressure up to 322 MPa was applied with a hydraulic cylinder. A small current up to 10 A was flown in the stack sample through REBCO tape leads spliced above and below the stack. The latter had a bending radius larger than 6 mm to prevent the critical current degradation in REBCO leads. The voltage was measured just outside the compressed area. Stack samples included stacks of bare 4-mm wide REBCO tapes, as well as REBCO tapes alternated with 4-mm wide stainless-steel ribbons of 40 μm and 30 μm of thickness. We herein present the results of these transverse resistance measurements. Results show a stronger dependence on pressure for smaller pressure vs. larger ones. Also, of the two components of contact resistance, i.e. contact and bulk, the latter was negligible.

Tamagnini, E. [Turin Polytechnic]↗

Analysis of Unsteady Tip and Endwall Heat Transfer in a Highly Loaded Transonic Turbine Stage

In a previous study, vane-rotor shock interactions and heat transfer on the rotor blade of a highly loaded transonic turbine stage were simulated. The geometry consists of a high pressure turbine vane and downstream rotor blade. This study focuses on the physics of flow and heat transfer in the rotor tip, casing and hub regions. The simulation was performed using the Unsteady Reynolds-Averaged Navier-Stokes (URANS) code MSU-TURBO. A low Reynolds number k-epsilon model was utilized to model turbulence. The rotor blade in question has a tip gap height of 2.1 percent of the blade height. The Reynolds number of the flow is approximately 3x10(exp 6) per meter. Unsteadiness was observed at the tip surface that results in intermittent "hot spots". It is demonstrated that unsteadiness in the tip gap is governed by inviscid effects due to high speed flow and is not strongly dependent on pressure ratio across the tip gap contrary to published observations that have primarily dealt with subsonic tip flows. The high relative Mach numbers in the tip gap lead to a choking of the leakage flow that translates to a relative attenuation of losses at higher loading. The efficacy of new tip geometry is discussed to minimize heat flux at the tip while maintaining choked conditions. In addition, an explanation is provided that shows the mechanism behind the rise in stagnation temperature on the casing to values above the absolute total temperature at the inlet. It is concluded that even in steady mode, work transfer to the near tip fluid occurs due to relative shearing by the casing. This is believed to be the first such explanation of the work transfer phenomenon in the open literature. The difference in pattern between steady and time-averaged heat flux at the hub is also explained.

Shyam, Vikram↗

Spectral distortions to momentum and scalar exchanges by non-turbulent motion and patchy landscape variability

Modifications to the spectra of turbulent velocity and scalars and co-spectra of vertical fluxes of momentum and scalars due to patchy landscape heterogeneity and non-stationarity are explored for a Mediterranean ecosystem. About 9 months of high frequency measurements of the three velocity components, water vapor concentration, carbon dioxide concentration, and air temperature were analyzed for different seasons (spring/summer) and prevalent wind directions (southeast/northwest). The two wind directions sampled a contrast of clumped and patchy landscape comprised of olive trees (southeast) and wall bounded flow disturbed by the presence of few upwind trees (northwest). The measured spectra and co-spectra were also compared to theoretical scaling forms from stationary, planar homogeneous flow, in the absence of subsidence as derived from the Kansas experiment. To assess the role of low frequency non-turbulent motion on the spectral and co-spectral content, a 5-min Fourier cutoff was introduced and the analysis was limited to near-neutral conditions where the boundary layer depth is shallow compared to its unstable counterpart. It was shown that the velocity statistics were not appreciably impacted by the low-frequency motion causing non-stationarity. Moreover, the turbulent scalar fluxes were also shown not to be significantly impacted by such low frequency motion. The scalar variances were impacted, especially the water vapor variance and its concomitant spectral shape. When the non-turbulent motion was filtered, the scalar spectra at low wavenumbers followed expectations from the so-called attached eddy hypothesis (i.e. exhibited a $k^{-1}_x$ scaling with $k_x$ defining the longitudinal wavenumber) applicable for near-neutral conditions. For momentum co-spectra, the canonical shapes from the Kansas experiment appear to describe well the measurements here and in both dominant directions and seasons with some adjustment to the integral time scales based on wind direction. For the scalar co-spectra, deviations from the Kansas experiment were prevalent. The most noticeable and surprising deviations were their slow decay with increased sampling frequency at inertial subrange scales. This slow decay was shown not to contribute appreciably to the overall scalar fluxes. At those fine scales, predictions from local isotropy were expected to hold. The scalar co-spectral deviations from local isotropy were then discussed using a simplified co-spectral budget model where scalar–scalar co-spectra naturally emerged and the interplay between landscape heterogeneity and a scale-dependent pressure-scalar de-correlation time was postulated. It is also envisaged that the findings here offer a preliminary template for analyzing eddy-covariance data in situations that deviate from ideal conditions, especially regarding low-frequency modulations of scalar spectra and vertical scalar flux co-spectra.

Canopy turbulence↗