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At least 487 records · Page 27

Probing Active-Site Relocation in Cu/SSZ-13 SCR Catalysts during Hydrothermal Aging by in situ EPR Spectroscopy, Kinetic Studies, and DFT Calculations

Cu/SSZ-13 selective catalytic reduction catalysts display activity loss after mild hydrothermal aging without support degradation or loss of isolated Cu ion content. By applying electron paramagnetic resonance spectroscopy to compare hydrated, dehydrated and NH3-saturated catalysts before and after hydrothermal aging, as well as density functional theory calculations, it is found that hydrothermal aging induces Cu relocation, leading to stronger Cu-support interactions. This is particularly evidenced by ZCuOH conversion to Z2Cu, which leads to the generation of a unique structure with two Cu(II) ions positioned in a double 6-membered ring prism. The Cu(II) ions that do not undergo such dramatic changes also appear to stay closer to framework windows as evidenced by the overall increased anisotropy during EPR measurements. In situ EPR measurements under SCR conditions demonstrate that, in comparison to the fresh catalyst, higher percentages of Cu species stay as Cu(II) in the aged catalyst. This suggests that the reduction half-cycle of the SCR redox, i.e., Cu(II) ? Cu(I), becomes slower for the hydrothermally aged catalyst.

42 ENGINEERING↗

ULF waves in the magnetosphere

Research efforts in the area of magnetospheric ULF waves in the 1987-1990 period are reviewed. Attention is given to externally excited hydromagnetic waves including field line resonance, the global cavity mode, bow-shock-associated upstream waves, and Kelvin-Helmholtz waves. Consideration is given to internally excited Pc 4-5 pulsations and the role of these pulsations in the diffusion of ring-current ions based on the observed properties of the pulsations.

Takahashi, Kazue↗

A high-volume resonator for L-band DNP-NMR

DNP-NMR and EPR experiments that operate at or greater than L-band (i.e., ν 0 (e – ) = 1–2 GHz) are typically limited to maximum sample volumes of several hundred µL. These experiments rely on well-known resonator designs for DNP/EPR irradiation such as the loop-gap resonator and Alderman-Grant coil, where their maximum volumes limit further application to imaging experiments and high-throughput screening beyond L-band. Herein, we demonstrate a birdcage (BC) resonator design that can accommodate several mL of sample while operating around 1.5 GHz. The sample volume is maximized by using two identical BC resonators in a stacked configuration. Simulations are used to optimize the BC design and the performance is validated experimentally with liquid-state Overhauser-DNP-NMR experiments. This BC design exploits just the parasitic capacitance of conductive rings and features no fixed tuning capacitors. An enhancement of –77 is achieved on a 10 mM 4-Amino-TEMPO in H 2 O sample for a 5 mL sample volume. Finally, the associated sample heating is minimal due to the low-E-fields generated and the large sample mass with +3.4 K when driving 100 W for several seconds.

47 OTHER INSTRUMENTATION↗

Measuring a Fiber-Optic Delay Line Using a Mode-Locked Laser

The figure schematically depicts a laboratory setup for determining the optical length of a fiber-optic delay line at a precision greater than that obtainable by use of optical time-domain reflectometry or of mechanical measurement of length during the delay-line-winding process. In this setup, the delay line becomes part of the resonant optical cavity that governs the frequency of oscillation of a mode-locked laser. The length can then be determined from frequency-domain measurements, as described below. The laboratory setup is basically an all-fiber ring laser in which the delay line constitutes part of the ring. Another part of the ring - the laser gain medium - is an erbium-doped fiber amplifier pumped by a diode laser at a wavelength of 980 nm. The loop also includes an optical isolator, two polarization controllers, and a polarizing beam splitter. The optical isolator enforces unidirectional lasing. The polarization beam splitter allows light in only one polarization mode to pass through the ring; light in the orthogonal polarization mode is rejected from the ring and utilized as a diagnostic output, which is fed to an optical spectrum analyzer and a photodetector. The photodetector output is fed to a radio-frequency spectrum analyzer and an oscilloscope. The fiber ring laser can generate continuous-wave radiation in non-mode-locked operation or ultrashort optical pulses in mode-locked operation. The mode-locked operation exhibited by this ring is said to be passive in the sense that no electro-optical modulator or other active optical component is used to achieve it. Passive mode locking is achieved by exploiting optical nonlinearity of passive components in such a manner as to obtain ultra-short optical pulses. In this setup, the particular nonlinear optical property exploited to achieve passive mode locking is nonlinear polarization rotation. This or any ring laser can support oscillation in multiple modes as long as sufficient gain is present to overcome losses in the ring. When mode locking is achieved, oscillation occurs in all the modes having the same phase and same polarization. The frequency interval between modes, often denoted the free spectral range (FSR), is given by c/nL, where c is the speed of light in vacuum, n is the effective index of refraction of the fiber, and L is the total length of optical path around the ring. Therefore, the length of the fiber-optic delay line, as part of the length around the ring, can be calculated from the FSRs measured with and without the delay line incorporated into the ring. For this purpose, the FSR measurements are made by use of the optical and radio-frequency spectrum analyzers. In experimentation on a 10-km-long fiber-optic delay line, it was found that this setup made it possible to measure the length to within a fractional error of about 3 10(exp -6), corresponding to a length error of 3 cm. In contrast, measurements by optical time-domain reflectometry and mechanical measurement were found to be much less precise: For optical time-domain reflectometry, the fractional error was found no less than 10(exp -4) (corresponding to a length error of 1 m) and for mechanical measurement, the fractional error was found to be about 10(exp -2) (corresponding to a length error of 100 m).

Tu, Meirong↗

Motion of trapped electrons and protons in Saturn's inner magnetosphere

A summary is given of basic formulas for the guiding center motion of energetic charged particles trapped in a dipolar magnetic field. These formulas for longitudinal drift rates, latitudinal bounce periods, equatorial gyroradii, and equatorial gyroperiods are then stated in convenient numerical form for electrons and protons as functions of kinetic energy E, magnetic shell parameter L, and equatorial pitch angle alpha 0 for a slightly simplified model of the observed magnetic field of Saturn. To aid in the study of the interaction of charged particles with the rings and inner satellites of Saturn, additional formulas are given for the time interval between successive encounters of charged particles with a satellite in a circular prograde orbit and for the energy of electrons whose longitudinal angular velocity is resonant, or synchronous, with the Keplerian angular velocity of such a satellite.

Thomsen, M. F.↗

Broad frequency tuning of a Nb$_{3}$Sn superconducting microwave cavity for dark matter searches

We demonstrate a novel broad-frequency tuning mechanism for superconducting microwave cavities designed for dark matter searches. Using a Nb$_3$Sn-coated cigar-shaped cavity operating at approximately 9 GHz, we achieve continuous frequency tuning exceeding 1 GHz by mechanically separating the two cavity halves: a "tuning-by-opening" technique. Finite-element method simulations predict that radiative losses do not degrade the quality factor even for large openings, as a closed cavity with an intrinsic quality factor of $10^7$ maintains this value for apertures up to 9 mm, corresponding to a tuning range from 9.0 to 7.5 GHz. Experimental validation using both copper ring spacers and a continuous sliding mechanism confirms $Q_0$ values exceeding the dark matter quality factor across the entire explored frequency range, despite mechanical imperfections and film non-uniformities. This tuning approach avoids inserting elements into the resonant volume, making it particularly suitable for high-Q superconducting cavities in axion haloscope experiments and readily applicable to REBCO-based implementations capable of operating in multi-tesla magnetic fields.

Maiello, D. [Padua U.; INFN, Padua] (ORCID:0009000↗

An Extremely Stable, Highly Soluble Monosubstituted Anthraquinone for Aqueous Redox Flow Batteries

An extremely stable, energy-dense (53.6 Ah L –1 , 2 M transferrable electrons), low crossover (permeability of <1 × 10 –13 cm 2 s –1 using Nafion 212 (Nafion is a trademark polymer from DuPont)), and potentially inexpensive anthraquinone with 2-2-propionate ether anthraquinone structure (abbreviated 2-2PEAQ) is synthesized and extensively evaluated under practically relevant conditions for use in the negolyte of an aqueous redox flow battery. 2-2PEAQ shows a high stability with a fade rate of 0.03–0.05% per day at different applied current densities, cut-off voltage windows, and concentrations (0.1 and 1.0 M ) in both a full cell paired with a ferro/ferricyanide posolyte as well as a symmetric cell. 2-2PEAQ is further shown to have extreme long-term stability, losing only ≈0.01% per day when an electrochemical rejuvenation strategy is employed. From post-mortem analysis (nuclear magnetic resonance (NMR), liquid chromatography–mass spectrometry (LC-MS), and cyclic voltammetry (CV)) two degradation mechanisms are deduced: side chain loss and anthrone formation. 2-2PEAQ with the ether linkages attached on carbons non-adjacent to the central ring is found to have three times lower fade rate compared to its isomer with ether linkages on the carbon adjacent to the central quinone ring. Here, the present study introduces a viable negolyte candidate for grid-scale aqueous organic redox flow batteries.

25 ENERGY STORAGE↗

Gas-Phase Synthesis of Coronene through Stepwise Directed Ring Annulation

Molecular beam experiments together with electronic structure calculations provide the first evidence of a complex network of elementary gas-phase reactions culminating in the bottom-up preparation of the 24π aromatic coronene (C 24 H 12 ) molecule–a representative peri-fused polycyclic aromatic hydrocarbon (PAH) central to the complex chemistry of combustion systems and circumstellar envelopes of carbon stars. The gas-phase synthesis of coronene proceeds via aryl radical-mediated ring annulations through benzo[e]pyrene (C 20 H 12 ) and benzo[ghi]perylene (C 22 H 12 ) involving armchair-, zigzag-, and arm-zig-edged aromatic intermediates, highlighting the chemical diversity of molecular mass growth processes to polycyclic aromatic hydrocarbons. Furthermore, the isomer-selective identification of five- to six-ringed aromatics culminating with the detection of coronene is accomplished through photoionization and is based upon photoionization efficiency curves along with photoion mass-selected threshold photoelectron spectra, providing a versatile concept of molecular mass growth processes via aromatic and resonantly stabilized free radical intermediates to two-dimensional carbonaceous nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A dynamical history of the inner Neptunian satellites

The dynamical history of Neptune's satellite system is presently inferred on the basis of a Triton capture-origin scenario in which that moon's elongated postcapture orbit generated chaotic perturbations of the original satellites' eccentricities; this, in turn, led to mutual collisions among the inner satellites until a ring of debris was formed. Neptune's inner satellite system thereby reformed on equatorial orbits after the orbtal circularization of Triton. Attention is given to the 4.7-deg inclination of 1989N6, which may be due to a temporary inclination-resonance capture.

Banfield, Don↗

On the possibility of footprint compression with one lens in nonlinear accelerator lattice

Electromagnetic interaction of colliding beams along with other nonlinear fields often limits the beams' lifetimes and luminosities. Nonlinearities result in the spread of betatron frequencies (footprint) and, thus, may enhance dynamic diffusion of particles due to high order resonances. One of the possible ways to eliminate nonlinearities and overcome the corresponding difficulties is compensation of nonlinear forces, but, in practice, it is hardly possible to obtain exact linearity of the system. The compensation with a single nonlinear lens cannot cope with distributed nonlinearities, nonlinearities due to parasitic crossings, etc. Here, we present a method to compute parameters of nonlinear element (lens) that eliminates both the footprint and resonance strength without achieving full compensation.

43 PARTICLE ACCELERATORS↗

CO 2 capture from wet flue gas using a water-stable and cost-effective metal-organic framework

We report the use of MIL-120 as a water-stable and cost-effective metal-organic framework (MOF) for selectively capturing CO 2 from wet flue gas. Synthesized using inexpensive and environmentally benign reagents in water, MIL-120 possesses one-dimensional pores decorated with hydroxyl-bridged Al(III) ions and benzene rings with an interstitial spacing of 4.78 Å. Carbon dioxide isotherms show steep uptake at low pressure, and the affinity of MIL-120 for CO 2 is 44 kJ mol –1 . CO 2 -loading 13 C solid-state nuclear magnetic resonance and Fourier transform infrared spectra tracking the sorption of CO 2 into MIL-120 revealed that the interplay of pore size, functionality, and dimensionality is vital for CO 2 restriction within the pores of MIL-120. Breakthrough experiments reveal that MIL-120 can capture CO 2 from dry and wet flue gas with uptake capacities of 1.215 and 1.118 mmol g –1 , respectively. Our work highlights the synthetic benefits of MIL-120 and elucidates its selective capture of CO 2 from wet flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Instabilities driven by the fundamental crabbing mode

The Electron Ion Collider (EIC) requires crab cavities to correct for crossing angle effects. These cavities produce a time varying horizontal kick that makes the collision head on in the center of mass frame of the bunches. This results in a luminosity that is very close to the the luminosity obtained without a crossing angle. Producing the kick requires a transverse RF field. This field requires a superconducting resonator and reasonable power levels require loaded quality factors of order a million. This results is a very large transverse impedance for the crabbing mode. The horizontal beta function is large and this, coupled with the large transverse impedance of the resonator can lead to strong instabilities. In the first section of the paper a simple model is used to describe the situation without feedback. There are large ranges of tune leading to strong instabilities in both the electron and hadron storage rings of the EIC. These estimates are confirmed with simulations. In the second section, RF feedback is used to reduce the apparent impedance of the crabbing mode. Simulating the actual feedback would require both a significant rewrite of the tracking code and a significant reduction in computational speed. Instead, the apparent impedance is fitted using one pole filters, which allows use of the existing simulation code. In the third section a transverse damping system is outlined.

43 PARTICLE ACCELERATORS↗

Modeling and Simulation of Rotary Sloshing in Launch Vehicles

The nonlinear dynamics of propellant sloshing during orbital ascent are usually neglected in the flight control analysis of large boost vehicles under the assumption that the viscous damping of the fluid is sufficient to suppress nonlinear phenomena and confine the fluid to small, planar free surface displacements. In this case, the sloshing dynamics can be modeled using a spring-mass-damper or linearized pendulum mechanical analog. However, large, smooth-wall tanks without significant internal hardware or ring baffles are still susceptible to nonlinear effects. In particular, rotary sloshing can present a risk to flight control as it involves the formation of a stable limit cycle which can lead to undesirable roll coupling. The underlying phenomena of jump resonance does not manifest in linear models, but can be reproduced using a nonlinear spherical pendulum or the Bauer paraboloid model developed during the Apollo/Saturn program. In this paper, a detailed analysis of the rotary sloshing dynamics of these mechanical analogs is presented, and discussed in the context of flight control stability. High-fidelity simulations of a representative boost vehicle are used to verify the semi-analytical predictions of the nonlinear dynamic response.

Modeling↗

X-ray spectroscopic identification of strain and structure-based resonances in a series of saturated carbon-cage molecules: Adamantane, twistane, octahedrane, and cubane

Novel nanocarbons such as fullerenes, nanotubes, graphene, and nanodiamond reside at the cutting edge of nanoscience and technology. Along with chemical functionalization, geometric constraints (such as extreme curvature in nanotubes or defects within or at the surfaces of diamond nanoparticles) significantly alter the electronic states of the nanocarbon material. Understanding the effects of steric strain on the electronic structure is critical to developing nanoelectronic applications based on these materials. This paper presents a fundamental study of how strain affects the electronic structure in a benchmark series of some fundamental saturated carbon cage compounds. Adamantane, C10H16, the smallest diamondoid and arguably the smallest nanodiamond crystallite, has carbon atoms essentially commensurate with diamond lattice positions and possesses by far the least molecular strain of this series. Twistane also is a C10H16 isomer but the fixed cyclohexane twist conformation of the central ring introduces additional strain into the cage. Octahedrane [(CH)12] and cubane [(CH)8] are considerably more strained, culminating in cubane where carbon–carbon bonds lie either parallel or orthogonal to one another. Using gas-phase near-edge x-ray absorption fine structure spectroscopy to probe the unoccupied electronic states, we observe two major progressions across this series. First, a broad C–C σ* resonance in the absorption splits into two more narrow and intense resonances with increasing strain. Second, the first manifold of states previously associated with tertiary C–H σ* in the diamondoid series appears to broaden and shift to lower energy. This feature is more than twice as intense in cubane than in octahedrane, even though these two molecules have only tertiary carbons, with the chemical formula (CH)x. The spectral differences are entirely due to the shape of the molecules; in particular, in cubane, the features arise from a high degree of p-p interaction between parallel C–C bonds. In contrast to the conventional wisdom that near-edge x-ray absorption is primarily an atomically localized spectroscopy, molecular shape and associated strain lead to the dominant features in spectra acquired from this fundamental series of carbon cage structures.

36 MATERIALS SCIENCE↗

Pick-Up Ion Instabilities at Planetary Magnetospheres

This effort involved the analysis of low frequency waves as observed by the Galileo spacecraft near the Galilean moon, Io. Io is a significant source of material, especially SO2, and various products of dissociation, and further these atoms and molecules are readily ionized. The initial velocity of the ions is essentially that of the neutral species, i.e., the Keplerian velocity. The plasma, on the other hand is co-rotating, and there is a differential flow of the order 57 km/s between the plasma and the neutral particles. Thus pick-up ion instabilities are Rely to occur within the Jovian magnetosphere. Indeed, magnetometer observations from the Galileo spacecraft clearly show ion cyclotron waves that have been identified with a large variety of plasma species, such as O+, S++ (which has the same gyro-frequency as O+), S+, and SO2+. Typically, however, the dominant frequency is near the SO2+ gyro-frequency. The research effort was originally planned to be a team effort between Robert J. Strangeway as the Principal Investigator, and Debbie Huddleston, who was an Assistant Research Geophysicist at UCLA. Unfortunately, Dr. Huddleston took a position within Industry. The effort was therefore descoped, and Dr. Strangeway instead pursued a collaboration with Dr. Xochitl Blanco-Cano, of the Instituto de Geofisica, Universidad Nacional Autonoma de Mexico. This has proved to be a productive collaboration, with several papers and publications arising out of the effort. The magnetic field oscillations near lo generally fall into two types: ion cyclotron waves, with frequencies near an ion gyro-frequency, and lower frequency mirror-mode waves. The ion cyclotron waves are mainly transverse, and frequently propagate along the ambient magnetic field. The mirror-mode waves are compressional waves, and they have essentially zero frequency in the plasma rest frame. One of the purposes of our investigation is to understand what controls the types of wave modes that occur, since both wave modes can be drive unstable by the pressure anisotropy associated with the pick up ions. The pick ion velocity is perpendicular to the ambient magnetic field, and is generally much larger than the thermal velocity, at least initially. At its simplest, we found that the ion cyclotron waves are controlled by the parameters of the species in gyro-resonance with the wave. Thus, while the growth rates for the lower mass (higher gyro-frequency) pick-up ions are generally larger, we found that the heavier SO2+ ion cyclotron waves are generally preferred. This is because one of the effects of the wave instability is to diffuse the ions in pitch angle and energy. The lower mass ions therefore consist of both a ring of recently created pick-up ions, and a thermal background. This thermal background quenches the ion cyclotron instability. SO2+ is different, however. Being a molecule, the species can also dissociate. Our analysis suggests that the dissociation acts on a time scale comparable to or faster than the velocity space diffusion time scale. There are consequently no thermal SO2+ ions to quench the instability. We have also investigated the mirror-mode. This mode can at times grow more rapidly than the individual ion cyclotron waves. This is mainly because the mirror-mode can grow off the pressure anisotropy of the individual species with which the waves are in resonance. Lastly, as part of this effort we have begun to investigate the instability for obliquely propagating modes. Galileo observations show that at times the ion cyclotron waves are significantly elliptically polarized, and further the wave vector is at a large angle to the field, significant growth can occur for oblique propagation. Depending on the group velocity of the waves, it is possible that obliquely propagating modes have higher advective growth rate, but this has yet to be determined.

Strangeway, Robert J.↗

Midday Pc 1-2 pulsations observed at a subcleft location

A class of unstructured Pc 1-2 pulsation activity, as identified on Bar I (70.2 N) records taken during 1968-1972, is found to be present in midday hours on about half of the days in summer months. The events have some tendency to occur in the later part of the ring current recovery phase, especially at times of moderate AE when the cleft lines are just poleward of Bar I. The source lines of the Pc 1-2 are found to lie essentially outside the plasmapause. In terms of the proton cyclotron resonance instability the most likely source regions of the Bar I Pc 1-2 are the detached plasma regions convecting sunward on the dayside and the portion of the cleft plasma on the last closed field lines.

Heacock, R. R.↗

Dynamic properties of elastomer cartridge specimens under a rotating load

This paper presents the results of a program of analysis and test to determine the dynamic properties of elastomer cartridges operating under a rotating load. These measured properties were compared to predictions based on results of unidirectional tests with the same elastomer material. The test method for the dynamic stiffness and damping measurements was essentially the same as the Base Excitation Resonant Mass Method. The primary difference is that the exciting force used for these most recent tests was exerted by rotating unbalance in a rotational test rig rather than a shake table. The specimens tested were: two rectangular cross-section, continuous ring cartridges of different cross-section and three cylindrical button cartridges of different button thickness. Tests were performed for strains from about 0.0001 to about 0.01 (double amplitude). Material properties and prediction equations determined from reciprocating tests were used to make numerical predictions of stiffness, damping, and loss coefficient for the test elements, with encouraging results. Strain was shown to be an important parameter in determining these dynamic properties, particularly damping and loss coefficient.

Darlow, M. S.↗

The Relationship Between the Background and Transient Signals in Schumann Resonances

Two distinct measures of the Earth's Schumann resonances-the background and the transients--are studied through comparisons at the mesoscale and at the continental scale. A rough proportionality is shown between the far more abundant afternoon lightning activity and the larger positive mesoscale discharges that make sprites and simultaneously ring the Earth-ionosphere cavity to levels higher than the integration of all other lightnings.

Williams, E.↗