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At least 415 records · Page 23

Chromium silicide formation by ion mixing

The formation of CrSi2 by ion mixing was studied as a function of temperature, silicide thickness and irradiated interface. Samples were prepared by annealing evaporated couples of Cr on Si and Si on Cr at 450 C for short times to form Si/CrSi2/Cr sandwiches. Xenon beams with energies up to 300 keV and fluences up to 8 x 10 to the 15th per sq cm were used for mixing at temperatures between 20 and 300 C. Penetrating only the Cr/CrSi2 interface at temperatures above 150 C induces further growth of the silicide as a uniform stoichiometric layer. The growth rate does not depend on the thickness of the initially formed silicide at least up to a thickness of 150 nm. The amount of growth depends linearly on the density of energy deposited at the interface. The growth is temperature dependent with an apparent activation energy of 0.2 eV. Irradiating only through the Si/CrSi2 interface does not induce silicide growth. It is concluded that the formation of CrSi2 by ion beam mixing is an interface-limited process and that the limiting reaction occurs at the Cr/CrSi2 interface.

Shreter, U.↗

A sharp immersed method for 2D flow-body interactions using the vorticity-velocity Navier-Stokes equations

Immersed methods discretize boundary conditions for complex geometries on background Cartesian grids. Here, this makes such methods especially suitable for two-way coupled flow-body problems, where the body mechanics are partially driven by hydrodynamic forces. However, for the vorticity-velocity form of the Navier-Stokes equations, existing immersed geometry discretizations for two-way coupled problems only achieve first order spatial accuracy near solid boundaries. Here we introduce a sharp-interface approach based on the immersed interface method to handle the one- and two-way coupling between an incompressible flow and one or more rigid bodies using the 2D vorticity-velocity Navier-Stokes equations. Our main contributions are three-fold. First, we develop and analyze a moving boundary treatment for sharp immersed methods that can be applied to PDEs with implicitly defined boundary conditions, such as those commonly imposed on the vorticity field. Second, we develop a two-way coupling methodology for the vorticity-velocity Navier-Stokes equations based on control-volume momentum balance that does not require the pressure field. Third, we show through extensive testing and validation that our resulting flow-body solver reaches second-order accuracy for most practical scenarios, and provides significant efficiency benefits compared to a representative first-order approach.

42 ENGINEERING↗

High-Throughput Characterization and Optimization of Polyamide Hydrolase Activity Using Open Port Sampling Interface Mass Spectrometry

Enzymatic biodegradation of polymers, such as polyamides (PA), has the potential to cost-effectively reduce plastic waste, but enhancements in degradation efficiency are needed. Engineering enzymes through directed evolution is one pathway toward identification of critical domains needed for improving activity. However, screening such enzymatic libraries (100s-to-1000s of samples) is time-consuming. Here we demonstrate the use of robotic autosampler (PAL) and immediate drop on demand technology (I.DOT) liquid handling systems coupled with open-port sampling interface-mass spectrometry (OPSI-MS) to screen for PA6 and PA66 hydrolysis by 6-aminohexanoate-oligomer endo-hydrolase (nylon hydrolase, NylC) in a high-throughput (8–20 s/sample) manner. The OPSI-MS technique required minimal sample preparation and was amenable to 96-well plate formats for automated processing. Enzymatic hydrolysis of PA characteristically produced soluble linear oligomer products that could be identified by OPSI-MS. Incubation temperatures and times were optimized for PA6 (65 °C, 24 h) and PA66 (75 °C, 24 h) over 108 experiments. In addition, the I.DOT/OPSI-MS quantified production of PA6 linear dimer (8.3 ± 1.6 μg/mL) and PA66 linear monomer (13.5 ± 1.5 μg/mL) by NylC with a lower limit of detection of 0.029 and 0.032 μg/mL, respectively. For PA6 and PA66, linear oligomer production corresponded to 0.096 ± 0.018% and 0.204 ± 0.028% conversion of dry pellet mass, respectively. The developed methodology is expected to be utilized to assess enzymatic hydrolysis of engineered enzyme libraries, comprising hundreds to thousands of individual samples.

47 OTHER INSTRUMENTATION↗

Hubble Space Telescope-Space Shuttle interface dynamic verification test

A test program has been developed for the interface between the Space Shuttle Orbiter and the Hubble Space Telescope which couples a standard modal test for a simple suspended structure with a novel, 'interface verification' test. While the free-free modal test is used to verify the high loads generating structural modes due to the interaction of internal components of the structure with the rest of the structure, the interface verification test verifies the character of the high-loading generating modes in which the structure reacts against the booster interface. The novel method excites the structure at a single payload-booster interface DOF, while all other interfaces are left free to move.

Blair, Mark A.↗

Structure/Interface Coupling Effect for High-Voltage LiCoO 2 Cathodes

LiCoO 2 (LCO) is widely applied in today's rechargeable battery markets for consumer electronic devices. However, LCO operations at high voltage are hindered by accelerated structure degradation and electrode/electrolyte interface decomposition. To overcome these challenges, co-modified LCO (defined as CB-Mg-LCO) that couples pillar structures with interface shielding are successfully synthesized for achieving high-energy-density and structurally stable cathode material. Benefitting from the "Mg-pillar" effect, irreversible phase transitions are significantly suppressed and highly reversible Li + shuttling is enabled. Interestingly, bonding effects between the interfacial lattice oxygen of CB-Mg-LCO and amorphous Co x B y coating layer are found to elevate the formation energy of oxygen vacancies, thereby considerably mitigating lattice oxygen loss and inhibiting irreversible phase transformation. Meanwhile, interface shielding effects are also beneficial for mitigating parasitic electrode/electrolyte reactions, subsequent Co dissolution, and ultimately enable a robust electrode/electrolyte interface. As a result, the as-designed CB-Mg-LCO cathode achieves a high capacity and excellent cycle stability with 94.6% capacity retention at an extremely high cut-off voltage of 4.6 V. We report these findings provide new insights for cathode material modification methods, which serves to guide future cathode material design.

25 ENERGY STORAGE↗

Phenomenology of Intermediate Molecular Dynamics at Metal-Oxide Interfaces

Reaction intermediates buried within a solid-liquid interface are difficult targets for physiochemical measurements. They are inherently molecular and locally dynamic, while their surroundings are extended by a periodic lattice on one side and the solvent dielectric on the other. Challenges compound on a metal-oxide surface of varied sites and especially so at its aqueous interface of many prominent reactions. Recently, phenomenological theory coupled with optical spectroscopy has become a more prominent tool for isolating the intermediates and their molecular dynamics. The following article reviews three examples of the SrTiO3-aqueous interface subject to the oxygen evolution from water: reaction-dependent component analyses of time-resolved intermediates, a Fano resonance of a mode at the metal-oxide–water interface, and reaction isotherms of metastable intermediates. The phenomenology uses parameters to encase what is unknown at a microscopic level to then circumscribe the clear and macroscopically tuned trends seen in the spectroscopic data.

Chemistry↗

Coupled Data Assimilation for Integrated Earth System Analysis and Prediction: Goals, Challenges, and Recommendations

The purpose of this report is to identify fundamental issues for coupled data assimilation (CDA), such as gaps in science and limitations in forecasting systems, in order to provide guidance to the World Meteorological Organization (WMO) on how to facilitate more rapid progress internationally. Coupled Earth system modeling provides the opportunity to extend skillful atmospheric forecasts beyond the traditional two-week barrier by extracting skill from low-frequency state components such as the land, ocean, and sea ice. More generally, coupled models are needed to support seamless prediction systems that span timescales from weather, subseasonal to seasonal (S2S), multiyear, and decadal. Therefore, initialization methods are needed for coupled Earth system models, either applied to each individual component (called Weakly Coupled Data Assimilation - WCDA) or applied the coupled Earth system model as a whole (called Strongly Coupled Data Assimilation - SCDA). Using CDA, in which model forecasts and potentially the state estimation are performed jointly, each model domain benefits from observations in other domains either directly using error covariance information known at the time of the analysis (SCDA), or indirectly through flux interactions at the model boundaries (WCDA). Because the non-atmospheric domains are generally under-observed compared to the atmosphere, CDA provides a significant advantage over single-domain analyses. Next, we provide a synopsis of goals, challenges, and recommendations to advance CDA: Goals: (a) Extend predictive skill beyond the current capability of NWP (e.g. as demonstrated by improving forecast skill scores), (b) produce physically consistent initial conditions for coupled numerical prediction systems and reanalyses (including consistent fluxes at the domain interfaces), (c) make best use of existing observations by allowing observations from each domain to influence and improve the full earth system analysis, (d) develop a robust observation-based identification and understanding of mechanisms that determine the variability of weather and climate, (e) identify critical weaknesses in coupled models and the earth observing system, (f) generate full-field estimates of unobserved or sparsely observed variables, (g) improve the estimation of the external forcings causing changes to climate, (h) transition successes from idealized CDA experiments to real-world applications. Challenges: (a) Modeling at the interfaces between interacting components of coupled Earth system models may be inadequate for estimating uncertainty or error covariances between domains, (b) current data assimilation methods may be insufficient to simultaneously analyze domains containing multiple spatiotemporal scales of interest, (c) there is no standardization of observation data or their delivery systems across domains, (d) the size and complexity of many large-scale coupled Earth system models makes it is difficult to accurately represent uncertainty due to model parameters and coupling parameters, (e) model errors lead to local biases that can transfer between the different Earth system components and lead to coupled model biases and long-term model drift, (e) information propagation across model components with different spatiotemporal scales is extremely complicated, and must be improved in current coupled modeling frameworks, (h) there is insufficient knowledge on how to represent evolving errors in non-atmospheric model components (e.g. as sea ice, land and ocean) on the timescales of NWP.

CDA↗

A Statistical Approach for the Concurrent Coupling of Molecular Dynamics and Finite Element Methods

Molecular dynamics (MD) methods are opening new opportunities for simulating the fundamental processes of material behavior at the atomistic level. However, increasing the size of the MD domain quickly presents intractable computational demands. A robust approach to surmount this computational limitation has been to unite continuum modeling procedures such as the finite element method (FEM) with MD analyses thereby reducing the region of atomic scale refinement. The challenging problem is to seamlessly connect the two inherently different simulation techniques at their interface. In the present work, a new approach to MD-FEM coupling is developed based on a restatement of the typical boundary value problem used to define a coupled domain. The method uses statistical averaging of the atomistic MD domain to provide displacement interface boundary conditions to the surrounding continuum FEM region, which, in return, generates interface reaction forces applied as piecewise constant traction boundary conditions to the MD domain. The two systems are computationally disconnected and communicate only through a continuous update of their boundary conditions. With the use of statistical averages of the atomistic quantities to couple the two computational schemes, the developed approach is referred to as an embedded statistical coupling method (ESCM) as opposed to a direct coupling method where interface atoms and FEM nodes are individually related. The methodology is inherently applicable to three-dimensional domains, avoids discretization of the continuum model down to atomic scales, and permits arbitrary temperatures to be applied.

Saether, E.↗

A compartmentalized model of multiphase chemical kinetics

There are significant challenges in predicting multiphase chemical kinetics due to the complex coupling of reaction and mass transport across a phase boundary (i.e., interface). Here, we describe a framework for predicting multiphase kinetics that embeds the elementary kinetic steps of reaction, solvation, and diffusion into a coarse grain spatial description of two phases. The model is constructed to bridge the short-timescale interfacial dynamics observed in molecular simulations with the longer timescales observed in kinetic experiments. A simple set of governing differential equations is derived, which, when solved numerically or analytically, yield accurate predictions of multiphase kinetics in microdroplets. Although the equations are formulated for gas-liquid reactions, the underlying conceptual framework is general and can be applied to transformations in other two-phase systems (solid-liquid, liquid-liquid, etc.).

Chemical kinetics and dynamics↗

Investigation of pyruvic acid photolysis at the air-liquid interface as a source of aqueous secondary organic aerosols

Pyruvic acid (PA) is a ubiquitous 2-oxocarboxylic acid in the atmosphere. Its photochemical process at the air-liquid (a-l) interface has been suggested as an important source of aqueous secondary organic aerosols. Here, we investigated the photochemical reaction pathways of PA at the a-l interface using synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) microreactor. Results from mass spectral analysis and the determination of appearance energies (AEs) indicate that photolysis of PA can generate radicals, then they recombine with carboxylic acids and simple molecular oligomers. Furthermore, the preliminary products could form larger oligomers via radical reaction or esterification in the presence of hydroxyl and carboxyl functional groups. Mass spectral comparison shows that most photochemical reactions would complete within 4 h. The expanded photochemistry-driven reaction flowchart of PA is proposed based on the newly discovered products. Our results reveal that the interfacial PA photochemical reactions have different mechanisms from the bulk liquid due to the interfacial properties, such as molecular density, composition, and ion concentration. Our findings show that in situ mass spectral analysis with bright photon ionization is useful to elucidate the contribution of a-l interfacial reactions leading to aqSOA formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exhaust Nozzle for a Multitube Detonative Combustion Engine

An improved type of exhaust nozzle has been invented to help optimize the performances of multitube detonative combustion engines. The invention is applicable to both air-breathing and rocket engines used to propel some aircraft and spacecraft, respectively. In a detonative combustion engine, thrust is generated through the expulsion of combustion products from a detonation process in which combustion takes place in a reaction zone coupled to a shock wave. The combustion releases energy to sustain the shock wave, while the shock wave enhances the combustion in the reaction zone. The coupled shockwave/reaction zone, commonly referred to as a detonation, propagates through the reactants at very high speed . typically of the order of several thousands of feet per second (of the order of 1 km/s). The very high speed of the detonation forces combustion to occur very rapidly, thereby contributing to high thermodynamic efficiency. A detonative combustion engine of the type to which the present invention applies includes multiple parallel cylindrical combustion tubes, each closed at the front end and open at the rear end. Each tube is filled with a fuel/oxidizer mixture, and then a detonation wave is initiated at the closed end. The wave propagates rapidly through the fuel/oxidizer mixture, producing very high pressure due to the rapid combustion. The high pressure acting on the closed end of the tube contributes to forward thrust. When the detonation wave reaches the open end of the tube, it produces a blast wave, behind which the high-pressure combustion products are expelled from the tube. The process of filling each combustion tube with a detonable fuel/oxidizer mixture and then producing a detonation repeated rapidly to obtain repeated pulses of thrust. Moreover, the multiple combustion tubes are filled and fired in a repeating sequence. Hence, the pressure at the outlet of each combustion tube varies cyclically. A nozzle of the present invention channels the expansion of the pulsed combustion gases from the multiple combustion tubes into a common exhaust stream, in such a manner as to enhance performance in two ways: (1) It reduces the cyclic variations of pressure at the outlets of the combustion tubes so as to keep the pressure approximately constant near the optimum level needed for filling the tubes, regardless of atmospheric pressure at the altitude of operation; and (2) It maximizes the transfer of momentum from the exhaust gas to the engine, thereby maximizing thrust. The figure depicts a typical engine equipped with a nozzle according to the invention. The nozzle includes an interface section comprising multiple intake ports that couple the outlets of the combustion tubes to a common plenum. Proceeding from its upstream to its downstream end, the interface section tapers to a larger cross-sectional area for flow. This taper fosters expansion of the exhaust gases flowing from the outlets of the combustion tubes and contributes to the desired equalization of exhaust combustion pressure. The cross-sectional area for flow in the common plenum is greater than, or at least equal to, the combined cross-sectional flow areas of the combustor tubes. In the common plenum, the exhaust streams from the individual combustion tubes mix to form a single compound subsonic exhaust stream. Downstream of the common plenum is the throat that tapers to a smaller flow cross section. In this throat, the exhaust gases become compressed to form a compound sonic gas stream. Downstream of the throat is an expansion section, which typically has a bell or a conical shape. (The expansion section can be truncated or even eliminated in the case of an air-breathing engine.) After entering the expansion section, the exhaust gases expand rapidly from compound sonic to compound supersonic speeds and are then vented to the environment. The basic invention admits of numerous variations. For example, the combustion tubes can be arranged around the central axin a symmetrical or asymmetrical pattern other than the one shown in the figure. For another example, the flow cross-sectional area(s) of one or more of the intake ports in the interface section, of the common plenum, the throat, and/or the expansion section can be varied, either symmetrically or asymmetrically, to adjust dynamics of the exhaust stream or to direct the thrust vector away from the central axis.

Bratkovich, Thomas E.↗

High-Cooperativity Coupling of Rare-Earth Spins to a Planar Superconducting Resonator

The interfacing of a superconducting microwave resonator with rare-earth-doped crystals presents a promising hybrid quantum system for applications including spin-assisted transducers and memories. The coupling strength between the spins of the rare-earth ions and the microwave photons is characterized by the cooperativity. Here, we report an ultrahigh cooperativity of C~650 between rare-earth spins and a planar superconducting microwave resonator that features a highly uniform magnetic field for harnessing the strong anisotropic coupling strength of erbium-doped yttrium orthosilicate. This cooperativity rivals that from a bulk dielectric resonator and may pave a path for efficient coupling of spins with microwave photons on an integrated platform.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ferroelectric Self-Polarization Controlled Magnetic Stratification and Magnetic Coupling in Ultrathin La 0.67 Sr 0.33 MnO 3 Films

Multiferroic oxide heterostructures consisting of ferromagnetic and ferroelectric components hold the promise for nonvolatile magnetic control via ferroelectric polarization, advantageous for the low-dissipation spintronics. Modern understanding of the magnetoelectric coupling in these systems involves structural, orbital, and magnetic reconstructions at interfaces. Previous works have long proposed polarization-dependent interfacial magnetic structures; however, direct evidence is still missing, which requires advanced characterization tools with near-atomic-scale spatial resolutions. Here, extensive polarized neutron reflectometry (PNR) studies have determined the magnetic depth profiles of PbZr 0.2 Ti 0.8 O 3 /La 0.67 Sr 0.33 MnO 3 (PZT/LSMO) bilayers with opposite self-polarizations. When the LSMO is 2–3 nm thick, the bilayers show two magnetic transitions on cooling. However, temperature-dependent magnetization is different below the lower-temperature transition for opposite polarizations. PNR finds that the LSMO splits into two magnetic sublayers, but the inter-sublayer magnetic couplings are of opposite signs for the two polarizations. Near-edge X-ray absorption spectroscopy further shows contrasts in both the Mn valences and the Mn–O bond anisotropy between the two polarizations. Finally, this work completes the puzzle for the magnetoelectric coupling model at the PZT/LSMO interface, showing a synergic interplay among multiple degrees of freedom toward emergent functionalities at complex oxide interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

System and method for responding to ground and flight system malfunctions

A system for on-board anomaly resolution for a vehicle has a data repository. The data repository stores data related to different systems, subsystems, and components of the vehicle. The data stored is encoded in a tree-based structure. A query engine is coupled to the data repository. The query engine provides a user and automated interface and provides contextual query to the data repository. An inference engine is coupled to the query engine. The inference engine compares current anomaly data to contextual data stored in the data repository using inference rules. The inference engine generates a potential solution to the current anomaly by referencing the data stored in the data repository.

Fussell, Ronald M.↗

Domain coupling in activation of a family C GPCR

Abstract The G protein-coupled metabotropic glutamate receptors form homodimers and heterodimers with highly diverse responses to glutamate and varying physiological functions. We employ molecular dynamics, single-molecule spectroscopy and hydrogen–deuterium exchange to dissect the activation pathway triggered by glutamate. We find that activation entails multiple loosely coupled steps, including formation of an agonist-bound, pre-active intermediate whose transition to active conformations forms dimerization interface contacts that set efficacy. The agonist-bound receptor populates at least two additional intermediates en route to G protein-coupling conformations. Sequential transitions into these states act as ‘gates’, which attenuate the effects of glutamate. Thus, the agonist-bound receptor is remarkably dynamic, with low occupancy of G protein-coupling conformations, providing considerable headroom for modulation by allosteric ligands. Sequence variation within the dimerization interface, as well as altered conformational coupling in receptor heterodimers, may contribute to precise decoding of glutamate signals over broad spatial and temporal scales.

Biochemistry & Molecular Biology↗

Unitary quantum lattice simulations for Maxwell equations in vacuum and in dielectric media

Utilizing the similarity between the spinor representation of the Dirac and the Maxwell equations that has been recognized since the early days of relativistic quantum mechanics, a quantum lattice algorithm (QLA) representation of unitary collision-stream operators of Maxwell's equations is derived for both homogeneous and inhomogeneous media. A second-order accurate 4-spinor scheme is developed and tested successfully for two-dimensional (2-D) propagation of a Gaussian pulse in a uniform medium whereas for normal (1-D) incidence of an electromagnetic Gaussian wave packet onto a dielectric interface requires 8-component spinors because of the coupling between the two electromagnetic polarizations. In particular, the well-known phase change, field amplitudes and profile widths are recovered by the QLA asymptotic profiles without the imposition of electromagnetic boundary conditions at the interface. The QLA simulations yield the time-dependent electromagnetic fields as the wave packet enters and straddles the dielectric boundary. QLA involves unitary interleaved non-commuting collision and streaming operators that can be coded onto a quantum computer: the non-commutation being the very reason why one perturbatively recovers the Maxwell equations.

Physics↗

Interface structures of inclined ZnO thin film on (0 1 1)-MgO substrate with bulk-like optical properties

Combining different phase structure materials with unique properties to design novel devices plays a significant role in the development of modern electronics. Here, we explore the characteristics of this type of complex interface and epitaxy structures based on the coupling between hexagonal ZnO film and cubic MgO substrate. The ZnO film was prepared by the molecular beam epitaxy technique on the MgO (0 1 1) substrate. The analysis results from the in situ reflection high energy electron diffraction patterns, X-ray diffraction (XRD)-pole figures and high resolution transmission electron microscopy images demonstrate that the film exhibits two-fold symmetry domains with a growth direction deviated from c-axis at about 31º along the [0 1 0] MgO or [0 $\bar{1}$ 0] MgO azimuth. Despite the intertwined diffusion from Zn and Mg atoms in the interface, which is the possible origin of a blue shift of about 0.083 eV in the Photoluminescence (PL) spectrum, the inclined film shows a full width at half maximum value that is close to the reported value from the high quality film. Finally, this work hopefully provides useful insights to the design and exploration of the novel optoelectronic devices that involve the integration of materials with different structure and different properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

SPARC: Structural properties associated with residue constraints

SPARC facilitates the generation of plausible hypotheses regarding underlying biochemical mechanisms by structurally characterizing protein sequence constraints. Such constraints appear as residues co-conserved in functionally related subgroups, as subtle pairwise correlations (i.e., direct couplings), and as correlations among these sequence features or with structural features. SPARC performs three types of analyses. First, based on pairwise sequence correlations, it estimates the biological relevance of alternative conformations and of homomeric contacts, as illustrated here for death domains. Second, it estimates the statistical significance of the correspondence between directly coupled residue pairs and interactions at heterodimeric interfaces. Third, given molecular dynamics simulated structures, it characterizes interactions among constrained residues or between such residues and ligands that: (a) are stably maintained during the simulation; (b) undergo correlated formation and/or disruption of interactions with other constrained residues; or (c) switch between alternative interactions. We illustrate this for two homohexameric complexes: the bacterial enhancer binding protein (bEBP) NtrC1, which activates transcription by remodeling RNA polymerase (RNAP) containing σ 54 , and for DnaB helicase, which opens DNA at the bacterial replication fork. Based on the NtrC1 analysis, we hypothesize possible mechanisms for inhibiting ATP hydrolysis until ADP is released from an adjacent subunit and for coupling ATP hydrolysis to restructuring of σ 54 binding loops. Based on the DnaB analysis, we hypothesize that DnaB ‘grabs’ ssDNA by flipping every fourth base and inserting it into cavities between subunits and that flipping of a DnaB-specific glutamine residue triggers ATP hydrolysis.

97 MATHEMATICS AND COMPUTING↗