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At least 739 records · Page 41

The W-W02 Oxygen Fugacity Buffer at High Pressures and Temperatures: Implications for f02 Buffering and Metal-silicate Partitioning

Oxygen fugacity (fO2) controls multivalent phase equilibria and partitioning of redox-sensitive elements, and it is important to understand this thermodynamic parameter in experimental and natural systems. The coexistence of a metal and its oxide at equilibrium constitutes an oxygen buffer which can be used to control or calculate fO2 in high pressure experiments. Application of 1-bar buffers to high pressure conditions can lead to inaccuracies in fO2 calculations because of unconstrained pressure dependencies. Extending fO2 buffers to pressures and temperatures corresponding to the Earth's deep interior requires precise determinations of the difference in volume (Delta) V) between the buffer phases. Synchrotron x-ray diffraction data were obtained using diamond anvil cells (DAC) and a multi anvil press (MAP) to measure unit cell volumes of W and WO2 at pressures and temperatures up to 70 GPa and 2300 K. These data were fitted to Birch-Murnaghan 3rd-order thermal equations of state using a thermal pressure approach; parameters for W are KT = 306 GPa, KT' = 4.06, and αKT = 0.00417 GPa K-1. Two structural phase transitions were observed for WO2 at 4 and 32 GPa with structures in P21/c, Pnma and C2/c space groups. Equations of state were fitted for these phases over their respective pressure ranges yielding the parameters KT = 190, 213, 300 GPa, KT' = 4.24, 5.17, 4 (fixed), and αKT = 0.00506, 0.00419, 0.00467 GPa K-1 for the P21/c, Pnma and C2/c phases, respectively. The W-WO2 buffer (WWO) was extended to high pressure by inverting the W and WO2 equations of state to obtain phase volumes at discrete pressures (1-bar to 100 GPa, 1 GPa increments) along isotherms (300 to 3000K, 100 K increments). The slope of the absolute fO2 of the WWO buffer is positive with increasing temperature up to approximately 70 GPa and is negative above this pressure. The slope is positive along isotherms from 1000 to 3000K with increasing pressure up to at least 100 GPa. The WWO buffer is at a higher fO2 than the IW buffer at pressures lower than 40 GPa, and the magnitude of this difference decreases at higher pressures. This qualitatively indicates an increasingly lithophile character for W at higher pressures. The WWO buffer was quantitatively applied to W metal-silicate partitioning by using the WWO-IW buffer difference in combination with literature data on W metal-silicate partitioning to model the exchange coefficient (KD) for the Fe-W exchange reaction. This approach captures the pressure dependence of W metal-silicate partitioning using the WWO-IW buffer difference and models the activities of the components in the silicate and metallic phases using an expression of the Gibbs excess energy of mixing. Calculation of KD along a peridotite liquidus predicts a decrease in W siderophility at higher pressures that supports the qualitative behavior predicted by the WWO-IW buffer difference, and agrees with findings of others. Comparing the competing effects of temperature and pressure on W metal-silicate partitioning, our results indicate that pressure exerts a greater effect.

Shofner, G. A.↗

Robust controllers for the Middeck Active Control Experiment using Popov controller synthesis

Recent work in robust control with real parameter uncertainties has focused on absolute stability and its connections to real mu theory. In particular, the research has investigated the Popov stability criterion and its associated Lur'e-Postnikov Liapunov functions. State space representations of this Popov stability analysis tests are included in an H2 design formulation to provide a powerful technique for robust controller synthesis. This synthesis approach uses a state space optimization procedure to design controllers that minimize an overbound of an H2 cost functional and satisfy stability analysis tests based on the Popov multiplier. The controller and stability multiplier coefficients are optimized simultaneously, which avoids the iteration and curve-fitting procedures required by the D-K algorithm of mu synthesis. While previous work has demonstrated this synthesis approach on benchmark control problems, the purpose of this paper is to use Popov controller synthesis to design robust compensators for the Middeck Active Control Experiment (MACE).

How, Jonathan P.↗

M558 radioactive tracer diffusion

This experiment was performed in Skylab 3 with two objectives in mind. First, the experimental self-diffusion coefficients for liquid zinc were to be determined in a convection-free environment. Secondly the reduction in convective mixing in earth gravity by going into the zero-gravity environment of space was to be estimated. The experiment was designed to utilize high temperatures and linear thermal gradients provided by the M518 Multipurpose Electric Furnace, and the radioactivity of zinc-65 of 245-day half-life to investigate self-diffusion in liquid zinc. The distribution of zinc-65 tracer, after melting, maintaining at soak temperature for 1 hour of soak time and then resolidifying, was obtained by sample sectioning. The concentration of activity of each section (microcurie-gram) was plotted against positions along the sample axial and radial position. Experimental data and theoretical results from solution of Fick's law of diffusion in one dimensional were compared. Samples tested on earth showed very rapid diffusion. Diffusion coefficient in unit gravity was 50 times the zero-gravity diffusion coefficient of Skylab.

Ukanwa, A. O.↗

An active particle diffusion theory of flame quenching for laminar flames / Dorothy M. Simon and Frank E. Belles

An equation for quenching distance based on the destruction of chain carriers by the surface is derived. The equation expresses the quenching distance in terms of the diffusion coefficients and partial pressures of the chain carriers and gas phase molecules, the efficiency of the surface as a chain breaker, the total pressure of the mixture, and a constant which depends on the geometry of the quenching surface. Quenching distances measured by flashback for propane-air flames are shown to be consistent with the mechanism. The derived equation is used with the lean inflammability limit and a rate constant calculated from burning velocity data to estimate quenching distances for propane-air (hydrocarbon lean) flames satisfactorily.

Simon, Dorothy M↗

Active Aerodynamic Load Control for Wind Turbines

The goal of this project was to develop and demonstrate an advanced dielectric barrier discharge (DBD) plasma actuator technology. We set out to demonstrate the efficacy and impact of the new actuator technology as a key component of an active load control system for wind turbines. A DBD plasma actuator consists of a thin layer of dielectric material separating a pair of offset electrodes. One of those electrodes is embedded between the dielectric layer and a non-conductive substrate, while the other is exposed to air. When driven by an appropriate high voltage waveform, the device ionizes the air near the surface of the dielectric and adjacent to the exposed electrode. Collisions between the ions in the plasma and neutral air molecules result in a wall-jet – a region of induced air velocity that can be used to modify the flow around a lifting body. Use of the device near the trailing edge of a wind turbine blade, designed in such a way as to amplify the effects of the flow-modifying device, can result in large changes to the global forces experienced by the blade. Because of the fast response time of the device, it can allow the turbine to react in real time to changes in the wind associated with turbulence, wind shear, gusts, and the like, when paired with appropriate sensors and control algorithms. The goal of this project was to increase the capacity of the device to induce velocity on its surface at the levels required by large, utility-scale wind turbines. The first technical goal was to increase the induced velocity from the current industry-best of about 4 m/s to 10 m/s by modifying the electrical waveform used to drive the device and by introducing a semi-conductive surface coating to control electrostatic charge build-up on the surface. The second goal was to use the device to modify the lift on a representative airfoil in a wind tunnel, demonstrating a reduction in lift coefficient of 0.2 or better. The third goal was to produce an actuator-induced velocity of 20 m/s. Alongside our partners at the University of Texas at Dallas, we also applied modern, advanced design methods to optimize the impact of the technology on the design of wind turbines. We also had planned to install a segmented, active load control system on a test turbine to demonstrate the ability to reduce unsteady aerodynamic forces on the turbine associated with changes in the wind. The highest induced velocity achieved during this research was 11 m/s. However, practical design constraints limited the change in lift coefficient to about 0.12 for a representative airfoil in the wind tunnel at a Reynolds number of 400,000. The primary conclusion is that the plasma actuator control authority remains insufficient for practical purposes when extrapolated to Reynolds numbers over 1 million. The potential impact of the active lift control concept was evaluated through detailed simulations for three wind turbine sizes: a 3.4MW onshore turbine, a 10MW offshore turbine, and a 15MW offshore turbine. A feedback control system was designed for each turbine within two scenarios: one where the active lift control is used as a retrofit capability on the baseline design, and the other where the designers were permitted to “upscale” the turbines in order increase annual energy production. The levelized cost of energy was then evaluated for the range of turbine sizes and design configuration. It was found that the LCOE reduction associated with active lift control fell in the range of 0.7% to 7.2%, with the highest reduction associated with upscaling the 3.4MW turbine.

17 WIND ENERGY↗

On the Relationship Between Global Land-Ocean Temperature and Various Descriptors of Solar-Geomagnetic Activity and Climate

Examined are sunspot cycle- (SC-) length averages of the annual January-December values of the Global Land-Ocean Temperature Index ( ) in relation to SC-length averages of annual values of various descriptors of solar-geomagnetic activity and climate, incorporating lags of 0-5 yr. For the overall interval SC12-SC23, the is inferred to correlate best against the parameter incorporating lag = 5 yr, where the parameter refers to the resultant aa value having removed that portion of the annual aa average value due to the yearly variation of sunspot number (SSN). The inferred correlation between the and is statistically important at confidence level cl > 99.9%, having a coefficient of linear correlation r = 0.865 and standard error of estimate se = 0.149 degC. Excluding the most recent cycles SC22 and SC23, the inferred correlation is stronger, having r = 0.969 and se = 0.048 degC. With respect to the overall trend in the , which has been upwards towards warmer temperatures since SC12 (1878-1888), solar-geomagnetic activity parameters are now trending downwards (since SC19). For SC20-SC23, in contrast, comparison of the against SC-length averages of the annual value of the Mauna Loa carbon dioxide ( ) index is found to be highly statistically important (cl >> 99.9%), having r = 0.9994 and se = 0.012 degC for lag = 2 yr. On the basis of the inferred preferential linear correlation between the and , the current ongoing SC24 is inferred to have warmer than was seen in SC23 (i.e., >0.526 degC), probably in excess of 0.68 degC (relative to the 1951-1980 base period).

Wilson, Robert M.↗

Microwave remote sensing of snowpacks

The interaction mechanisms responsible for the microwave backscattering and emission behavior of snow were investigated, and models were developed relating the backscattering coefficient (sigma) and apparent temperature (T) to the physical parameters of the snowpack. The microwave responses to snow wetness, snow water equivalent, snow surface roughness, and to diurnal variations were investigated. Snow wetness was shown to have an increasing effect with increasing frequency and angle of incidence for both active and passive cases. Increasing snow wetness was observed to decrease the magnitude sigma and increase T. Snow water equivalent was also observed to exhibit a significant influence sigma and T. Snow surface configuration (roughness) was observed to be significant only for wet snow surface conditions. Diurnal variations were as large as 15 dB for sigma at 35 GHz and 120 K for T at 37 GHz. Simple models for sigma and T of a snowpack scene were developed in terms of the most significant ground-truth parameters. The coefficients for these models were then evaluated; the fits to the sigma and T measurements were generally good. Finally, areas of needed additional observations were outlined and experiments were specified to further the understanding of the microwave-snowpack interaction mechanisms.

Stiles, W. H.↗

A two-dimensional analytical unit cell model for redox flow battery evaluation and optimization

Cell performance optimization is important for improving the overall system efficiency of a redox flow battery. To gain better insights into key controlling factors of system efficiency, this work first proposed a theoretical model for a unit flow battery cell by extending a two-dimensional analytic model to a full battery cell. Such a model is then used for cell performance optimization after validating it with experimental and numerical modeling data. With the model results, the activation, equilibrium, and pump energy losses are identified as the dominant sources of battery energy losses. Further, a guideline for reducing these sources is also proposed. Following the guideline, the mass transport coefficient is shown as a key control factor of the equilibrium energy loss and Coulombic efficiency (CE). Approaches are then proposed to improve CE and the overall system efficiency. The mass transport is also revealed as the mechanism of pump rate optimization where an optimal pump rate significantly reduces the equilibrium energy loss. With both low equilibrium and pump energy losses, an optimal electrode porosity or specific area design can further improve a battery's system efficiency based on an optimal porosity predicted by the present model. The model also demonstrates distinct behaviors and overestimation in the system efficiency when reduced to a zero-dimensional model with neglected mass transport resistance. With the new model, the guideline, and new insights, this work provides a reliable and efficient tool for the evaluation and optimization of redox flow battery design in practical applications.

25 ENERGY STORAGE↗

Tribology of two-dimensional materials: From mechanisms to modulating strategies

Two-dimensional (2D) materials are crystalline materials made of a single or a few layers of atoms. They have been an active research subject in recent years because of their unique physical and chemical properties. In particular, 2D materials such as graphene, hexagonal BN, and MoS 2 exhibit some of the lowest friction coefficients and wear rates, making them attractive for enhancing the efficiency, durability, and environmental compatibility of future mechanical systems. This review will focus on recent advances in the tribology of 2D materials. Starting from general physical characteristics, the essential friction and wear behavior of 2D materials together with the associated mechanisms are reviewed for both interlayer and surface sliding. Influences of the atomic structures of the slip interfaces and environmental factors are discussed, with special attention given to various strategies for achieving friction modulation and superlubricity. Finally, the emerging engineering applications of 2D materials, as well as future prospects, are summarized.

36 MATERIALS SCIENCE↗

Modeling Substrate Utilization, Metabolite Production, and Uranium Immobilization in Shewanella oneidensis Biofilms

In this study, we developed a two-dimensional mathematical model to predict substrate utilization and metabolite production rates in Shewanella oneidensis MR-1 biofilm in the presence and absence of uranium (U). In our model, lactate and fumarate are used as the electron donor and the electron acceptor, respectively. The model includes the production of extracellular polymeric substances (EPS). The EPS bound to the cell surface and the EPS distributed in the biofilm were considered bound EPS (bEPS) and loosely associated EPS (laEPS), respectively. COMSOL ® Multiphysics finite element analysis software was used to solve the model numerically (model file provided in the Supplementary Material). The input variables of the model were the lactate and fumarate concentrations, cell density, EPS density, half saturation constant for fumarate, and diffusion coefficients of the substrates and metabolites. To estimate unknown parameters and calibrate the model, we used a custom designed biofilm reactor placed inside a nuclear magnetic resonance (NMR) microimaging and spectroscopy system and measured substrate utilization and metabolite production rates. From these data we estimated the yield coefficients, maximum substrate utilization rate, half saturation constant for lactate, stoichiometric ratio of fumarate and acetate to lactate and stoichiometric ratio of succinate to fumarate. These parameters are critical to predicting the activity of biofilms and are not available in the literature. Lastly, the model was used to predict uranium immobilization in S. oneidensis MR-1 biofilms by considering reduction and adsorption processes in the cells and in the EPS. We found that the majority of immobilization was due to cells, and that EPS were less efficient at immobilizing U. Furthermore, most of the immobilization occurred within the top 10 µm of the biofilm. To the best of our knowledge, this research is one of the first biofilm immobilization mathematical models based on experimental observation. It has the ability to predict the relative contributions to U immobilization of laEPS, bEPS and cells.

59 BASIC BIOLOGICAL SCIENCES↗

Determining the parameters of the prognostic operator for undamped fluctuations by the use of the D sub m(kappa; alpha 1,..., alpha sub m)

The prognostic operator is defined as the matrix or integral operation which, when applied to a set of known values of the vector for various earlier moments of time, predicts a value for the vector at a future moment by the amount ahead of time. If the vector represents a function that decays with time, then the predicted values of the function are given as series expansions in terms of the same functions but with unknown coefficients if some change in the process occurs at the moment of prediction. As examples of such changes are considered: (1) the circulation mechanisms of the atmosphere under the influence of solar activity; (2) brightness fields fluctuations; and (3) wave formations or currents in the ocean after a change in wind field.

Dmitriyev, A. A.↗

Soil respiration across a permafrost transition zone: spatial structure and environmental correlates

Soil respiration is a key ecosystem function whereby shifts in respiration rates can shift systems from carbon sinks to sources. Soil respiration in permafrost-associated systems is particularly important given climate change driven permafrost thaw that leads to significant uncertainty in resulting ecosystem carbon dynamics. Here we characterize the spatial structure and environmental drivers of soil respiration across a permafrost transition zone. We find that soil respiration is characterized by a non-linear threshold that occurs at active-layer depths greater than 140 cm. We also find that within each season, tree basal area is a dominant driver of soil respiration regardless of spatial scale, but only in spatial domains with significant spatial variability in basal area. Our analyses further show that spatial variation (the coefficient of variation) and mean-variance power-law scaling of soil respiration in our boreal system are consistent with previous work in other ecosystems (e.g., tropical forests) and in population ecology, respectively. Comparing our results to those in other ecosystems suggests that temporally stable features such as tree-stand structure are often primary drivers of spatial variation in soil respiration. If so, this provides an opportunity to better estimate the magnitude and spatial variation in soil respiration through remote sensing. Finally, combining such an approach with broader knowledge of thresholding behavior – here related to active layer depth – would provide empirical constraints on models aimed at predicting ecosystem responses to ongoing permafrost thaw.

54 ENVIRONMENTAL SCIENCES↗

A theoretical/experimental program to develop active optical pollution sensors

Light detection and ranging (LIDAR) technology was applied to the assessment of air quality, and its usefulness was evaluated by actual field tests. Necessary hardware was successfully constructed and operated in the field. Measurements of necessary physical parameters, such as SO2 absorption coefficients were successfully completed and theoretical predictions of differential absorption performance were reported. Plume modeling improvements were proposed. A full scale field test of equipment, data analysis and auxiliary data support was conducted in Maryland during September 1976.

Mills, F. S.↗

A charge-transfer resistance model and Arrhenius activation analysis for hydrogen ion transmission across single-layer graphene

Transmission rates for protons and deuterons across single-layer graphene embedded in Nafion | graphene | Nafion sandwich structures are measured as a function of temperature in electrochemical hydrogen pump cells. Rates of ion transmission through graphene are obtained in the form of area-normalized ion-transfer resistances, and are interpreted in terms of ion-exchange current densities and standard heterogeneous ion-transfer rate constants. An encounter pre-equilibrium model for the ion-transfer step is then used to provide rate constants for the fundamental microscopic step of ion (proton or deuteron) transmission across graphene. Application of this rate model to interpret variable-temperature data on proton and deuteron transmission rates provides values for the activation energy and pre-exponential factor for the fundamental ion transmission step across graphene. Activation energies obtained from the Arrhenius plots for proton and deuteron transmission are as follows; for proton, E act = 48 ± 2 kJ/mole (0.50 ± 0.02 eV) and for deuteron, E act = 53 ± 5 kJ/mole (0.55 ± 0.05 eV). The difference between these two values of approximately 5 kJ/mole is in good agreement with the expected difference in vibrational zero-point energies for O—H and O-D bonds, albeit with some uncertainty given the uncertainties in the activation energy values. Pre-exponential frequency factor values of 8.3 ± 0.4 × 10 13 s -1 and is 4.7 ± 0.5 × 10 13 s -1 were obtained for proton and deuteron transmission respectively across graphene. These pre-factor values are both quite large, on the order of the values predicted from the Eyring – Polanyi equation with a transmission coefficient near one. The ratio of 1.8 for the rate pre-factors (H/D) is in reasonable agreement with the value of 1.3 for the ratio of bond vibrational frequencies for O—H and O-D stretching, respectively. Taken together, these data support a model in which proton and deuteron transmission across graphene are largely adiabatic processes for which the differences in transmission rate at room temperature are due largely to differences in activation energies.

2D materials↗

High-temperature deformation behavior of the extruded Ti-22Al-25Nb alloy fabricated by powder metallurgy

Highlights: • The high-temperature deformation behavior of the extruded Ti-22Al-25Nb alloy was analyzed. • A true strain-compensated Arrhenius-type constitutive model was established. • The processing maps of true strains 0.2, 0.4, and 0.6 were constructed to optimize the processing parameters. • Microstructural evolution and deformation mechanism in different conditions were explained. - Abstract: The hot-deformation behavior of the extruded Ti-22Al-25Nb alloy was investigated by compression testing in the 1213–1333 K temperature range, under a 0.001–1.0 s{sup −1} strain-rate range. The activation energy, Q, at a deformation strain of 0.3, was calculated to be 574.80 kJ mol{sup −1}. A strain-compensated Arrhenius-type constitutive model was established for this alloy, with an average absolute relative error (AARE) and correlation coefficient (R) of 7.64% and 0.994, respectively. Based on the dynamic materials model (DMM), processing maps were developed by combining the power dissipation and instability maps. An instability region was identified in the 1213–1278 K temperature range and 0.022–1.0 s{sup −1} strain-rate range. The microstructure of specimens deformed under different conditions were analyzed to characterize the corresponding deformation mechanisms. The main softening mechanisms in the stability regions were dynamic recrystallization (DRX) and dynamic globularization. The grain size of the specimen deformed at 1313 K/0.001 s{sup −1} was approximately 15.2 μm.

36 MATERIALS SCIENCE↗

Theory-Based Mechanism for Fluoromethane Combustion I: Thermochemistry and Abstraction Reactions

A new detailed chemical kinetic mechanism is presented for small fluorinated hydrocarbons. Ab initio electronic structure theory is used to provide heats of formation with subchemical accuracy. The ANL0 method is extended to include fluorine. The resulting heats of formation at 0 K are in excellent agreement with 36 benchmark species in the Active Thermochemical Tables, with a mean error of μ = –0.02 kJ/mol and a standard deviation of σ = 0.91 kJ/mol. The thermophysical properties for 92 small-molecule H/C/O/F species are computed. The rate coefficients for 40+ H-abstraction reactions involving H, O, F, OH, OF, HO 2 , and various methyl radicals with CH 4 , CH 3 F, CH 2 F 2 , CHF 3 , CH 2 O, and CHFO are discussed. Here, the computed rate constants are in excellent agreement with the available literature. Additionally, 30+ rate constants are provided for F abstraction, which are several orders of magnitude smaller than H abstraction. The thermophysical properties and rate constants are provided in a mechanism. This mechanism is the first in a series of theory-based investigations into the thermal destruction of per- and polyfluorinated species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Translational and Rotational Motion of C8 Aromatics Adsorbed in Isotropic Porous Media (MOF-5): NMR Studies and MD Simulations

For this, we combined nuclear magnetic resonance (NMR) and molecular dynamics (MD) simulation to study xylene behavior in MOF-5, probing the effects of adsorbate geometry in a weakly interacting model isotropic metal organic framework (MOF) system. We employed NMR diffusometry and relaxometry techniques at low field (13 MHz) to quantify the self-diffusion coefficients (D s ) and the longitudinal relaxation times (T 1 ) of xylenes in MOF-5 as a function of temperature at the saturated loading for each xylene. These experiments reveal the translational motion activation energies to be 15.3, 19.7, and 21.2 kj mol -1 and the rotational activation energies to be 47.26, 12.88, and 11.55 for the (p-, m-, o-) xylene isomers, respectively. Paraxylene exhibits faster translational motion, yet shows four times the activation energy barrier for rotational motion vis-à-vis the other isomers. MD simulations performed on these model systems corroborate the findings for paraxylene and suggest that paraxylene has the lower free energy barrier for hopping away from its binding sites, yet has the slowest rotational motion in the plane of the xylene molecule.

36 MATERIALS SCIENCE↗

Influence of Heterointerfaces on the Kinetics of Oxygen Surface Exchange on Epitaxial La 1.85 Sr 0.15 CuO 4 Thin Films

Considerable attention has been directed to understanding the influence of heterointerfaces between Ruddlesden–Popper (RP) phases and ABO 3 perovskites on the kinetics of oxygen electrocatalysis at elevated temperatures. Here, we report the effect of heterointerfaces on the oxygen surface exchange kinetics by employing heteroepitaxial oxide thin films formed by decorating LaNiO 3 (LNO) on La 1.85 Sr 0.15 CuO 4 (LSCO) thin films. Regardless of LNO decoration, tensile in-plane strain on LSCO films does not change. The oxygen surface exchange coefficients (kchem) of LSCO films extracted from electrical conductivity relaxation curves significantly increase with partial decorations of LNO, whereas full LNO coverage leads to the reduction in the kchem of LSCO films. The activation energy for oxygen exchange in LSCO films significantly decreases with partial LNO decorations in contrast with the full coverage of LNO. Optical spectroscopy reveals the increased oxygen vacancies in the partially covered LSCO films relative to the undecorated LSCO film. We attribute the enhanced oxygen surface exchange kinetics of LSCO to the increased oxygen vacancies by creating the heterointerface between LSCO and LNO.

25 ENERGY STORAGE↗