Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “rates”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Compendium of photovoltaic degradation rates

Abstract Published data on photovoltaic (PV) degradation measurements were aggregated and re‐examined. The subject has seen an increased interest in recent years resulting in more than 11 000 degradation rates in almost 200 studies from 40 different countries. As studies have grown in number and size, we found an impact from sampling bias attributable to size and accuracy. Because of the correlational nature of this study we examined the data in several ways to minimize this bias. We found median degradation for x‐Si technologies in the 0.5–0.6%/year range with the mean in the 0.8–0.9%/year range. Hetero‐interface technology (HIT) and microcrystalline silicon (µc‐Si) technologies, although not as plentiful, exhibit degradation around 1%/year and resemble thin‐film products more closely than x‐Si. Several studies showing low degradation for copper indium gallium selenide (CIGS) have emerged. Higher degradation for cadmium telluride (CdTe) has been reported, but these findings could reflect a convolution of less accurate studies and longer stabilization periods for some products. Significant deviations for beginning‐of‐life measurements with respect to nameplate rating have been documented over the last 35 years. Therefore, degradation rates that use nameplate rating as reference may be significantly impacted. Studies that used nameplate rating as reference but used solar simulators showed less variation than similar studies using outdoor measurements, even when accounting for different climates. This could be associated with confounding effects of measurement uncertainty and soiling that take place outdoors. Hotter climates and mounting configurations that lead to sustained higher temperatures may lead to higher degradation in some, but not all, products. Wear‐out non‐linearities for the worst performing modules have been documented in a few select studies that took multiple measurements of an ensemble of modules during the lifetime of the system. However, the majority of these modules exhibit a fairly linear decline. Modeling these non‐linearities, whether they occur at the beginning‐of‐life or end‐of‐life in the PV life cycle, has an important impact on the levelized cost of energy. Copyright © 2016 John Wiley & Sons, Ltd.

Jordan, Dirk C.↗
DOE OSTI2016

Use of Pyranometers to Estimate PV Module Degradation Rates in the Field

Methodology is described that uses relative measurements to estimate the degradation rates of PV modules in the field. The importance of calibration and cleaning is discussed. The number of years of field measurements needed to measure degradation rates with data from the field is cut in half using relative comparisons.

14 SOLAR ENERGY↗
DOE OSTI2015

The contribution of low-energy protons to the total on-orbit SEU rate

Low- and high-energy proton experimental data and error rate predictions are presented for many bulk Si and SOI circuits from the 20-90 nm technology nodes to quantify how much low-energy protons (LEPs) can contribute to the total on-orbit single-event upset (SEU) rate. Every effort was made to predict LEP error rates that are conservatively high; even secondary protons generated in the spacecraft shielding have been included in the analysis. Across all the environments and circuits investigated, and when operating within 10% of the nominal operating voltage, LEPs were found to increase the total SEU rate to up to 4.3 times as high as it would have been in the absence of LEPs. Therefore, the best approach to account for LEP effects may be to calculate the total error rate from high-energy protons and heavy ions, and then multiply it by a safety margin of 5. If that error rate can be tolerated then our findings suggest that it is justified to waive LEP tests in certain situations. Trends were observed in the LEP angular responses of the circuits tested. As a result, grazing angles were the worst case for the SOI circuits, whereas the worst-case angle was at or near normal incidence for the bulk circuits.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2013

Upscaling Calcite Growth Rates from the Mesoscale to the Macroscale

Quantitative prediction of mineral reaction rates in the subsurface remains a daunting task partly because a key parameter for macroscopic models, the reactive site density, is poorly constrained. Here we report atomic force microscopy (AFM) measurements on the calcite surface of monomolecular step densities, treated as equivalent to the reactive site density, as a function of aqueous calcium-to-carbonate ratio and saturation index. Data for the obtuse step orientation are combined with existing step velocity measurements to generate a model that predicts overall macroscopic calcite growth rates. The model is quantitatively consistent with several published macroscopic rates under a range of alkaline solution conditions, particularly for two of the most comprehensive data sets without the need for additional fit parameters. The model reproduces peak growth rates and its functional form is simple enough to be incorporated into reactive transport or other macroscopic models designed for predictions in porous media. However, it currently cannot model equilibrium, pH effects, and may overestimate rates at high aqueous calcium-to-carbonate ratios. The discrepancies in rates at high calcium-to-carbonate ratios may be due to differences in pre-treatment, such as exposing the seed material to SI 1.0 to generate/develop growth hillocks, or other factors.

Bracco, Jacquelyn N.↗
DOE OSTI2012

An investigation of the effect of pore scale flow on average geochemical reaction rates using direct numerical simulation

The scale-dependence of geochemical reaction rates hinders their use in continuum scale models intended for the interpretation and prediction of chemical fate and transport in subsurface environments such as those considered for geologic sequestration of CO 2 . Processes that take place at the pore scale, especially those involving mass transport limitations to reactive surfaces, may contribute to the discrepancy commonly observed between laboratory-determined and continuum-scale or field rates. In this study we investigate the dependence of mineral dissolution rates on the pore structure of the porous media by means of pore scale modeling of flow and multicomponent reactive transport. The pore scale model is composed of high-performance simulation tools and algorithms for incompressible flow and conservative transport combined with a general-purpose multicomponent geochemical reaction code. The model performs direct numerical simulation of reactive transport based on an operator-splitting approach to coupling transport and reactions. The approach is validated with a Poiseuille flow single-pore experiment and verified with an equivalent 1-D continuum-scale model of a capillary tube packed with calcite spheres. Using the case of calcite dissolution as an example, the high-resolution model is used to demonstrate that nonuniformity in the flow field at the pore scale has the effect of decreasing the overall reactivity of the system, even when systems with identical reactive surface area are considered. In conclusion, the effect becomes more pronounced as the heterogeneity of the reactive grain packing increases, particularly where the flow slows sufficiently such that the solution approaches equilibrium locally and the average rate becomes transport-limited.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Enhancing the Lithiation Rate of Silicon Nanowires by the Inclusion of Tin

Silicon (Si) has a very high lithium storage capacity and is being explored as a negative electrode material in lithium-ion batteries (LIBs). Si nanowires can exhibit relatively stable performance for many cycles of charging; however, conductive carbon must often be added to the electrode layer to improve the rate capability due to the relatively low electrical conductivity of Si. The added carbon lowers the capacity of the electrode. Here, we show that the rate capability of Si in LIBs can be substantially enhanced by incorporating tin (Sn) into Si nanowires. The solubility of Sn in Si is very low (0.015 at%); yet, Sn used as a seed for supercritical fluid–liquid–solid (SFLS) growth can be trapped in Si nanowires with relatively high concentration (10 at%). Such Sn-containing Si nanowires and no added conductive carbon in the electrode layer, could be cycled in LIBs with high capacity (*1000 mA h g*1 over 100 cycles) at a current density of 2.8 A g*1 (1 C). Capacities exceeding that of graphite could still be reached at cycle rates as high as 2 C. Real-time in situ transmission electron microscopy (TEM) revealed that lithiation occurs five times faster in Si nanowires with significant amounts of Sn than in the Si nanowires without Sn, and twice as fast as in nanowires that were coated with carbon.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2013

Hydrogen Production using Nickel Electrocatalysts with Pendant Amines: Ligand Effects on Rates and Overpotentials

A Ni-based electrocatalyst for H2 production, [Ni(8PPh2NC6H4Br)2](BF4)2, featuring eight-membered cyclic diphosphine ligands incorporating a single amine base, 1-para-bromo-phenyl-3,7-triphenyl-1-aza-3,7-diphosphacycloheptane (8PPh2NC6H4Br) has been synthesized and characterized. X-ray ?diffraction studies reveal that the cation of [Ni(8PPh2NC6H4Br)2(CH3CN)](BF4)2 has a distorted trigonal bipyramidal geometry. In CH3CN [Ni(8PPh2NC6H4Br)2]2+ is an electrocatalyst for reduction of protons, and it has a maximum turnover frequency for H2 production of 800 s-1 with a 700 mV overpotential (at Ecat/2) when using [(DMF)H]OTf as the acid. Addition of H2O to acidic CH3CN solutions of [Ni(8PPh2NC6H4Br)2]2+ results in an increase of the turnover frequency for H2 production to a maximum of 3,300 s-1 with an overpotential of 760 mV at Ecat/2. Computational studies carried out on [Ni(8PPh2NC6H4Br)2]2+ indicate the observed catalytic rate is limited by formation of non-productive protonated isomers, diverting active catalyst from the catalytic cycle. The results of this research show that proton delivery from the exogenous acid to the correct position on the proton relay of the metal complex is essential for fast H2 production. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

H2 Production, Ni - electrocatalysis, pendant amin↗
DOE OSTI2015

Oscillating decay rate in electron capture and the neutrino mass difference

Reported oscillations in the rate of decay of certain ions by K-electron capture have raised questions about whether and how such oscillations can arise in quantum-mechanical theory and whether they can measure the neutrino mass difference. Here I show that simple principles of quantum mechanics answer some questions and clarify what must be performed theoretically or experimentally to answer some others. The principal result is that quantum mechanics does allow mass-difference-dependent oscillations in principle, but it imposes conditions not obeyed by the approximate dynamical models that have been put forth up to now. In particular, indirect coupling between two neutrino mass channels must be taken into account. What needs to be done experimentally and theoretically is discussed

Peshkin, Murray↗
DOE OSTI2015

Estimated dose rates to members of the public from external exposure to patients with {sup 131}I thyroid treatment

Purpose: Estimated dose rates that may result from exposure to patients who had been administered iodine-131 ({sup 131}I) as part of medical therapy were calculated. These effective dose rate estimates were compared with simplified assumptions under United States Nuclear Regulatory Commission Regulatory Guide 8.39, which does not consider body tissue attenuation nor time-dependent redistribution and excretion of the administered {sup 131}I. Methods: Dose rates were estimated for members of the public potentially exposed to external irradiation from patients recently treated with {sup 131}I. Tissue attenuation and iodine biokinetics were considered in the patient in a larger comprehensive effort to improve external dose rate estimates. The external dose rate estimates are based on Monte Carlo simulations using the Phantom with Movable Arms and Legs (PIMAL), previously developed by Oak Ridge National Laboratory and the United States Nuclear Regulatory Commission. PIMAL was employed to model the relative positions of the {sup 131}I patient and members of the public in three exposure scenarios: (1) traveling on a bus in a total of six seated or standing permutations, (2) two nursing home cases where a caregiver is seated at 30 cm from the patient’s bedside and a nursing home resident seated 250 cm away from the patient in an adjacent bed, and (3) two hotel cases where the patient and a guest are in adjacent rooms with beds on opposite sides of the common wall, with the patient and guest both in bed and either seated back-to-back or lying head to head. The biokinetic model predictions of the retention and distribution of {sup 131}I in the patient assumed a single voiding of urinary bladder contents that occurred during the trip at 2, 4, or 8 h after {sup 131}I administration for the public transportation cases, continuous first-order voiding for the nursing home cases, and regular periodic voiding at 4, 8, or 12 h after administration for the hotel room cases. Organ specific activities of {sup 131}I in the thyroid, bladder, and combined remaining tissues were calculated as a function of time after administration. Exposures to members of the public were considered for {sup 131}I patients with normal thyroid uptake (peak thyroid uptake of ∼27% of administered {sup 131}I), differentiated thyroid cancer (DTC, 5% uptake), and hyperthyroidism (80% uptake). Results: The scenario with the patient seated behind the member of the public yielded the highest dose rate estimate of seated public transportation exposure cases. The dose rate to the adjacent room guest was highest for the exposure scenario in which the hotel guest and patient are seated by a factor of ∼4 for the normal and differentiated thyroid cancer uptake cases and by a factor of ∼3 for the hyperthyroid case. Conclusions: It was determined that for all modeled cases, the DTC case yielded the lowest external dose rates, whereas the hyperthyroid case yielded the highest dose rates. In estimating external dose to members of the public from patients with {sup 131}I therapy, consideration must be given to (patient- and case-specific) administered {sup 131}I activities and duration of exposure for a more complete estimate. The method implemented here included a detailed calculation model, which provides a means to determine dose rate estimates for a range of scenarios. The method was demonstrated for variations of three scenarios, showing how dose rates are expected to vary with uptake, voiding pattern, and patient location.

60 APPLIED LIFE SCIENCES↗