Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “timescale”

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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal–Ligand Cooperativity

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [Co III Cp(P Ph 2 N Bn 2 )(CH 3 CN)] 2+ to [HCo III Cp(P Ph 2 NBn 2 )] + . This complex catalytically converts CO 2 to formate under CO 2 reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the P Ph 2 N Bn 2 ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation. We reveal three unique PCET mechanisms, and we show that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site en route to the thermodynamically favored cobalt hydride. Cyclic voltammograms recorded with proton sources that span a wide range of pK a values show four distinct regimes where the mechanism changes as a function of acid strength, acid concentration, and timescale between electrochemical steps. Peak shift analysis was used to determine proton transfer rate constants where applicable. Furthermore, this work highlights the astute choices that must be made when designing catalytic systems, including the basicity and kinetic accessibility of protonation sites, acid strength, acid concentration, and timescale between electron transfer steps, to maximize catalyst stability and efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Charge Recombination with Fractional Reaction Orders in Water-Splitting Dye-sensitized Photoelectrochemical Cells

In water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs), charge recombination competes with catalytic water oxidation to determine the overall efficiency of the system. The kinetics of these processes have been difficult to understand because transient absorbance (TA) experiments typically show nearly complete charge recombination on the sub-millisecond timescale; in contrast, electrochemical measurements such as open circuit photovoltage decay suggest a charge recombination timescale that is 2-3 orders of magnitude longer. Here we explore these processes with dye-sensitized nanocrystalline TiO 2 and TiO 2 /Ta 2 O 5 core-shell photoanodes in aqueous electrolytes using TA spectroscopy, intensity-modulated photovoltage spectroscopy (IMVS), and photoelectrochemical impedance spectroscopy (PEIS). The fast recombination rates measured by TA result from strong laser excitation that leads to high electron occupancy in TiO 2 , whereas IMVS modulates the concentration of charge-separated states near solar irradiance levels. The recombination processes measured by electrochemical methods such as IMVS, PEIS, and transient photovoltage are the discharging of injected electrons in TiO 2 , as evidenced by the close agreement betweeen the nearly first-order recombination rates probed by IMVS and the RC time constants derived from PEIS data. However, IMVS measurements at variable probe light intensity reveal that the reaction orders for the recombination of injected electrons with oxidized sensitizer molecules are far from unity. In conclusion, this kinetic analysis is relevant to understanding steady-state recombination rates in full WS-DSPECs in which molecular and nanoparticle catalysts are used to oxidize water.

14 SOLAR ENERGY↗
DOE OSTI2018

Pitch Angle Scattering and Loss of Radiation Belt Electrons in Broadband Electromagnetic Waves

A magnetic conjunction between Van Allen Probes spacecraft and the Balloon Array for Radiation-belt Relativistic Electron Losses (BARREL) demonstrates the simultaneous occurrence of broadband Alfvénic fluctuations and multi-timescale modulation of enhanced atmospheric X-ray bremsstrahlung emission. The properties of the Alfvénic fluctuations are utilized to build a model for pitch angle scattering in the outer radiation belt on electron gyro-radii scale field structures. It is observed that this scattering may lead to the transport of electrons into the loss cone over an energy range from hundreds of keV to multi-MeV on diffusive timescales on the order of hours. This process may account for modulation of atmospheric X-ray fluxes observed from balloons and constitute a significant loss process for the radiation belts.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Global Impacts of Arctic Sea Ice Loss Mediated by the Atlantic Meridional Overturning Circulation

We explore the global impacts of Arctic sea ice decline in climate model perturbation experiments focusing on the temporal evolution of induced changes. We find that climate response to a realistic reduction in sea ice cover varies dramatically between shorter decadal and longer multidecadal to centennial timescales. During the first two decades, when atmospheric processes dominate, sea ice decline induces a “bipolar seesaw” pattern in surface temperature with warming in the Northern and cooling in the Southern Hemisphere, leading to a northward displacement of the Intertropical Convergence Zone and an expansion of Antarctic sea ice. In contrast, on multidecadal and longer timescales, the weakening of the Atlantic meridional overturning circulation, caused by upper-ocean buoyancy anomalies spreading from the Arctic, mediates direct sea ice impacts and nearly reverses the original response pattern outside the Arctic. Lastly, the Southern Hemisphere warms, a Warming Hole emerges in the North Atlantic, the Intertropical Convergence Zone shifts southward, and Antarctic sea ice contracts.

58 GEOSCIENCES↗
DOE OSTI2018

Experimental Poroviscoelasticity of Common Sedimentary Rocks

The success of geoenergy applications such as petroleum recovery or geological storage of CO 2 depends on properly addressing the physical coupling between the pore fluid diffusion and mechanical deformation of the subsurface rock. Constitutive models should include short-term hydromechanical interactions and long-term behavior and should incorporate the principles behind the mathematical models for poroelastic and poroviscoelastic responses. However, the viscous parameters in constitutive relationships still need to be validated and estimated. In this work, we experimentally quantify the time-dependent response of fluid-filled sedimentary rocks at room temperature and isotropic stress states. Drained, undrained, and unjacketed geomechanical tests are performed to measure the poroelastic parameters for Berea sandstone, Apulian limestone, clay-rich material, and Opalinus clay (shale). A poroviscous model parameter, the bulk viscosity, is included in the constitutive relationships. The bulk viscosity is estimated under constant isotropic stress conditions from time-dependent deformation of rock in the drained regime for timescales ~10 5 s and from observations of the pore pressure growth under undrained conditions at timescales of ~10 4 s. The bulk viscosity is on the order of 10 15 –10 16 Pa s for sandstone, limestone, and shale and ~10 13 Pa s for clay-rich material, and it decreases with an increase in pore pressure despite a corresponding decrease in the effective stress. In the long term, fluid pressure can asymptotically approach minimum principal stress, which in natural reservoirs may lead to liquefaction or rock embrittlement, causing slip instabilities and earthquakes and creating high-permeability channels in low-permeable rock.

58 GEOSCIENCES↗
DOE OSTI2018

Temporal Characteristics of Cloud Radiative Effects on the Greenland Ice Sheet: Discoveries From Multiyear Automatic Weather Station Measurements

The impact of clouds on Greenland's surface melt is difficult to quantify due to the limited amount of in situ observations. To better quantify cloud radiative effects (CRE), we utilize 29 automatic weather stations and provide the first analysis on seasonal and hourly timescales in both accumulation and ablation zones. Seasonal CRE shows opposing cycles across geographical regions. CRE generally increases during melt season in the north of Greenland, mainly due to longwave CRE enhancement by cloud fraction and liquid water. CRE decreases from May to July and increases afterwards in the middle and south of Greenland, mainly due to strengthened shortwave CRE caused by surface albedo reduction. This finding resolves the contrasting seasonal distributions in previous studies at different Arctic locations. Longwave seasonal cycle also shifts from increasing in the north to decreasing in the south, implying spatial variations in cloud and atmospheric conditions. On hourly timescales, longwave downwelling radiation exhibits a bimodal distribution peaking at ~-70 W/m 2 (i.e., clear state) and ~0 W/m 2 (i.e., cloudy state), suggesting that Greenland alternates between fairly clear and overcast. In the cloudy state, CRE strongly correlates with the combined influence of solar zenith angle and albedo (r = 0.85, p < 0.01) probably because clouds are thick enough for CRE to become saturated. The close relationship between CRE and albedo over dark surfaces suggests a stabilizing feedback: Net CRE is negative at low albedo caused by snow melt and snow metamorphism and thus tends to increase albedo and decelerate surface melt.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

SiO 2 –SiC Mixtures at High Pressures and Temperatures: Implications for Planetary Bodies Containing SiC

We present results from high–pressure and high–temperature experiments on mixtures of SiC and SiO 2 to explore the stability of SiC in the presence of oxygen–rich silicates at planetary mantle conditions. We observe no evidence of the ambient pressure predicted oxidation products, CO or SiO, resulting from oxidation reactions between SiC and SiO 2 at pressures up to ~40 GPa and temperatures up to ~2500 K. We observe the decomposition of SiC through releasing C, resulting in vacancies in the SiC lattice and consequently the contracted SiC ambient volume V0 observed in the heated regions of sample. The decomposition is further supported by the observations of diamond formation and the expanded SiO 2 V0 in the heated regions of samples indicating the incorporation of C into SiO2 stishovite. We provide a new interpretation of SiC decomposition on laboratory timescales, in which kinetics prevent the reaction from reaching equilibrium. We consider how the equilibrium decomposition reaction of SiC will influence the differentiation of a SiC–containing body on planetary timescales and find that the decomposition products may become isolated during early planetary differentiation. Here, the resulting presence of elemental Si and C within a planetary body may have important consequences for the compositions of the mantles and atmospheres of such planets.

36 MATERIALS SCIENCE↗
DOE OSTI2019

The Relationship Between U.S. East Coast Sea Level and the Atlantic Meridional Overturning Circulation: A Review

Abstract Scientific and societal interest in the relationship between the Atlantic Meridional Overturning Circulation (AMOC) and U.S. East Coast sea level has intensified over the past decade, largely due to (1) projected, and potentially ongoing, enhancement of sea level rise associated with AMOC weakening and (2) the potential for observations of U.S. East Coast sea level to inform reconstructions of North Atlantic circulation and climate. These implications have inspired a wealth of model‐ and observation‐based analyses. Here, we review this research, finding consistent support in numerical models for an antiphase relationship between AMOC strength and dynamic sea level. However, simulations exhibit substantial along‐coast and intermodel differences in the amplitude of AMOC‐associated dynamic sea level variability. Observational analyses focusing on shorter (generally less than decadal) timescales show robust relationships between some components of the North Atlantic large‐scale circulation and coastal sea level variability, but the causal relationships between different observational metrics, AMOC, and sea level are often unclear. We highlight the importance of existing and future research seeking to understand relationships between AMOC and its component currents, the role of ageostrophic processes near the coast, and the interplay of local and remote forcing. Such research will help reconcile the results of different numerical simulations with each other and with observations, inform the physical origins of covariability, and reveal the sensitivity of scaling relationships to forcing, timescale, and model representation. This information will, in turn, provide a more complete characterization of uncertainty in relevant relationships, leading to more robust reconstructions and projections.

Little, Christopher M.↗
DOE OSTI2019

Mooring and Seafloor Pressure End Point Measurements at the Southern Entrance of the Solomon Sea: Subseasonal to Interannual Flow Variability

Variability of the flow across the Solomon Sea's southern entrance was examined using end point subsurface moorings and seafloor pressure sensors, reconstructed velocity profiles based on satellite-derived surface velocity and bottom pressure-derived subsurface velocity, and 1993–2017 proxy volume transport based on satellite altimetry. The reconstructed velocity correctly represents the fluctuating surface flow and subsurface core providing a high-frequency continuous observing system for this sea. The mean equatorward volume transport over 0- to 500-m depth layer is 15.2 Sv (1 Sv ≡ 106 m3/s) during July 2012 to May 2017. The measurements resolve the full spectrum of the volume transport including energetic subseasonal variability that fluctuates by as much as 25 Sv over one week. At low-frequency timescales, the study finds that linear Rossby waves forced by Ekman pumping in the interior of the Pacific influence not only seasonal fluctuations as found by previous studies but also interannual variability. As found previously, the El Niño–Southern Oscillation highly influences interannual volume transport. During the 2015/2016 El Niño, observations show the seasonal cycle to be suppressed from the second half of 2014, prior to the mature phase of the El Niño, to September 2016 along with an increase in across-transect transport. At subseasonal timescales, local Ekman pumping and remote wind stress curl are responsible for a third of the subseasonal variance. Finally, the study highlights the importance of high-frequency observations at the southern entrance of the Solomon Sea and the ability of a linear Rossby model to represent the low-frequency variability of the transport.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

The Role of Chemistry in Fracture Pattern Development and Opportunities to Advance Interpretations of Geological Materials

Abstract Fracture pattern development has been a challenging area of research in the Earth sciences for more than 100 years. Much has been learned about the spatial and temporal complexity inherent to these systems, but severe challenges remain. Future advances will require new approaches. Chemical processes play a larger role in opening‐mode fracture pattern development than has hitherto been appreciated. This review examines relationships between mechanical and geochemical processes that influence the fracture patterns recorded in natural settings. For fractures formed in diagenetic settings (~50 to 200 °C), we review evidence of chemical reactions in fractures and show how a chemical perspective helps solve problems in fracture analysis. We also outline impediments to subsurface pattern measurement and interpretation, assess implications of discoveries in fracture history reconstruction for process‐based models, review models of fracture cementation and chemically assisted fracture growth, and discuss promising paths for future work. To accurately predict the mechanical and fluid flow properties of fracture systems, a processes‐based approach is needed. Progress is possible using observational, experimental, and modeling approaches that view fracture patterns and properties as the result of coupled mechanical and chemical processes. A critical area is reconstructing patterns through time. Such data sets are essential for developing and testing predictive models. Other topics that need work include models of crystal growth and dissolution rates under geological conditions, cement mechanical effects, and subcritical crack propagation. Advances in machine learning and 3‐D imaging present opportunities for a mechanistic understanding of fracture formation and development, enabling prediction of spatial and temporal complexity over geologic timescales. Geophysical research with a chemical perspective is needed to correctly identify and interpret fractures from geophysical measurements during site characterization and monitoring of subsurface engineering activities.

58 GEOSCIENCES↗
DOE OSTI2020

Direct Observation of Shock‐Induced Disordering of Enstatite Below the Melting Temperature

Abstract We report in situ structural measurements of shock‐compressed single crystal orthoenstatite up to 337 ± 55 GPa on the Hugoniot, obtained by coupling ultrafast X‐ray diffraction to laser‐driven shock compression. Shock compression induces a disordering of the crystalline structure evidenced by the appearance of a diffuse X‐ray diffraction signal at nanosecond timescales at 80 ± 13 GPa on the Hugoniot, well below the equilibrium melting pressure (>170 GPa). The formation of bridgmanite and post‐perovskite have been indirectly reported in microsecond‐scale plate‐impact experiments. Therefore, we interpret the high‐pressure disordered state we observed at nanosecond scale as an intermediate structure from which bridgmanite and post‐perovskite crystallize at longer timescales. This evidence of a disordered structure of MgSiO 3 on the Hugoniot indicates that the degree of polymerization of silicates is a key parameter to constrain the actual thermodynamics of shocks in natural environments.

Hernandez, J. ‐A.↗
DOE OSTI2020

Disentangling the Impact of the COVID‐19 Lockdowns on Urban NO 2 From Natural Variability

Abstract TROPOMI satellite data show substantial drops in nitrogen dioxide (NO 2 ) during COVID‐19 physical distancing. To attribute NO 2 changes to NO x emissions changes over short timescales, one must account for meteorology. We find that meteorological patterns were especially favorable for low NO 2 in much of the United States in spring 2020, complicating comparisons with spring 2019. Meteorological variations between years can cause column NO 2 differences of ~15% over monthly timescales. After accounting for solar angle and meteorological considerations, we calculate that NO 2 drops ranged between 9.2% and 43.4% among 20 cities in North America, with a median of 21.6%. Of the studied cities, largest NO 2 drops (>30%) were in San Jose, Los Angeles, and Toronto, and smallest drops (<12%) were in Miami, Minneapolis, and Dallas. These normalized NO 2 changes can be used to highlight locations with greater activity changes and better understand the sources contributing to adverse air quality in each city.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Demons in the North Atlantic: Variability of Deep Ocean Ventilation

Abstract Translation of atmospheric forcing variability into the ocean interior via ocean ventilation is an important aspect of transient climate change. On a seasonal timescale in the subtropics, this translation is mediated by a so‐called “Demon” that prevents access to all except late‐winter mixed‐layer water. Here, we use an eddy‐permitting numerical circulation model to investigate a similar process operating on longer (interannual) timescales in the subpolar North Atlantic. We find that variations in atmospheric forcing are mediated in their translation to the ocean interior, with year‐to‐year changes in the late‐winter mixed layer depth being the critical factor. The signature of persistent strong atmospheric forcing driving deep mixed layers is preferentially ventilated to the interior when the forcing is ceased. Susceptibility to this effect depends on the location and density of subduction—with the rate at which newly ventilated water escapes its region of subduction being the crucial factor.

MacGilchrist, G. A.↗
DOE OSTI2021

Linking Deep and Shallow Convective Mass Fluxes via an Assumed Entrainment Distribution in CAM5‐CLUBB: Parameterization and Simulated Precipitation Variability

Abstract We modify the Zhang‐McFarlane (ZM) deep convection scheme in the Community Atmosphere Model version 5 to couple it with a unified parameterization for boundary‐layer turbulence and shallow convection, that is, Cloud Layers Unified by Binormals (CLUBB). By assuming a lognormal distribution of entrainment rate across the entire moist convective regimes, we link mass fluxes between shallow and deep convection, which are partitioned by the entrainment rate of the shallowest deep convective plume. Hence, a new deep convective closure is established which is coupled to the sub‐grid vertical motion variability in CLUBB. The convection feedback (or memory) effects are also considered to decrease the entrainment spectrum width and enhance the vertical velocity variability that further affect deep convection. Results show that the revised scheme improves the precipitation simulations in terms of the mean state and variability at various timescales, such as the alleviated double‐intertropical convergence zone and more realistic simulations of the seasonal variation of monsoon precipitation over East Asia, Madden‐Julian Oscillation, and precipitation diurnal phase propagations downstream of large terrains. The improvements are still seen in many aspects such as the mean‐state precipitation when turning off the convection feedback impacts in the revised scheme, emphasizing the benefits of using the modified mass‐flux closure. However, the convection feedbacks have considerable effects on the precipitation diurnal cycle simulations over regions with late‐afternoon precipitation peaks. Overall, the revised scheme provides a unified treatment for sub‐grid vertical motions across regimes of boundary‐layer turbulence, shallow convection, and deep convection, leading to better‐simulated precipitation at various timescales.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Assessing Decadal Predictability in an Earth-System Model Using Explainable Neural Networks

We show that explainable neural networks can identify regions of oceanic variability that contribute predictability on decadal timescales in a fully coupled Earth-system model. The neural networks learn to use sea-surface temperature anomalies to predict future continental surface temperature anomalies. We then use a neural-network explainability method called layerwise relevance propagation to infer which oceanic patterns lead to accurate predictions made by the neural networks. In particular, regions within the North Atlantic Ocean and North Pacific Ocean lend the most predictability for surface temperature across continental North America. We apply the proposed methodology to decadal variability, although the concept is generalizable to other timescales of predictability. Furthermore, while our approach focuses on predictable patterns of internal variability within climate models, it should be generalizable to observational data as well. Our study contributes to the growing evidence that explainable neural networks are important tools for advancing geoscientific knowledge.

58 GEOSCIENCES↗
DOE OSTI2022

Increased Variability of Biomass Burning Emissions in CMIP6 Amplifies Hydrologic Cycle in the CESM2 Large Ensemble

Abstract Historical simulations performed for the Coupled Model Intercomparison Project Phase 6 used biomass burning emissions between 1997 and 2014 containing higher spatial and temporal variability compared to emission inventories specified for earlier years, and compared to emissions used in previous (e.g., CMIP5) simulation intercomparisons. Using the Community Earth System Model version 2 Large Ensemble, we show this increased biomass burning emissions variability leads to amplification of the hydrologic cycle poleward of 40°N. Notably, the high variability of biomass burning emissions leads to increased latent heat fluxes, column‐integrated precipitable water, and precipitation. Greater ocean heat uptake, weaker meridional energy transport from the tropics, greater atmospheric shortwave and longwave absorption, and lower relative humidity act to moderate this hydrologic cycle amplification. Our results suggest it is not only the secular changes (on multidecadal timescales) in biomass burning emissions that impact the hydrologic cycle, but also the shorter timescale variability in emissions.

Heyblom, Kyle B.↗
DOE OSTI2022

Quantifying the Effect of Climate Change on Midlatitude Subseasonal Prediction Skill Provided by the Tropics

Abstract Subseasonal timescales (∼2 weeks–2 months) are known for their lack of predictability, however, specific Earth system states known to have a strong influence on these timescales can be harnessed to improve prediction skill (known as “forecasts of opportunity”). As the climate continues warming, it is hypothesized these states may change and consequently, their importance for subseasonal prediction may also be impacted. Here, we examine changes to midlatitude subseasonal prediction skill provided by the tropics under anthropogenic warming using artificial neural networks to quantify skill. The network is tasked to predict the sign of the 500 hPa geopotential height for historical and future time periods in the Community Earth System Model Version 2 ‐ Large Ensemble across the Northern Hemisphere at a 3 week lead using tropical precipitation. We show prediction skill changes substantially in key midlatitude regions and these changes appear linked to changes in seasonal variability with the largest differences in accuracy occurring during forecasts of opportunity.

Mayer, Kirsten J.↗