Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Conditional diffusion models”

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 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Liquid chloroform structure from computer simulation with a full ab initio intermolecular interaction potential

We have calculated the intermolecular interaction energies of the chloroform dimer in 12 orientations using the second-order Møller-Plesset perturbation theory. Single point energies of important geometries were calibrated by the coupled cluster with single and double and perturbative triple excitation method. Dunning's correlation consistent basis sets up to aug-cc-pVQZ have been employed in extrapolating the interaction energies to the complete basis set limit values. With the ab initio potential data we constructed a 5-site force field model for molecular dynamics simulations. We compared the simulation results with recent experiments and obtained quantitative agreements for the detailed atomwise radial distribution functions. Our results were also consistent with previous results using empirical force fields with polarization effects. Moreover, the calculated diffusion coefficients reproduced the experimental data over a wide range of thermodynamic conditions. To the best of our knowledge, this is the first ab initio force field which is capable of competing with existing empirical force fields for liquid chloroform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

THE CIRCUMGALACTIC MEDIUM OF MASSIVE GALAXIES AT z {approx} 3: A TEST FOR STELLAR FEEDBACK, GALACTIC OUTFLOWS, AND COLD STREAMS

We present new results on the kinematics, thermal and ionization state, and spatial distribution of metal-enriched gas in the circumgalactic medium (CGM) of massive galaxies at redshift {approx}3, using the Eris suite of cosmological hydrodynamic ''zoom-in'' simulations. The reference run adopts a blastwave scheme for supernova feedback that produces large-scale galactic outflows, a star formation recipe based on a high gas density threshold, metal-dependent radiative cooling, and a model for the diffusion of metals and thermal energy. The effect of the local UV radiation field is added in post-processing. The CGM (defined as all gas at R > 0.2 R{sub vir} = 10 kpc, where R{sub vir} is the virial radius) contains multiple phases having a wide range of physical conditions, with more than half of its heavy elements locked in a warm-hot component at T > 10{sup 5} K. Synthetic spectra, generated by drawing sightlines through the CGM, produce interstellar absorption-line strengths of Ly{alpha}, C II, C IV, Si II, and Si IV as a function of the galactocentric impact parameter (scaled to the virial radius) that are in broad agreement with those observed at high redshift by Steidel et al. The covering factor of absorbing material declines less rapidly with impact parameter for Ly{alpha} and C IV compared to C II, Si IV, and Si II, with Ly{alpha} remaining strong (W{sub Ly{alpha}} > 300 mA) to {approx}> 5 R{sub vir} = 250 kpc. Only about one third of all the gas within R{sub vir} is outflowing. The fraction of sightlines within one virial radius that intercept optically thick, N{sub H{sub I}}>10{sup 17.2} cm{sup -2} material is 27%, in agreement with recent observations by Rudie et al. Such optically thick absorption is shown to trace inflowing ''cold'' streams that penetrate deep inside the virial radius. The streams, enriched to metallicities above 0.01 solar by previous episodes of star formation in the main host and in nearby dwarfs, are the origin of strong (N{sub C{sub II}}>10{sup 13} cm{sup -2}) C II absorption with a covering factor of 22% within R{sub vir} and 10% within 2 R{sub vir}. Galactic outflows do not cause any substantial suppression of the cold accretion mode. The central galaxy is surrounded by a large O VI halo, with a typical column density N{sub O{sub VI}} {approx}> 10{sup 14} cm{sup -2} and a near unity covering factor maintained all the way out to 150 kpc. This matches the trends recently observed in star-forming galaxies at low redshift by Tumlinson et al. Our zoom-in simulations of this single system appear then to reproduce quantitatively the complex baryonic processes that determine the exchange of matter, energy, and metals between galaxies and their surroundings.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

Fundamental Study of Disposition and Release of Methane in a Shale Gas Reservoir

The recent boom in shale gas production through hydrofracturing has reshaped the energy production landscape in the United States. Wellbore production rates vary greatly among the wells within a single field and decline rapidly with time, thus bring up a serious concern with the sustainability of shale gas production. Shale gas production starts with creating a fracture network by injecting a pressurized fluid in a wellbore. The induced fractures are then held open by proppant particles. During production, gas releases from the mudstone matrix, migrates to nearby fractures, and ultimately reaches a production wellbore. Given the relatively high permeability of the induced fractures, gas release and migration in low-permeability shale matrix is likely to be a limiting step for long-term wellbore production. Therefore, a clear understanding of the underlying mechanisms of methane disposition and release in shale matrix is crucial for the development of new technologies to maximize gas production and recovery. Shale is a natural nanocomposite material with distinct characteristics of nanometer-scale pore sizes, extremely low permeability, high clay contents, significant amounts of organic carbon, and large spatial heterogeneities. Our work has shown that nanopore confinement plays an important role in methane disposition and release in shale matrix. Using molecular simulations, we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~ 30 - 47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. The long-term production decline appears controlled by the second stage of gas release. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3 - 35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. We have successfully established experimental capabilities for measuring gas sorption and desorption on shale and model materials under a wide range of physical and chemical conditions. Both low and high pressure measurements show significant sorption of CH 4 and CO 2 onto clays, implying that methane adsorbed on clay minerals could contribute a significant portion of gas-in-place in an unconventional reservoir. We have also studied the potential impact of the interaction of shale with hydrofracking fluid on gas sorption. We have found that the CH 4 -CO 2 sorption capacity for the reacted sample is systematically lower (by a factor of ~2) than that for the unreacted (raw) sample. This difference in sorption capacity may result from a mineralogical or surface chemistry change of the shale sample induced by fluid-rock interaction. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2022

A Phase-Field Model for In-Space Manufacturing of Binary Alloys

The integrity of the final printed components is mostly dictated by the adhesion between the particles and phases that form upon solidification, which is a major problem in printing metallic parts using available In-Space Manufacturing (ISM) technologies based on the Fused Deposition Modeling (FDM) methodology. Understanding the melting/solidification process helps increase particle adherence and allows to produce components with greater mechanical integrity. We developed a phase-field model of solidification for binary alloys. The phase-field approach is unique in capturing the microstructure with computationally tractable costs. The developed phase-field model of solidification of binary alloys satisfies the stability conditions at all temperatures. The suggested model is tuned for Ni-Cu alloy feedstocks. We derived the Ginzburg-Landau equations governing the phase transformation kinetics and solved them analytically for the dilute solution. We calculated the concentration profile as a function of interface velocity for a one-dimensional steady-state diffuse interface neglecting elasticity and obtained the partition coefficient, k, as a function of interface velocity. Numerical simulations for the diluted solution are used to study the interface velocity as a function of undercooling for the classic sharp interface model, partitionless solidification, and thin interface.

36 MATERIALS SCIENCE↗
NASA NTRS1972

Radiative transfer effects on reflected shock waves. II - Absorbing gas.

Radiative cooling effects behind a reflected shock wave are calculated for an absorbing-emitting gas by means of an expansion procedure in the small density ratio across the shock front. For a gray gas shock layer with an optical thickness of order unity or less the absorption integral is simplified by use of the local temperature approximation, whereas for larger optical thicknesses a Rosseland diffusion type of solution is matched with the local temperature approximation solution. The calculations show that the shock wave will attenuate at first and then accelerate to a constant velocity. Under appropriate conditions the gas enthalpy near the wall may increase at intermediate times before ultimately decreasing to zero. A two-band absorption model yields end-wall radiant-heat fluxes which agree well with available shock-tube measurements.

Su, F. Y.↗
DOE OSTI2019

Fuel Matrix Degradation Model Development Update: Alloy Corrosion Rates and Hydrogen Generation

This work is being performed as part of the DOE NE Spent Fuel and Waste Science and Technology Campaign, Argillite and Crystalline Rock R&D work packages: SF-19AN01030101 and SF-19AN01030201. This document meets the milestone M4SF-19AN010301013 for Argillite R&D and the milestone M4SF-19AN010302013 for Crystalline R&D. The fuel matrix degradation (FMD) model calculates the degradation rate of spent UO2 fuel based on fundamental electrochemical theory and thermodynamics. The model provides the quantitative basis for radionuclide source term predictions in the generic disposal system analysis (GDSA) performance assessment (PA) model. The FMD model has been implemented in a manner that facilitates its integration with the GDSA-PA code and a preliminary, integrated FMD-GDSA model has been successfully tested (Jerden et al., 2017). The specific focus of on-going work is to accurately and quantitatively represent the generation of H2 in a breached waste package and its effect on the spent fuel degradation rate so that this key process can be accurately represented in PA models. It has been shown experimentally that millimolar concentrations of dissolved H2 in contact with spent fuel will inhibit oxidative dissolution and decrease the fuel degradation rates by as much as three orders of magnitude (e.g., Röllin et al., 2001, Ollila, 2008). This will lead to a significant decrease in the radionuclide source term values used in repository PA models. Sensitivity studies using the FMD model have shown that the dissolved H2 concentration is the dominant environmental variable affecting the UO2 spent fuel dissolution rate as long as a source of H2 persists in the breached waste package (Jerden et al., 2015). Therefore, on-going experimental and modeling efforts focus on H2 production, accumulation and interfacial reactions within a breached waste package. The anoxic corrosion of metallic engineering materials within a breached waste package will be the main source of H2 in crystalline and argillite rock repository systems. The most important H2-producing alloys present within a waste package include stainless steel, carbon steel, and aluminum alloys and the Zircaloy fuel cladding. A steel corrosion module was added to the FMD model to account for these H2 sources and couple the H2 generation rate with fuel degradation processes (Jerden et al., 2017). As discussed below, there is a need for experimental data from electrochemical corrosion tests to quantify the H2 generation rates due to the corrosion of these waste package alloys as a function of key environmental variables (Eh, pH, groundwater chemistry). This report presents results from series of electrochemical corrosion tests with materials present in waste packages that provide information needed to parameterize and validate the FMD model. The alloys tested include 316L stainless steel (316SS), AISI 4320 carbon steel (C-steel) and Zircaloy-4 fuel cladding (unirradiated). Potentiodynamic polarization and potentiostatic polarization tests were performed in buffer solutions at pH 4, 7 and 10 with NaCl concentrations of 0, 4 and 100 millimolar (mM). The potentiostatic tests were performed at voltages varying from 0.5 volts down to -0.66 volts, vs the standard hydrogen electrode (SHE), and all tests were performed at laboratory ambient temperatures (~22 °C). The corrosion rates measured during the electrochemical tests were used as direct input to a new FMD/in-package chemistry model that is being developed to provide accurate long-term spent fuel degradation rates as chemical conditions (Eh, pH, speciation) evolve within a breached waste package. This new model was developed by coupling the FMD model with the reactive transport code X1t, which is a module within the Geochemist’s Workbench (GWB) reaction path modeling code (Jerden et al., 2019). The reactive transport model consists of a 1D domain discretized with 21 reaction diffusion cells and includes a single waste packag

Jerden, James↗
DOE OSTI2023

Numerical investigation and experimental validation of water condensation in the gas diffusion layer with different properties

Liquid water in porous media hinders the transport of reactant to catalyst layer, where the electrochemical reactions occur, which in turn, reduces performance and lifetime of a proton exchange membrane fuel cell (PEMFC). In this study, two types of gas diffusion layer (GDL) materials are used to study the two-phase saturation distribution in a PEMFC. The correlations between the effective and anisotropic transport properties and porosity of the two GDLs are solved by the pore scale model. In addition, the anisotropic liquid water permeability and the relationship between saturation pressure and capillary pressure is determined by using the Lattice-Boltzmann method. Fuel cell performance as well as liquid water distribution in the GDL using neutron radiography are obtained for validation. Under wet conditions, the cell with Freudenberg GDL performs better than that using Toray GDL, especially at high current densities. The results of the two-phase model simulation show that the peak water saturation for Toray GDL occurs in the catalyst layer and can reach 40%, while the peak water saturation for Freudenberg GDL occurs inside the GDL directly under the ribs and only reaches 25% saturation. The combined results provide key insights to enable high power density operation of a PEMFC through GDL material optimization.

42 ENGINEERING↗
DOE OSTI2018

Ecosystem fluxes of carbonyl sulfide in an old-growth forest: temporal dynamics and responses to diffuse radiation and heat waves

Carbonyl sulfide (OCS) has recently emerged as a tracer for terrestrial carbon uptake. While physiological studies relating OCS fluxes to leaf stomatal dynamics have been established at leaf and branch scales and incorporated into global carbon cycle models, the quantity of data from ecosystem-scale field studies remains limited. In this study, we employ established theoretical relationships to infer ecosystem-scale plant OCS uptake from mixing ratio measurements. OCS fluxes showed a pronounced diurnal cycle, with maximum uptake at midday. OCS uptake was found to scale within dependent measurements of CO 2 fluxes over a 60 m tall old-growth forest in the Pacific Northwest of the US (45°49'13.76" N,121 °57'06.88" W) at daily and monthly timescales under mid–high light conditions across the growing season in 2015. OCS fluxes were strongly influenced by the fraction of down welling diffuse light. Finally, we examine the effect of sequential heat waves on fluxes of OCS, CO 2 , and H 2 O. Our results bolster previous evidence that ecosystem OCS uptake is strongly related to stomatal dynamics,and measuring this gas improves constraints on estimating photosynthetic rates at the ecosystem scale.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1992

The diffuse interstellar cloud toward HD 179406 (20 Aquilae)

An analysis of the diffuse interstellar cloud complex in front of HD 179406 (20 Aql) is presented. Along this sight line, multispectral absortion- and emission-line studies have uncovered at least three distinct velocity components due to individual clouds. A dominant velocity component is seen in both the absorption and emission-line data sets at 3 +/- 1 km/s. It is argued that the cloud associated with this velocity component is responsible for most of the atomic and all of the molecular gas in front of 20 Aql. The present chemical and physical analysis of the cloud combines the diagnostic tools of radio emission-line data with those of UV and optical absorption data. Using non-LTE models to synthesize the observed absorption profiles, (C-12)O and (C-13)O column densities along this line of sight are determined. The (C-12)O/(C-13)O abundance ratio was found to be 50 +/- 15, similar to that found by Wannier et al. toward Zeta Oph. The physical conditions of the cloud have been investigated using ultraviolet absorption lines. Measurements indicate that the dominant absorption cloud has a gas pressure similar to that found in the local diffuse molecular cloud in Ophiuchus with nT = 20,000/cu cm K.

Hanson, Margaret M.↗
NASA NTRS1999

A Validated All-Pressure Fluid Drop Model and Lewis Number Effects for a Binary Mixture

The differences between subcritical liquid drop and supercritical fluid drop behavior are discussed. Under subcritical, evaporative high emission rate conditions, a film layer is present in the inner part of the drop surface which contributes to the unique determination of the boundary conditions; it is this film layer which contributes to the solution's convective-diffusive character. In contrast, under supercritical condition as the boundary conditions contain a degree of arbitrariness due to the absence of a surface, and the solution has then a purely diffusive character. Results from simulations of a free fluid drop under no-gravity conditions are compared to microgravity experimental data from suspended, large drop experiments at high, low and intermediary temperatures and in a range of pressures encompassing the sub-and supercritical regime. Despite the difference between the conditions of the simulations and experiments (suspension vs. free floating), the time rate of variation of the drop diameter square is remarkably well predicted in the linear curve regime. The drop diameter is determined in the simulations from the location of the maximum density gradient, and agrees well with the data. It is also shown that the classical calculation of the Lewis number gives qualitatively erroneous results at supercritical conditions, but that an effective Lewis number previously defined gives qualitatively correct estimates of the length scales for heat and mass transfer at all pressures.

Harstad, K.↗
DOE OSTI2021

Experimental and computational study of the microporous layer and hydrophobic treatment in the gas diffusion layer of a proton exchange membrane fuel cell

Enabling fuel cell operation at high current density is critical for developing competitive alternative power system to replace internal combustion engine. However, liquid water management continues to be a challenge for high humidity or high current density operation. Water condensation in the porous media hinders efficient oxygen transport to the catalyst layer, which in turns, reduces fuel cell performance. To improve water management capability, the gas diffusion layer is often impregnated with Polytetrafluoroethylene (PTFE) and coated with a thin microporous layer, which have shown to improve fuel cell performance, especially under wet conditions. However, the fundamental mechanism that drives the performance enhancement is still not well understood. In this work, the effects of PTFE impregnation and MPL were studied using both experimental and computational techniques. Both limiting current and polarization tests under dry and wet operating condition are conducted to study the oxygen transport resistance and fuel cell performance. In addition, a 2-D, two-phase, multi-physics PEMFC model is developed to simulate performance and gain a fundamental understanding of local water saturation and oxygen concentration. The combined results show that 5 wt% PTFE impregnation with MPL significantly enhances liquid water management, which enables higher current density operation of a fuel cell.

25 ENERGY STORAGE↗
DOE OSTI2018

27 Al Pulsed Field Gradient, Diffusion–NMR Spectroscopy of Solvation Dynamics and Ion Pairing in Alkaline Aluminate Solutions

Here, pulsed field gradient nuclear magnetic resonance (PFG-NMR) measurements were successfully applied to the 27 Al (I = 5/2) nucleus in concentrated electrolytes to investigate the diffusion of aluminate ions [Al(OH) 4 – ] in simulant high-level nuclear waste (3 M NaOH) between 25 and 85 °C. The temperature-dependent diffusion coefficients obtained from 1 H, 23 Na, and 27 Al PFG-NMR were well fit by a Vogel–Fulcher–Tammann model and a power law equation. Comparison of 27 Al diffusion coefficients of 0.1 M Al(OH) 4 – in ~3 M MOH (where M = Na + , K + , (CH 3 ) 4 N + ) at room temperature varied in agreement with the expected changes in solution viscosity via Stokes–Einstein relationship, confirming that the dominant Al species at these conditions are Al(OH) 4 – monomers. This 27 Al PFG-NMR study extends an established methodology to a previously unexplored nucleus enabling this experimental technique to be leverage for exploring ion transport, speciation, and solution structure in concentrated electrolytes.

Diffusion↗
DOE OSTI2018

Concussion, microvascular injury, and early tauopathy in young athletes after impact head injury and an impact concussion mouse model

The mechanisms underpinning concussion, traumatic brain injury, and chronic traumatic encephalopathy, and the relationships between these disorders, are poorly understood. We examined post-mortem brains from teenage athletes in the acute-subacute period after mild closed-head impact injury and found astrocytosis, myelinated axonopathy, microvascular injury, perivascular neuroinflammation, and phosphorylated tau protein pathology. To investigate causal mechanisms, we developed a mouse model of lateral closed-head impact injury that uses momentum transfer to induce traumatic head acceleration. Unanaesthetized mice subjected to unilateral impact exhibited abrupt onset, transient course, and rapid resolution of a concussion-like syndrome characterized by altered arousal, contralateral hemiparesis, truncal ataxia, locomotor and balance impairments, and neurobehavioural deficits. Experimental impact injury was associated with axonopathy, blood–brain barrier disruption, astrocytosis, microgliosis (with activation of triggering receptor expressed on myeloid cells, TREM2), monocyte infiltration, and phosphorylated tauopathy in cerebral cortex ipsilateral and subjacent to impact. Phosphorylated tauopathy was detected in ipsilateral axons by 24 h, bilateral axons and soma by 2 weeks, and distant cortex bilaterally at 5.5 months post-injury. Impact pathologies co-localized with serum albumin extravasation in the brain that was diagnostically detectable in living mice by dynamic contrast-enhanced MRI. These pathologies were also accompanied by early, persistent, and bilateral impairment in axonal conduction velocity in the hippocampus and defective long-term potentiation of synaptic neurotransmission in the medial prefrontal cortex, brain regions distant from acute brain injury. Surprisingly, acute neurobehavioural deficits at the time of injury did not correlate with blood–brain barrier disruption, microgliosis, neuroinflammation, phosphorylated tauopathy, or electrophysiological dysfunction. Furthermore, concussion-like deficits were observed after impact injury, but not after blast exposure under experimental conditions matched for head kinematics. Computational modelling showed that impact injury generated focal point loading on the head and seven-fold greater peak shear stress in the brain compared to blast exposure. Moreover, intracerebral shear stress peaked before onset of gross head motion. By comparison, blast induced distributed force loading on the head and diffuse, lower magnitude shear stress in the brain. We conclude that force loading mechanics at the time of injury shape acute neurobehavioural responses, structural brain damage, and neuropathological sequelae triggered by neurotrauma. These results indicate that closed-head impact injuries, independent of concussive signs, can induce traumatic brain injury as well as early pathologies and functional sequelae associated with chronic traumatic encephalopathy. These results also shed light on the origins of concussion and relationship to traumatic brain injury and its aftermath.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Theoretical and experimental investigation of the equation of state of boron plasmas

We report a theoretical equation of state (EOS) table for boron across a wide range of temperatures (5.1 10 4 {5.2 10 8 K) and densities (0.25{49 g/cm 3 ), and experimental shock Hugoniot data at unprecedented high pressures (5608 118 GPa). The calculations are performed with first-principles methods combining path integral Monte Carlo (PIMC) at high temperatures and density functional theory molecular dynamics (DFT-MD) methods at lower temperatures. PIMC and DFT-MD cross-validate each other by providing coherent EOS (difference <1.5 Hartree/boron in energy and <5% in pressure) at 5.1 10 5 K. The Hugoniot measurement is conducted at the National Ignition Facility using a planar shock platform. The pressure-density relation found in our shock experiment is on top of the shock Hugoniot profile predicted with our first-principles EOS and a semi-empirical EOS table (LEOS 50). We investigate the self diffusivity and the effect of thermal and pressure-driven ionization on the EOS and shock compression behavior in high pressure and temperature conditions. We also study the sensitivity of a polar direct-drive exploding pusher platform to pressure variations based on applying pressure multipliers to LEOS 50 and by utilizing a new EOS model based on our ab initio simulations via 1D radiation-hydrodynamic calculations. The results are valuable for future theoretical and experimental studies and engineering design in high energy density research.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Utilizing Highly Scattered Light for Intelligence through Aerosols

This communication is the final report for the project Utilizing Highly Scattered Light for Intelligence through Aerosols funded by the Laboratory Directed Research and Development (LDRD) program at Sandia National Laboratories and lasting six months in 2019. Aerosols like fog reduce visibility and cause down-time that for critical systems or operations are unacceptable. Information is lost due to the random scattering and absorption of light by tiny particles. Computational diffuse optical imaging methods show promise for interpreting the light transmitted through fog, enabling sensing and imaging to improve situational awareness at depths 10 times greater than current methods. Developing this capability first requires verification and validation of diffusion models of light propagation in fog. For this reason, analytical models were developed and compared to experimental data captured at the Sandia National Laboratory Fog Chamber facility. A methodology was developed to incorporate the propagation of scattered light through the imaging optics to a pixel array. The diffusion approximation to the radiative transfer equation was found to predict light propagation in fog under the appropriate conditions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Microstructure-Based Degradation Modeling in Solid Oxide Cells

The presentation is intended for a graduate class in Georgia Southern University taught by Dr. Hayri Sezer on electrochemistry, SOFC and Li ion battery. It summaries NETL's recent works on microstructure-based modeling of degradation in solid oxide cells. It covers the degradation mechanism of Ni coarsening, Ni migration and the build-up of oxygen partial pressure inside the electrolyte. The phase-field models developed for Ni coarsening and migration are reviewed and the results are compared to experiments in literature to examine different diffusion mechanisms (Ni self-diffusion, Ni(OH)2 diffusion in pores and Ni(OH) surface diffusion) and driving forces (Ni(OH)x concentration and Ni-YSZ contact angle change). It also demonstrates the developed model for oxygen partial pressure and shows that the predicted oxygen partial pressure can explain the Ni oxidation in the hydrogen electrode and crack growth on the electrolyte-oxygen electrode interface under certain operating conditions.

nickel coarsening↗
DOE OSTI2016

Kinetics and mechanisms of the acid-base reaction between NH{sub 3} and HCOOH in interstellar ice analogs

Interstellar complex organic molecules are commonly observed during star formation, and are proposed to form through radical chemistry in icy grain mantles. Reactions between ions and neutral molecules in ices may provide an alternative cold channel to complexity, as ion-neutral reactions are thought to have low or even no-energy barriers. Here we present a study of the kinetics and mechanisms of a potential ion-generating, acid-base reaction between NH{sub 3} and HCOOH to form the salt NH{sub 4}{sup +}HCOO{sup −}. We observe salt growth at temperatures as low as 15 K, indicating that this reaction is feasible in cold environments. The kinetics of salt growth are best fit by a two-step model involving a slow “pre-reaction” step followed by a fast reaction step. The reaction energy barrier is determined to be 70 ± 30 K with a pre-exponential factor 1.4 ± 0.4 × 10{sup −3} s{sup −1}. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and orientation of reactant molecules. For a diffusion-limited case, the pre-reaction barrier is 770 ± 110 K with a pre-exponential factor of ∼7.6 × 10{sup −3} s{sup −1}. Acid-base chemistry of common ice constituents is thus a potential cold pathway to generating ions in interstellar ices.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Probabilistic estimation of depth-resolved profiles of soil thermal diffusivity from temperature time series

Abstract. Improving the quantification of soil thermal and physical properties is key to achieving a better understanding and prediction of soil hydro-biogeochemical processes and their responses to changes in atmospheric forcing. Obtaining such information at numerous locations and/or over time with conventional soil sampling is challenging. The increasing availability of low-cost, vertically resolved temperature sensor arrays offers promise for improving the estimation of soil thermal properties from temperature time series, and the possible indirect estimation of physical properties. Still, the reliability and limitations of such an approach need to be assessed. In the present study, we develop a parameter estimation approach based on a combination of thermal modeling, sliding time windows, Bayesian inference, and Markov chain Monte Carlo simulation to estimate thermal diffusivity and its uncertainty over time, at numerous locations and at an unprecedented vertical spatial resolution (i.e., down to 5 to 10 cm vertical resolution) from soil temperature time series. We provide the necessary framework to assess under which environmental conditions (soil temperature gradient, fluctuations, and trend), temperature sensor characteristics (bias and level of noise), and deployment geometries (sensor number and position) soil thermal diffusivity can be reliably inferred. We validate the method with synthetic experiments and field studies. The synthetic experiments show that in the presence of median diurnal fluctuations ≥ 1.5 ∘C at 5 cm below the ground surface, temperature gradients > 2 ∘C m−1, and a sliding time window of at least 4 d the proposed method provides reliable depth-resolved thermal diffusivity estimates with percentage errors ≤ 10 % and posterior relative standard deviations ≤ 5 % up to 1 m depth. Reliable thermal diffusivity under such environmental conditions also requires temperature sensors to be spaced precisely (with accuracy to a few millimeters), with a level of noise ≤ 0.02 ∘C, and with a bias defined by a standard deviation ≤ 0.01 ∘C. Finally, the application of the developed approach to field data indicates significant repeatability in results and similarity with independent measurements, as well as promise in using a sliding time window to estimate temporal changes in soil thermal diffusivity, as needed to potentially capture changes in bulk density or water content.

54 ENVIRONMENTAL SCIENCES↗