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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.

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At least 1,603 records · Page 89
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Modeling the Environment-Dependent Kinetics of Oxygen Reduction Reaction – a Continuum Model for Electric Double Layer

Here, for proton-exchange-membrane fuel cells (PEMFCs) to achieve broad commercialization, improved energy-conversion efficiency with minimal Pt-based electrocatalyst is required. Because the sluggish rate of oxygen reduction reaction (ORR) limits the efficiency of PEMFCs, the efficiency improvement requires a better understanding of ORR kinetics and mechanism to design better catalyst. To understand the ORR mechanism, theoretical and experimental analyses have been conducted. While previous studies reasonably explained the catalyst-dependent activity on single crystal catalysts in 0.1 M perchloric acid solution, the explicit effect of electrolyte and related microenvironments is not thoroughly understood. The change in the electrolyte alters the electric-double-layer (EDL) structure and thus the local microenvironment at the electrode/electrolyte interface. Thus, the structure of the EDL should be carefully analyzed to uncover the electrolyte-dependent reaction kinetics. In this talk, we propose a multiscale continuum model to predict the EDL structure and examine the effect of perchloric acid concentration on ORR activity on Pt (111). The model includes Density Potential Functional Theory (DPFT) for electron density and Modified Poisson Boltzmann equation for species’ density and electric potential. Also, the interaction between adsorbents and electric field is taken into account by minimizing the grand potential. After model validation with experimentally measured double-layer capacity data as a function of applied potential and concentration, the effect of the perchloric acid concentration (0.02 M – 0.2 M) on ORR activity is analyzed and discussed. It is shown that the model reproduces the specific activity obtained in the experiments when assuming the oxygen adsorption is limiting the rate, which can be attributed to the large energetic barrier for solvent reorganization. Then, extension of the model to PEMFC ionomer electrolytes will be introduced. Overall, the model framework and findings provide insights into the ORR mechanism and guidance on how to tailor catalyst materials for increased PEMFC performance.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS2010

Pathway Model of the Kinetics of the TGFbeta Antagonist Smad7 and Cross-Talk with the ATM and WNT Pathways

Signal transduction controls cellular and tissue responses to radiation. Transforming growth factor beta (TGFbeta) is an important regulator of cell growth and differentiation and tissue homeostasis, and is often dis-regulated in tumor formation. Mathematical models of signal transduction pathways can be used to elucidate how signal transduction varies with radiation quality, and dose and dose-rate. Furthermore, modeling of tissue specific responses can be considered through mechanistic based modeling. We developed a mathematical model of the negative feedback regulation by Smad7 in TGFbeta-Smad signaling and are exploring possible connections to the WNT/beta -catenin, and ATM/ATF2 signaling pathways. A pathway model of TGFbeta-Smad signaling that includes Smad7 kinetics based on data in the scientific literature is described. Kinetic terms included are TGFbeta/Smad transcriptional regulation of Smad7 through the Smad3-Smad4 complex, Smad7-Smurf1 translocation from nucleus to cytoplasm, and Smad7 negative feedback regulation of the TGFO receptor through direct binding to the TGFO receptor complex. The negative feedback controls operating in this pathway suggests non-linear responses in signal transduction, which are described mathematically. We then explored possibilities for cross-talk mediated by Smad7 between DNA damage responses mediated by ATM, and with the WNT pathway and consider the design of experiments to test model driven hypothesis. Numerical comparisons of the mathematical model to experiments and representative predictions are described.

Carra, Claudio↗
NASA NTRS1976

Atmospheric flow over two-dimensional bluff surface obstructions

The phenomenon of atmospheric flow over a two-dimensional surface obstruction, such as a building (modeled as a rectangular block, a fence or a forward-facing step), is analyzed by three methods: (1) an inviscid free streamline approach, (2) a turbulent boundary layer approach using an eddy viscosity turbulence model and a horizontal pressure gradient determined by the inviscid model, and (3) an approach using the full Navier-Stokes equations with three turbulence models; i.e., an eddy viscosity model, a turbulence kinetic-energy model and a two-equation model with an additional transport equation for the turbulence length scale. A comparison of the performance of the different turbulence models is given, indicating that only the two-equation model adequately accounts for the convective character of turbulence. Turbulence flow property predictions obtained from the turbulence kinetic-energy model with prescribed length scale are only insignificantly better than those obtained from the eddy viscosity model. A parametric study includes the effects of the variation of the characteristics parameters of the assumed logarithmic approach velocity profile. For the case of the forward-facing step, it is shown that in the downstream flow region an increase of the surface roughness gives rise to higher turbulence levels in the shear layer originating from the step corner.

Bitte, J.↗
DOE OSTI2021

Multiscale CFD simulation of biomass fast pyrolysis with a machine learning derived intra-particle model and detailed pyrolysis kinetics

Coupling particle and reactor scale models is as essential as reactor fluid dynamics and particle motion for accurate Computational Fluid Dynamic (CFD) simulations of biomass fast pyrolysis reactors due to intraparticle heat transfer and chemical reactions controlling conversion time and product distributions. Direct online coupling of a particle model with a reactor model is computationally expensive, while offline coupling is case-dependent. In this research, solutions from a series of particle pyrolysis simulations were regressed with Artificial Neural Network (ANN). Furthermoer, this machine learning-derived model predicted the same temperature and conversion profiles compared with particle resolved simulation while the isothermal approach overpredicted the temperature by 130 K and underpredicted the conversion time by 30 s. The ANN model was then integrated into CFD simulations of fluidized bed biomass fast pyrolysis with varied feedstocks via coupling PyTorch and MFiX. The averaged error of simulation predicted bio-oil yields with four feedstocks is 6.4%. This multi-scale approach provides an efficient tool for the coupled particle and reactor scale simulations of biomass pyrolysis.

09 BIOMASS FUELS↗
DOE OSTI2019

Comprehensive evaluation and parametric sensitivity of interatomic potential models for diffusion kinetics of Cr 2 O 3 in molecular dynamics

While molecular dynamics (MD) has proven to be a promising approach to investigate the diffusion properties, the grand challenge resides in evaluating potential model parameters to accurately replicate experimentally measured properties. The Buckingham potential model with Columbic interaction is widely employed in MD simulations of chromia (Cr 2 O 3 ) systems, as it allows for reasonable computational cost and accuracy. However, considering the well-known limitation of classical potential models in simultaneous reproduction of various physical phenomena, further comprehensive evaluation of the potential is required for calculation of diffusion properties. In this study, we benchmark the performance of three different Buckingham models with the experimental data by calculating structural, thermodynamic, and mechanical properties of defect-free Cr 2 O 3 , and diffusion properties of Cr 2 O 3 with vacancy defects. Available Buckingham models display limited accuracies, consolidating the necessity of retraining the potential parameters for all properties impacting the diffusion dynamics. Oversimplification in parameterization procedures is suggested to impede the universal performance in property reproduction. Furthermore, this research also demonstrates effective guidelines for choosing a proper parameter set of current Buckingham potential for MD simulation with Cr 2 O 3 depending on properties and for potential reparameterization.

36 MATERIALS SCIENCE↗
DOE OSTI2019

A thermal model to describe kinetic dispersion in rubber nanocomposites: The effect of mixing time on dispersion

Nanocomposites can be produced by a variety of processes. A common approach used in industry is to mix a viscous polymer such as an elastomer compound, with nanofillers in a Brabender mixer or in a calendar. Dispersion has been quantified using a mixing index, DR, that is based on micrographs of reinforced elastomers on the micron-scale. A recently observed technique based on x-ray scattering allows for an alternative nano-scale description of dispersion based on a thermal-dispersion model where an analogy is made between temperature for thermal dispersion and nanocomposite processing conditions such as mixing time, mixing geometry, and viscosity for kinetic dispersion. In this paper the impact of mixing time on dispersion is explored taking advantage of the van der Waals equation to describe excluded volume and interaction energy in the dispersion. It is found that the thermal-dispersion analogy is well behaved and can determine the wetting time for nano-scale incorporation of elastomer into filler. The nano-scale excluded volume depends only on the filler type and does not seem to be sensitive to bound rubber. The pseudo-interaction energy is strongly dependent on viscosity and polymer chemistry. The thermal-dispersion model offers a novel approach to understanding kinetic dispersion in nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Modeling the Free Carrier Recombination Kinetics in PTB7:PCBM Organic Photovoltaics

Currently the exact recombination mechanism of free carriers in organic photovoltaic (OPV) devices is poorly understood. Often a reduced Langevin model is used to describe the decay behavior of electrons and holes. Here we propose a novel, simple kinetic model that accurately describes the decay behavior of free carriers in the PTB7:PCBM organic photovoltaic blend. In order to accurately describe the recombination behavior of free carriers as measured by time-resolved microwave conductivity (TRMC), this model needs to only take into account free and trapped holes in the polymer, and free electrons in the fullerene. The model is consistent for different PTB7:PCBM blend ratios and spans a light intensity range of over 3 orders of magnitude. Furthermore, the model demonstrates that dark carriers exist in the polymer and interact with photoinduced charge carriers, and that the trapping and detrapping rates of the holes are of high importance to the overall carrier lifetime.

14 SOLAR ENERGY↗
DOE OSTI2018

Experimental and kinetic analysis for particle scale modeling of a CuO-Fe 2 O 3 -Al 2 O 3 oxygen carrier during reduction with H 2 in chemical looping combustion applications [Experimental and kinetic analysis for particle scale modeling of a CuO-Fe 2 O 3 -Al 2 O 3 oxygen carrier during reduction with CO in chemical looping combustion applications]

A kinetic analysis of the H 2 reduction of a CuO-Fe 2 O 3 -Al 2 O 3 oxygen carrier in gas phase fueled Chemical Looping Combustion of synthesis gas was utilized to derive particle scale representation. An experimentally driven study was carried out to provide an array of operational data sets for kinetic modelling approaches. The impact of key operational variables on the kinetics of the novel oxygen carrier were examined, with emphasis on the application of reliable phenomena driven particle scale models to describe the reduction behavior. Due to the novel nature of the material, a series of experimental studies were carried out to provide a fundamental understanding of how the material changed as oxygen was depleted from the structure due to reduction with H 2 . This include quantification of the complex mixed metal oxide phase and changes due to lattice oxygen depletion. It was found that H 2 reduction occurs in a multistep process where CuFeAlO 4 → Cu 0+ + FeAl 2 O 4 → Cu 0+ + Fe 0+ + Al 2 O 3 as oxygen is depleted from the structure. This multistep process was successfully emulated through the use of a two interface Grainy pellet model in which reaction (kinetic) control was the main rate limiting step. This is validated through the examination of other potential rate limiting resistances. In conclusion, the model emulates changes in key operation variables with good accuracy.

42 ENGINEERING↗
DOE OSTI2025

Mechanistic insights into nitrogen activation on atomic Ru clusters in self-pillared pentasil using operando atomistic models and experimental kinetics

Alternative catalysts to the industrial Haber Bosch process have been of significant interest in the field of heterogeneous catalysis, yet realizing ammonia synthesis under mild conditions (e.g., 300 °C and 10 bar) is challenging due to the low per-pass conversion. One strategy is to promote the associative ammonia synthesis mechanism which eschews direct N-N bond cleavage. Here, in this work, we use self-pillared pentasil, a self-pillared hierarchical zeolite built by thin MFI zeolite nanosheets, as a support for subnanometric Ru clusters to synthesize ammonia. We show that Ru remains well-dispersed during reaction and further demonstrate that ammonia synthesis rates are higher than Cs-Ru/MgO. Reaction kinetics show a positive order in H 2 providing evidence for the associative mechanism, which then becomes negative in H 2 if Ru is allowed to aggregate into nanoparticles. Operando Density Functional Theory models for Ru speciation in SPP, free energy diagrams, and microkinetic modeling were then applied to develop a reaction mechanism that involves sequential hydrogenation of N 2 from metallic Ru clusters. For this hydrogenation to occur, there are site requirements for N 2 to adopt a bridge-bound configuration that facilitates sequential hydrogenation on single sites and metal clusters. These site requirements in turn inform the design of improved zeolite-supported ammonia synthesis catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Potential improvements in brain dose estimates for internal emitters

Background: Element-specific biokinetic models are used to reconstruct doses to systemic tissues from internal emitters. Typically, a systemic model for a radionuclide explicitly depicts only its dominant repositories. Remaining tissues and fluids are aggregated into a pool called Other tissue in which the radionuclide is assumed to be uniformly distributed. In the systemic biokinetic models used in radiation protection, the brain usually is addressed as an implicit mass fraction of Other tissue rather than an explicitly depicted repository. Additionally, due to increasing interest in radiation effects on the brain, efforts are underway to improve brain dosimetry for internal radiation sources. Methods: We assessed potential improvements in brain dosimetry for internal emitters by explicitly modelling brain kinetics rather than treating the brain as a mass fraction of Other tissue. We selected ten elements for which brain kinetics can be modeled using published biokinetic data. Injection dose coefficients were calculated for a relatively long-lived radioisotope of each element using each of two versions of the ICRP’s latest systemic biokinetic model for each element, the original version and a modified version differing only in the treatment of brain. If the ICRP model contained an explicit brain pool, the modified version depicted brain instead as a mass fraction of Other tissue. If the ICRP model included brain in Other tissue, the modified version included an explicit brain pool with kinetics based on best available brain-specific data.Results: The result for a given radionuclide is expressed as a ratio A:B, where A and B are the dose coefficients based on the versions of the model with and without an explicit brain pool, respectively. The following ratios A:B were obtained for the 10 radionuclides addressed here: 241 Am, 0.13; 207 Bi, 0.57; 234 U, 0.81; 239 Pu, 0.96; 203 Hg (vapor), 1.4; 134 Cs, 1.5; 54 Mn, 1.7; 210 Po, 1.7; 226 Ra, 1.9; 210 Pb, 3.3. These ratios indicate that a dose estimate for brain based on a biokinetic model with brain implicitly contained in Other tissue may substantially underestimate or substantially overestimate a dose estimate that reflects best available brain-specific biokinetic data. Of course, the reliability of the latter estimate depends on the quality of the underlying biokinetic data.Conclusions: Finally, where feasible, the brain should be depicted explicitly in biokinetic models used in epidemiological studies addressing adverse effects of ionizing radiation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Modeling hepatitis C virus kinetics during liver transplantation highlights the role of the liver in virus clearance

While the liver, specifically hepatocytes, are widely accepted as the main source of hepatitis C virus (HCV) production, the role of the liver/hepatocytes in clearance of circulating HCV remains unknown. Frequent HCV kinetic data were recorded and mathematically modeled from five liver transplant patients throughout the anhepatic (absence of liver) phase and for 4 hr post-reperfusion. During the anhepatic phase, HCV remained at pre-anhepatic levels (n = 3) or declined (n = 2) with t 1/2 ~1 hr. Immediately post-reperfusion, virus declined in a biphasic manner in four patients consisting of a rapid decline (t 1/2 = 5 min) followed by a slower decline (t 1/2 = 67 min). Consistent with the majority of patients in the anhepatic phase, when we monitored HCV clearance at 37°C from culture medium in the absence/presence of chronically infected hepatoma cells that were inhibited from secreting HCV, the HCV t 1/2 in cell culture was longer in the absence of chronically HCV-infected cells. The results suggest that the liver plays a major role in the clearance of circulating HCV and that hepatocytes may be involved.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Strongly Heated Turbulent Flow in a Channel with Pin Fins

Large-eddy simulations (LES) were performed to study the turbulent flow in a channel of height H with a staggered array of pin fins with diameter D = H/2 as a function of heating loads that are relevant to the cooling of turbine blades and vanes. The following three heating loads were investigated—wall-to-coolant temperatures of Tw/Tc = 1.01, 2.0, and 4.0 - where the Reynolds number at the channel inlet was 10,000 and the back pressure at the channel outlet was 1 bar. For the LES, two different subgrid-scale models—the dynamic kinetic energy model (DKEM) and the wall-adapting local eddy-viscosity model (WALE)—were examined and compared. This study was validated by comparing with data from direct numerical simulation and experimental measurements. The results obtained show high heating loads to create wall jets next to all heated surfaces that significantly alter the structure of the turbulent flow. Results generated on effects of heat loads on the mean and fluctuating components of velocity and temperature, turbulent kinetic energy, the anisotropy of the Reynolds stresses, and velocity-temperature correlations can be used to improve existing RANS models.

42 ENGINEERING↗
NASA NTRS1994

Analysis of subgrid models using direct and large-eddy simulations of isotropic turbulence

Direct and large eddy simulations of forced and decaying isotropic turbulence have been performed using a pseudospectral and a finite-difference code. Subgrid models that include a one-equation subgrid kinetic energy model with and without a stochastic backscatter forcing term and a new scale similarity model have been analyzed in both Fourier space and physical space. The Fourier space analysis showed that the energy transfer across the cutoff wavenumber k(sub c) is dominated by local interaction. The correlation between the exact and the modeled (by a spectral eddy viscosity) nonlinear terms and the subgrid energy transfer in physical space was found to be quite low. In physical space, a similar correlation analysis was carried out using top hat filtering. Results show that the subgrid stress and the energy flux predicted by the subgrid models correlates very well with the exact data. The scale similarity model showed very high correlation for reasonable grid resolution. However, with decrease in grid resolution, the scale similarity model became more uncorrelated, when compared to the kinetic energy subgrid model. The subgrid models were then used for large-eddy simulations for a range of Reynolds number. It was determined that the dissipation was modeled poorly and that the correlation with the exact results was quite low for all the models. In general, for coarse grid resolution, the scale similarity model consistently showed very low correlation while the kinetic energy model showed a relatively higher correlation. These results suggest that to use the scale similarity model relatively fine grid resolution may be required, whereas, the kinetic energy model could be used even in coarse grid.

Menon, S.↗
DOE OSTI2022

Assessment of Physics Models for Phase Transition Kinetics

The time dependence of phase diagrams and how to model rate dependent transitions remains one of the key unanswered questions in physics. When a material is loaded dynamically through equilibrium phase boundaries, it is the kinetics that determines the real time expression of a phase transition. Here we report the atomic and nanosecond-scale quantification of kinetics of shock-driven phase transition in multiple materials. We uniquely make use of a both a simple shock as well as shock-and-hold loading pathways compress different crystalline solids and induce structural phase transitions below melt. Coupling shock loading with time-resolved synchrotron x-ray diffraction (DXRD), we probe the structural transformations of these solids in the short-lived high pressure and temperature states generated. The novelty and power of using DXRD for the assessment of kinetics of phase transitions lies in the ability to discover and identify new phases and to examine kinetics without prior knowledge of a material's phase diagram. Our results provide a quantified expression and a physics model of kinetics of formation of high-pressure phases under shock loading: transition incubation time, evolution, completion time and crystallization rate.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling

A combination of periodic density functional theory (DFT, PW91-GGA) calculations, reaction kinetics experiments, and mean-field microkinetic modeling is used to derive insights on the reaction mechanism and determine the nature of the active site under reaction conditions for the vapor-phase decomposition of formic acid (FA, HCOOH) over Pt/C catalysts. Microkinetic models formulated using DFT energetics derived on the clean Pt(100) and Pt(111) required large parameter adjustments to reproduce the experimentally measured apparent activation energies and reaction orders. Further, these models predicted high surface coverage of adsorbed carbon monoxide (CO*), inconsistent with the environment of the active site in the DFT calculations on the clean surfaces. Consequently, we reperformed DFT calculations for the entire reaction network on partially CO*-covered (4/9 monolayer, ML) Pt(111) and Pt(100). The resultant microkinetic models, with thermochemistry and kinetics explicitly dependent on CO* coverage, were able to reproduce the experimentally determined activation energies and reaction orders, in addition to being self-consistent in CO* coverage. Our results suggest that Pt(100) is likely poisoned by CO* under typical reaction conditions and does not contribute significantly to the experimentally observed reactivity. Instead, we find that Pt(111) better represents the active site for FA decomposition reaction on Pt/C catalysts. The optimized model on 4/9 ML CO*-covered Pt(111) suggests that the reaction occurs via the carboxyl (COOH*) intermediate and that the spectator CO*-assisted pathways play a significant role under reaction conditions. Lastly, this study underscores the importance of spectator species on the energetics and the mechanism of a catalytic reaction and their key role in developing a model that better addresses the nature of the active site under realistic catalytic reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗