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NASA NTRS1993

A time-accurate finite volume method valid at all flow velocities

A finite volume method to solve the Navier-Stokes equations at all flow velocities (e.g., incompressible, subsonic, transonic, supersonic and hypersonic flows) is presented. The numerical method is based on a finite volume method that incorporates a pressure-staggered mesh and an incremental pressure equation for the conservation of mass. Comparison of three generally accepted time-advancing schemes, i.e., Simplified Marker-and-Cell (SMAC), Pressure-Implicit-Splitting of Operators (PISO), and Iterative-Time-Advancing (ITA) scheme, are made by solving a lid-driven polar cavity flow and self-sustained oscillatory flows over circular and square cylinders. Calculated results show that the ITA is the most stable numerically and yields the most accurate results. The SMAC is the most efficient computationally and is as stable as the ITA. It is shown that the PISO is the most weakly convergent and it exhibits an undesirable strong dependence on the time-step size. The degenerated numerical results obtained using the PISO are attributed to its second corrector step that cause the numerical results to deviate further from a divergence free velocity field. The accurate numerical results obtained using the ITA is attributed to its capability to resolve the nonlinearity of the Navier-Stokes equations. The present numerical method that incorporates the ITA is used to solve an unsteady transitional flow over an oscillating airfoil and a chemically reacting flow of hydrogen in a vitiated supersonic airstream. The turbulence fields in these flow cases are described using multiple-time-scale turbulence equations. For the unsteady transitional over an oscillating airfoil, the fluid flow is described using ensemble-averaged Navier-Stokes equations defined on the Lagrangian-Eulerian coordinates. It is shown that the numerical method successfully predicts the large dynamic stall vortex (DSV) and the trailing edge vortex (TEV) that are periodically generated by the oscillating airfoil. The calculated streaklines are in very good comparison with the experimentally obtained smoke picture. The calculated turbulent viscosity contours show that the transition from laminar to turbulent state and the relaminarization occur widely in space as well as in time. The ensemble-averaged velocity profiles are also in good agreement with the measured data and the good comparison indicates that the numerical method as well as the multipletime-scale turbulence equations successfully predict the unsteady transitional turbulence field. The chemical reactions for the hydrogen in the vitiated supersonic airstream are described using 9 chemical species and 48 reaction-steps. Consider that a fast chemistry can not be used to describe the fine details (such as the instability) of chemically reacting flows while a reduced chemical kinetics can not be used confidently due to the uncertainty contained in the reaction mechanisms. However, the use of a detailed finite rate chemistry may make it difficult to obtain a fully converged solution due to the coupling between the large number of flow, turbulence, and chemical equations. The numerical results obtained in the present study are in good agreement with the measured data. The good comparison is attributed to the numerical method that can yield strongly converged results for the reacting flow and to the use of the multiple-time-scale turbulence equations that can accurately describe the mixing of the fuel and the oxidant.

Kim, S.-W.↗
NASA NTRS1995

NASA Tech Briefs, November 1995

The contents include: 1) Mission Accomplished; 2) Resource Report: Marshall Space Flight Center; 3) NASA 1995 Software of the Year Award; 4) Microbolometers Based on Epitaxial YBa2Cu3O(sub 7-x) Thin Films; 5) Garnet Random-Access Memory; 6) Fabrication of SNS Weak Links on SOS Substrates; 7) High-Voltage MOSFET Switching Circuit; 8) Asymmetric Switching for a PWM H-Bridge Power Circuit; 9) Better Ohmic Contacts for InP Semiconductor Devices; 10) Low-Bandgap Thermovoltaic Materials and Devices; 11) Digital Frequency-Differencing Circuit; 12) Imaging Magnetometer; 13) Computer-Assisted Monitoring of a Complex System; 14) Buffered Telemetry Demodulator; 15) Compact Multifunction Inspection Head; 16) Optical Detection of Fractures in Ceramic Diaphragms; 17) Eddy-Current Detection of Cracks in Reinforced Carbon/Carbon; 18) Apparent Thermal Conductivity of Multilayer Insulation; 19) Optimizing Misch-Metal Compositions in Metal Hydride Anodes; 20) Device for Sampling Surface Contamination; 21) Probabilistic Failure Assessment for Fatigue; 22) Probabilistic Fatigue and Flaw-Propagation Analysis; 23) Windows Program for Driving the TDU-850 Printer; 24) Subband/Transform MATLAB Functions for Processing Images; 25) Computing Equilibrium Chemical Compositions; 26) Program Processes Thermocouple Readings; 27) ICAN-Second-Generation Integrated Composite Analyzer; 28) Integrated Composite Analyzer with Damping Capabilities; 29) Computing Efficiency of Transfer of Microwave Power; 30) Program Calculates Power Demands of Electronic Designs; 31) Cost-Estimation Program; 32) Program Estimates Areas Required by Electronic Designs; 33) Program to Balance Mapped Turbopump Assemblies; 34) BiblioTech; 35) Controlling Mirror Tilt With a Bimorph Actuator; 36) Burst-Disk Device Simulates Effect of Pyrotechnic Device; 37) Bearing-Mounting Concept Accommodates Thermal Expansion; 38) Parallel-Plate Acoustic Absorbers for Hot Environments; 39) Adjustable-Length Strut Withstands Large Cyclic Loads; 40) Tool Indicates Contact Angles in Bearing Raceways; 41) Gravity Slides With Magnetic Braking; 42) High-Torque, Lightweight, Pneumatically Driven Wrench for Small Spaces; 43) Device for Testing Compatibility of an O-Ring; 44) Magnetic Heat Pump Containing Flow Diverters; 45) Variable-Tilt Helicopter Rotor Mast; 46) "Beach-Ball" Robotic Rovers; 47) Apparatus Would Measure Temperatures of Ball Bearings; 48) Flexible Borescope for Inspecting Ducts; 49) Texturing Copper To Reduce Secondary Emission of Electrons; 50) Automated Laser Cutting in Three Dimensions; 51) Algorithm Helps Monitor Engine Operation; 52) Flexible Revision of Data-Processing Communications; 53) Software for Managing the Use of Land; 54) Thermal Strap Increases Cryocooling Efficiency; 55) Reversible Nut With Engagement Indication; 56) Control Algorithms for Kinematically Redundant Manipulators; 57) Computed Hydrogen-Flow Splits in a Rocket Engine; 58) Pressure and Thermal Modeling of Rocket Launches; 59) Field of View of a Spacecraft Antenna: Analysis and Software; 60) Digital Controller for Laser-Beam-Steering Subsystem; 61) More About Beam-Steering Subsystem for Laser Communication; 62) Digital Controller for Laser-Beam-Steering Subsystem: Part 2; 63) Interface Circuit Board for Space-Shuttle Communications; 64) Automated Planning of Spacecraft Telecommunications; 65) Artifacts of Spectral Analysis of Instrument Readings; 66) Neural-Network Controller for Vibration Suppression; 67) Adaptive Finite-Element Computation in Fracture Mechanics; 68) Attitude Control for the Cassini Spacecraft; 69) Analytical Model for Fluid Dynamics in a Microgravity Environment; 70) Study of Rocket-Engine Joints Bonded by NVCU/NARloy-Z; 71) Improved Silicon Nitride for Advanced Heat Engines; 72) Parameters for Welding Aluminum/Lithium Alloys; 73) Lightweight Composite Intertank Structure; 74) Foil Patches Seal Small Vacuum Leaks; 75) Data Base on Cables and Connectors; 76) Effect of Clock Mode on Radiation Hardnessf an ADC; and 77) Fault-Tolerant Control for a Robotic Inspection System.

Source record↗
DOE OSTI2023

Solar water splitting Pt-nanoparticle photosystem I thylakoid systems: Catalyst identification, location and oligomeric structure

In this study, photosynthetic conversion of light energy into chemical energy occurs in sheet-like membrane-bound compartments called thylakoids and is mediated by large integral membrane protein-pigment complexes called reaction centers (RCs). Oxygenic photosynthesis of higher plants, cyanobacteria and algae requires the symbiotic linking of two RCs, photosystem II (PSII) and photosystem I (PSI), to split water and assimilate carbon dioxide. Worldwide there is a large research investment in developing RC-based hybrids that utilize the highly evolved solar energy conversion capabilities of RCs to power catalytic reactions for solar fuel generation. Of particular interest is the solar-powered production of H 2 , a clean and renewable energy source that can replace carbonbased fossil fuels and help provide for ever-increasing global energy demands. Recently, we developed thylakoid membrane hybrids with abiotic catalysts and demonstrated that photosynthetic Z-scheme electron flow from the light-driven water oxidation at PSII can drive H 2 production from PSI. One of these hybrid systems was created by self-assembling Pt-nanoparticles (PtNPs) with the stromal subunits of PSI that extend beyond the membrane plane in both spinach and cyanobacterial thylakoids. Using PtNPs as site-specific probe molecules, we report the electron microscopic (EM) imaging of oligomeric structure, location and organization of PSI in thylakoid membranes and provide the first direct visualization of photosynthetic Z-scheme solar water-splitting biohybrids for clean H 2 production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Catalight─An Open-Source Automated Photocatalytic Reactor Package Illustrated through Plasmonic Acetylene Hydrogenation

An open-source and modular Python package, Catalight, is developed and demonstrated to automate (photo)catalysis measurements. (Photo)catalysis experiments require studying several parameters to evaluate performance, including the temperature, gas flow rate and composition, illumination power, and spectral profile. Catalight orchestrates measurements over this complicated parameter space and systematically stores, analyzes, and visualizes the results. To showcase the capabilities of Catalight, we perform an automated apparent activation barrier measurement of acetylene hydrogenation over a plasmonic AuPd catalyst on an Al 2 O 3 support, simultaneously varying laser power, wavelength, and temperature in a multiday experiment controlled by a simple Python script. Our chemical results unexpectedly show an increased activation barrier upon light excitation, contrary to previous findings for other plasmonic reactions and catalysts. We show that the reaction rate order with respect to both acetylene and hydrogen remains unchanged upon illumination, suggesting that molecular surface coverage is not changed by light. By analyzing the inhomogeneity of the laser-induced heating, we attribute these results to a partial photothermal effect combined with a photochemical/hot electron-driven mechanism. In conclusion, our findings highlight the capabilities of a new experiment automation tool; explore the photocatalytic mechanism for an industrially relevant reaction; and identify systematic sources of error in canonical photocatalysis experimental procedures.

Catalysts↗
DOE OSTI2025

An efficient hybrid downscaling framework to estimate high-resolution river hydrodynamics

Flow depth and velocity are the most important hydrodynamic variables that govern various river functions, including water resources, navigation, sediment transport, and biogeochemical cycling. Existing high-resolution flow depth simulations rely on either computationally expensive river hydrodynamic models (RHMs) or data-driven models with formidable training costs, whereas data-driven modeling of flow velocity has rarely been explored. Here, using the hybrid Low-fidelity, Spatial analysis, and Gaussian process learning (LSG) model, we developed a downscaling approach to construct high-resolution flow depth and velocity from a two-dimensional (2-D) RHM simulation at coarse resolution. The LSG models were trained and tested in an urban watershed in Houston using two different hurricane-driven flood events. The high-resolution (as fine as 30 m resolution) and low-resolution (mostly 1000 m resolution) meshes include 664 724 and 14 536 grid cells, respectively. The results showed that through downscaling, the simulation errors were reduced to less than one-fourth and one-third of the errors of the low-resolution 2-D RHM for flow depth and velocity, respectively. Our analysis further revealed that the dominant uncertainty sources of the downscaled hydrodynamics are different, with flow velocity dominated by the dimensionality reduction error, which we reduced by using a regionalized training procedure. The downscaling approach achieves an 84-fold acceleration in computational time compared to the high-resolution 2-D RHM, making high-fidelity ensemble flood modeling feasible. More importantly, the developed method provides an opportunity to couple large-scale hydrodynamical processes with local physical, chemical, and biological processes in river models.

Tan, Zeli [Pacific Northwest National Laboratory (↗
NASA NTRS1995

The Superorbital Expansion Tube concept, experiment and analysis

In response to the need for ground testing facilities for super orbital re-entry research, a small scale facility has been set up at the University of Queensland to demonstrate the superorbital expansion tube concept. This unique device is a free piston driven, triple diaphragm, impulse shock facility which uses the enthalpy multiplication mechanism of the unsteady expansion process and the addition of a secondary shock driver to further heat the driver gas. The pilot facility has been operated to produce quasi-steady test flows in air with shock velocities in excess of 13 km/s and with a usable test flow duration of the order of 15 micro sec. an experimental condition produced in the facility with total enthalpy of 108 MJ/kg and a total pressure of 335 MPa is reported. A simple analytical flow model which accounts for non-ideal rupture of the light tertiary diaphragm and the resulting entropy increase in the test gas is discussed. It is shown that equilibrium calculations more accurately model the unsteady expansion process than calculations assuming frozen chemistry. This is because the high enthalpy flows produced in the facility can only be achieved if the chemical energy stored in the test flow during shock heating of the test gas is partially returned to the flow during the process of unsteady expansion. Measurements of heat transfer rates to a flat plate demonstrate the usability of test flow for aerothermodynamic testing and comparison of these rates with empirical calculations confirms the usable accuracy of the flow model.

Neely, A. J.↗
DOE OSTI2026

Solar Heat for Industrial Processes: Integration with Chemical Reactors

The integration of solar thermal systems with chemical reactors has been proposed as part of a larger effort to develop and deploy solar heat for industrial processes (SHIP) technologies. A strong motivation for SHIP processes and technologies is the potential for high thermal efficiency coupled with low-cost thermal energy storage (TES) which can enable commercial deployment of such systems. While there are different ways to categorize SHIP technologies, one important such distinction is between directly irradiated systems and indirect off-sun process driven by a SHIP system. While directly irradiated systems can provide high thermal efficiencies and high fluxes, they usually require complex engineering solutions due to the need for redesigning the established processes and unit operations. In most cases, it is also more challenging to couple such a process to a TES system, losing some of the benefits of SHIP. On the other hand, using a SHIP system to drive an industrial process off-sun can allow better integration with existing process chains, easier TES capabilities, and potential for more applications fitting a specific SHIP technology. However, the integration of SHIP systems with the industrial processes is not fully explored in detail, especially in the case of high-temperature processes such as reforming, cracking, cement manufacturing, and iron/steelmaking. Many of these systems require heating fluxes of >50 kW/m^2, supplied via combustion of hydrocarbons in a fire box and benefitting from radiative heat transfer between the flue gases and the reaction zones. As such, using SHIP systems for such processes is more complex than providing the same thermal input in the form of a heat transfer medium (HTM) entering the reactor, kiln, or furnace. Moreover, in case convective heat transfer using SHIP is envisioned, for example using supercritical CO2 as the HTM from a particle receiver, the thermal integration might be more challenging than initially envisioned: lower heat transfer coefficients and limited approach temperature might require large flow rates, causing a mismatch between the process thermal requirements and the thermal capacity of the SHIP system. In addition, even if the heat exchange between SHIP and reactor is effective, there is still a cold leg HTM at the reaction temperature or slightly below it. Chemical plants usually include a set of heat exchangers, heat recovery steam generators, and even power generation units - in a tightly integrated design - to recover the flue gases which are eventually vented. With SHIP systems mostly operating on a closed HTM loop, bottoming the cold leg is crucial. In this talk, we will present different modeling results for a variety of syngas production reactions, using catalytic and chemical looping processes, and discuss some of the challenges and design considerations for off-sun chemical reactors using SHIP systems.

14 SOLAR ENERGY↗
DOE OSTI2020

Data from Stereoconvergent Reduction of Activated Alkenes by a Nicotinamide Free Synergistic Photobiocatalytic System

There is a growing interest in developing cooperative chemoenzymatic reactions to harness the reactivity of chemical catalysts and the selectivity of enzymes for the synthesis of nonracemic chiral compounds. However, existing chemoenzymatic systems with more than one chemical reaction and one enzymatic reaction working cooperatively are rare. Moreover, the application of oxidoreductases in cooperative chemoenzymatic reactions is limited by the necessity of using expensive and unstable redox equivalents such as nicotinamide cofactors. Here, we report a light-driven cooperative chemoenzymatic system comprised of a photoinduced electron transfer reaction (PET) and a photosensitized energy transfer reaction (PEnT) with an enzymatic reduction in one-pot to synthesize chiral building blocks of bioactive compounds. As a proof of concept, ene-reductase was directly regenerated by PET in the absence of external cofactors. Meanwhile, enzymatic reduction worked cooperatively with photocatalyst-catalyzed energy transfer that continuously replenished the reactive isomer from the less reactive one. The whole system stereoconvergently reduced E/Z mixtures of alkenes to the enantiopure products. Additionally, enantioselective enzymatic reduction worked competitively with photocatalyst-catalyzed racemic background reaction and side reactions to channel the overall electron flow to the single enantiopure product. Such a light-driven cooperative chemoenzymatic system holds great potential for asymmetric synthesis using inexpensive petroleum or biomass-derived alkenes.

Catalysis↗
NASA NTRS1994

Quasi-biennial oscillations of ozone and diabatic circulation in the equatorial stratosphere

The quasi-biennial oscillation (QBO) in ozone in the equatorial stratosphere is obtained by analyzing the Stratospheric Aerosol and Gas Experiment (SAGE) data from 1984 to 1989. The phase of the ozone QBO in the lower stratosphere is found to precede the zonal wind QBO by several months as opposed to the theoretically expected in-phase relationship between the two. A mechanistic model is developed to explore possible reasons for this disagreement. The model is capable of simulating the actual time evolution of the ozone QBO by introducing the observed zonal wind profile as input. The modeled results confirm the conventional view that the ozone QBO is generated by the vertical ozone advection that is driven to maintain the temperature structure against radiative damping. However, a series of experiments emphasizes the importance of the feedback of the ozone QBO to the diabatic heating through the absorption of solar radiation. Due to this effect, the phase of the ozone QBO shifts up to a quarter cycle ahead and approaches that of the temperature QBO. Because of this inphase relationship, the feedback of the ozone QBO to the diabatic heating acts to compensate for the radiative damping of the temperature structure, thus reducing the magnitude of the induced diabatic circulation. Because the reduction of the magnitude of the vertical motion facilitates downward transport of easterly momentum by the mean flow, this feedback process can help to resolve the insufficiency of the easterly momentum in driving the dynamical QBO in general circulation models (GCMs). It should be emphasized that more sophisticated models that allow for full interaction between the chemical species and radiative and dynamical processes should be developed to improve our understanding of both dynamical and ozone QBOs.

Hasebe, Fumio↗
NASA NTRS1999

Microgravity Transport Phenomena Experiment (MTPE) Overview

The Microgravity Transport Phenomena Experiment (MTPE) is a fluids experiment supported by the Fundamentals in Biotechnology program in association with the Human Exploration and Development of Space (BEDS) initiative. The MTP Experiment will investigate fluid transport phenomena both in ground based experiments and in the microgravity environment. Many fluid transport processes are affected by gravity. Osmotic flux kinetics in planar membrane systems have been shown to be influenced by gravimetric orientation, either through convective mixing caused by unstably stratified fluid layers, or through a stable fluid boundary layer structure that forms in association with the membrane. Coupled transport phenomena also show gravity related effects. Coefficients associated with coupled transport processes are defined in terms of a steady state condition. Buoyancy (gravity) driven convection interferes with the attainment of steady state, and the measurement of coupled processes. The MTP Experiment measures the kinetics of molecular migration that occurs in fluids, in response to the application of various driving potentials. Three separate driving potentials may be applied to the MTP Experiment fluids, either singly or in combination. The driving potentials include chemical potential, thermal potential, and electrical potential. Two separate fluid arrangements are used to study membrane mediated and bulk fluid transport phenomena. Transport processes of interest in membrane mediated systems include diffusion, osmosis, and streaming potential. Bulk fluid processes of interest include coupled phenomena such as the Soret Effect, Dufour Effect, Donnan Effect, and thermal diffusion potential. MTP Experiments are performed in the Microgravity Transport Apparatus (MTA), an instrument that has been developed specifically for precision measurement of transport processes. Experiment fluids are contained within the MTA fluid cells, designed to create a one dimensional flow geometry of constant cross sectional area, and to facilitate fluid filling and draining operations in microgravity. The fluid cells may be used singly for bulk solutions, or in a Stokes diaphragm configuration to investigate membrane mediated phenomena. Thermal and electrical driving potentials are applied to the experiment fluids through boundary plates located at the ends of the fluid cells. In the ground based instrument, two constant temperature baths circulate through reservoirs adjacent to the boundary plates, and establish the thermal environment within the fluid cells. The boundary plates also serve as electrodes for measurement and application of electrical potentials. The Fluid Manipulation System associated with the MTA is a computer controlled system that enables storage and transfer of experiment fluids during on orbit operations. The system is used to automatically initiate experiments and manipulate fluids by orchestrating pump and valve operations through scripted sequences. Unique technologies are incorporated in the MTA for measurement of fluid properties. Volumetric Flow Sensors have been developed for precision measurement of total fluid volume contained within the fluid cells over time. This data is most useful for measuring the kinetics of osmosis, where fluid is transported from one fluid cell to another through a semipermeable membrane. The MicroSensor Array has been designed to perform in situ measurement of several important fluid parameters, providing simultaneous measurement of solution composition at multiple locations within the experiment fluids. Micromachined sensors and interface electronics have been developed to measure temperature, electrical conductivity, pH, cation activity, and anion activity. The Profile Refractometer uses a laser optical system to directly image the fluid Index of Refraction profile that exists along the MTA fluid cell axis. A video system acquires images of the RI profile over time, and records the transport kinetics that occur upon application of chemical, thermal, or electrical driving potentials. Image processing algorithms have been developed to analyze the refractometer images on a pixel by pixel basis, calibrating and scaling the measured Index of Refraction profile to correlated solution properties of interest such as density, concentration, and temperature. Additional software has been developed to compile the processed images into a three dimensional matrix that contains fluid composition data as a function of experiment time and position in the fluid cell. These data are combined with data from the other sensor systems, and analyzed in the context of transport coefficients associated with the various transport phenomena. Analysis protocols have been developed to measure the transient kinetics, and steady state distribution of fluid components that occur in response to the applied driving potentials. The results are expressed in terms of effective transport coefficients. Experiments have been performed using a variety of solutes, and results generated are that are in agreement with published transport coefficient values.

Mason, Larry W.↗
DOE OSTI2020

Stereoconvergent Reduction of Activated Alkenes by a Nicotinamide Free Synergistic Photobiocatalytic System

There is a growing interest in developing cooperative chemoenzymatic reactions to harness the reactivity of chemical catalysts and the selectivity of enzymes for the synthesis of nonracemic chiral compounds. However, existing chemoenzymatic systems with more than one chemical reaction and one enzymatic reaction working cooperatively are rare. Moreover, the application of oxidoreductases in cooperative chemoenzymatic reactions is limited by the necessity of using expensive and unstable redox equivalents such as nicotinamide cofactors. Here we report a lightdriven cooperative chemoenzymatic system comprised of a photoinduced electron transfer reaction (PET) and a photosensitized energy transfer reaction (PEnT) with enzymatic reduction in one-pot to synthesize chiral building blocks of bioactive compounds. As a proof of concept, ene-reductase was directly regenerated by PET in the absence of external cofactors. Meanwhile, enzymatic reduction worked cooperatively with photocatalyst-catalyzed energy transfer that continuously replenished the reactive isomer from the less reactive one. The whole system stereoconvergently reduced E/Z mixtures of alkenes to the enantiopure products. Additionally, enantioselective enzymatic reduction worked competitively with photocatalyst-catalyzed racemic background reaction and side reactions to channel the overall electron flow to the single enantiopure product. As a result, such a light-driven cooperative chemoenzymatic system holds great potential for asymmetric synthesis using inexpensive petroleum or biomass derived alkenes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A physics-constrained neural ordinary differential equations approach for robust learning of stiff chemical kinetics

The high computational cost associated with solving for detailed chemistry poses a significant challenge for predictive computational fluid dynamics (CFD) simulations of turbulent reacting flows. While deep learning techniques have been explored to develop faster surrogate models, they often fail to integrate reliably with CFD solvers. This instability arises because traditional deep learning approaches optimize for training error without ensuring compatibility with ordinary differential equation (ODE) solvers, resulting in accumulation of errors over time. Recently, neuralODE (NODE) based approaches have been shown to be a promising technique to emulate and accelerate detailed chemistry computations. Here, in the present work, we extend this NODE framework for stiff chemical kinetics by incorporating mass conservation constraints directly into the loss function during training. This ensures that the total mass as well as the individual elemental species masses are conserved in an a-posteriori manner. Proof-of-concept studies are performed with the novel physics-constrained NODE (PC-NODE) approach for homogeneous autoignition of hydrogen-air mixture over a range of composition and thermodynamic conditions. It is demonstrated that the PC-NODE framework not only improves the physical consistency of the resulting data-driven model with respect to mass conservation criteria, but also improves training efficiency. PC-NODE is shown to achieve 2–100× speedup relative to the hydrogen-air detailed chemical mechanism depending on the type of the ODE solver (implicit or explicit) used during autoregressive inference tests. Lastly, a-posteriori studies are performed wherein the trained PC-NODE model is coupled with a CFD solver. It is shown that higher accuracy is achieved with PC-NODE relative to the purely data-driven NODE approach. Moreover, PC-NODE also exhibits robustness and generalizability to unseen initial conditions from within (interpolative capability) as well as outside (extrapolative capability) the training regime.

computational combustion↗
DOE OSTI2025

From clutter to clarity: Emergent neural operators via questionnaire metrics

Real-world datasets in chemical engineering and bioengineering processes—such as those from catalytic reactors, multiphase flows, polymerization reactors, bioreactors, and clinical trials—can often be unlabeled or disorganized, rendering the training of existing supervised learning models ineffective at learning the underlying dynamics. To salvage these datasets for decision-making, we first seek to obtain clarity from the cluttered data. Here, we present a framework for developing “structural” generative models, discovering emergent equations, and constructing efficient emulators from scrambled datasets by integrating unsupervised organizational learning techniques (Questionnaires) with advanced deep learning architectures (Deep Hidden Physics Models and Deep Operator Networks). Our approach is demonstrated on two illustrative model systems: (a) a 1D advection–diffusion partial differential equation representing a winding underground pipe and (b) an ensemble of Stuart–Landau oscillators, an agent-based system of coupled ordinary differential equations. In both cases, we successfully reconstruct meaningful spatial, temporal, and parameter embeddings from scrambled data, enabling good predictions of system dynamics. As a result, we highlight the framework’s potential for broader applications, enabling data-driven system identification in fields with inherently disorganized or hidden parameter spaces.

42 ENGINEERING↗
NASA NTRS2022

Coupling Carbon Oxidation and Surface Recession in Direct-Simulation Monte Carlo Code, SPARTA

Ablative thermal protection system (TPS) materials for spacecraft are composites that are often made out of carbon-based reinforcement and a polymeric matrix. They endure high-temperature oxidation and surface recession when re-entering Earth’s atmosphere. Ablation is the result of many coupled and competing thermal, mechanical, and chemical phenomena, and it is difficult to isolate the role of each on the overall degradation of the TPS. Here we develop an ablation model for material recession coupled explicitly to finite rate carbon oxidation in complex microstructures. In this work, Stochastic PArallel Rarified-gas Time-accurate Analyzer (SPARTA), a direct-simulation Monte Carlo (DSMC) code, is modified to allow oxidation-driven ablation of implicitly defined carbon surfaces. In SPARTA, implicit surfaces are generated from the grid corner point values via a marching cubes algorithm, therefore creating a new set of surface elements every time ablation is performed. The finite-rate oxidation model developed by Gopalan et. al, was adapted to tally surface reactions and other surface data on a per-grid cell basis. The ablation functionality was also adjusted so once the reactions have occurred, the number of reactions leading to CO formation can be converted to corner point reduction values; therefore, carbon removal is directly proportional to surface recession. We also develop robust algorithms which handle the evolution of the flow cells and solid material regions, including split cells (flow cell divided in two by a solid surface). Finally, we demonstrate our implicit chemistry model for 2D and 3D geometries by producing reaction statistics and detailed visualization of oxidation-induced material recession at the microscale.

V Arias↗
NASA NTRS1976

Electrochemical deposition of silver crystals aboard Skylab 4

Silver crystals were grown aboard Skylab 4 by an electro-chemical reaction and subsequently returned to earth for comparison with crystals grown at 1- and 5-g. Both the Skylab and earth-grown crystals show a variety of structures. Certain tendencies in structure dependency on gravity level, however, can be discerned. In addition, downward growing dendrite streamers; upward growing chunky crystal streamers; growth along an air/liquid interface; and ribbon, film, and fiber crystal habits were observed in experiments conducted on the ground with solutions of varying concentrations. It was also observed that the crystal structures of space and ground electro-deposited silver crystals were very similar to the structures of germanium selenide and germanium telluride crystals grown in space and on the ground by a vapor transport technique. Consideration of the data leads to the conclusions that: (1) the rate of electrochemical displacement of silver ions from a 5 percent aqueous solution by copper is predominantly diffussion controlled in space and kinetically controlled in 1- and higher-g because of augmentation of mass transport by convection; (2) downward and upward crystal streamers are the result of gravity-driven convection, the flow patterns of which can be delineated. Lateral growths along an air/liquid interface are the result of surface-tension-driven convection, the pattern of which also can be delineated; (3) electrolysis in space or low-g environments can produce either dendritic crystals with more perfect microcrystalline structures or massive, single crystals with fewer defects than those grown on ground or at higher g-levels. Ribbons or films of space-grown silicon crystals would find a ready market for electronic substrate and photocell applications. Space-grown dendritic, metal crystals present the possibility of unique catalysts. Large perfect crystals of various materials are desired for a number of electronic and optical applications; and (4) vapor transport growth of germanium selenide and germanium telluride is affected by convection mechanisms similar to the mechanisms hypothesized for the electrochemical deposition of silver crystals. Evidence and considerations leading to the preceding summaries and conclusions are presented. The implications of the findings and conclusions for technological applications are discussed, and recommendations for further experiments are presented.

Grodzka, P. G.↗
DOE OSTI2024

From Coherence to Function: Exploring the Connection in Chemical Systems

The role of quantum mechanical coherences or coherent superposition states in excited state processes has received considerable attention in the last two decades largely due to advancements in ultrafast laser spectroscopy. These coherence effects hold promise for enhancing the efficiency and robustness of functionally relevant processes, even when confronted with energy disorder and environmental fluctuations. Understanding coherence deeply drives us to unravel mechanisms and dynamics controlled by order and synchronization at a quantum mechanical level, envisioning optical control of coherence to enhance functions or create new ones in molecular and material systems. In this frontier, the interplay between electronic and vibrational dynamics, specifically the influence of vibrations in directing electronic dynamics, has emerged as the leading principle. Here, two energetically disparate quantum degrees of freedom work in-sync to dictate the trajectory of an excited state reaction. Moreover, with the vibrational degree being directly related to the structural composition of molecular or material systems, new molecular designs could be inspired by tailoring certain structural elements. In the realm of chemical kinetics, our understanding of the dynamics of chemical transformations is underpinned by fundamental theories, such as transition state theory, activated rate theory, and Marcus theory. These theories elucidate reaction rates by considering the energy barriers that must be overcome for reactants to transform into products. Those barriers are surmounted by the stochastic nature of energy gap fluctuations within reacting systems, emphasizing that the reaction coordinate, the pathway from reactants to products, is not rigidly defined by a specific vibrational motion but encompasses a diverse array of molecular motions. While less is known about the involvement of specific intramolecular vibrational modes, their significance in certain cases cannot be overlooked. In this Account, we summarize key experimental findings that offer deeper insights into the complex electronic–vibrational trajectories encompassing excited states afforded from state-of-the-art ultrafast laser spectroscopy in three exemplary processes: photoinduced electron transfer, singlet–triplet intersystem crossing, and intramolecular vibrational energy flow in molecular systems. We delve into the rapid decoherence, or loss of phase and amplitude correlations, of vibrational coherences along promoter vibrations during subpicosecond intersystem crossing dynamics in a series of binuclear platinum complexes. This rapid decoherence illustrates the vibration-driven reactive pathways from the Franck–Condon state to the curve crossing region. We also explore the generation of new vibrational coherences induced by impulsive reaction dynamics rather than by the laser pulse in these systems, which sheds light on specific energy dissipation pathways and thereby on the progression of the reaction trajectory in the vicinity of the curve crossing on the product side. Another property of vibrational coherences, amplitude, reveals how energy can flow from one vibration to another in the electronic excited state of a terpyridine–molybdenum complex hosting a nonreactive dinitrogen substrate. In conclusion, a slight change in vibrational energy triggers a quasi-resonant interaction, leading to constructive wavepacket interference and ultimately intramolecular vibrational redistribution from a Franck–Condon active terpyridine vibration to a dinitrogen stretching vibration, energizing the dinitrogen bond.

Electrical energy↗
DOE OSTI2021

Exogenous electricity flowing through cyanobacterial photosystem I drives CO 2 valorization with high energy efficiency

Nature's biocatalytic processes are driven by photosynthesis, whereby photosystems I and II are connected in series for light-stimulated generation of fuel products or electricity. Externally supplying electricity directly to the photosynthetic electron transfer chain (PETC) has numerous potential benefits, although strategies for achieving this goal have remained elusive. Here we report an integrated photo-electrochemical architecture which shuttles electrons directly to PETC in living cyanobacteria. The cathode of this architecture electrochemically interfaces with cyanobacterial cells that have a lack of photosystem II activity and cannot perform photosynthesis independently. Illumination of the cathode channels electrons from an external circuit to intracellular PETC through photosystem I, ultimately fueling cyanobacterial conversion of CO 2 into acetate. We observed acetate formation when supplying both illumination and exogenous electrons under intermittent conditions (e.g., in a 30 s supply plus 30 min interval condition of both light and exogenous electrons). The energy conversion efficiency for acetate production under programmed intermittent LED illumination (400–700 nm) and exogenous electron supply reached ca. 9%, when taking into account the number of photons and electrons received by the biotic system, and ca. 3% for total photons and electrons supplied to the cyanobacteria. This approach is applicable for generating various CO 2 reduction products by using engineered cyanobacteria, one of which has enabled electrophototrophic production of ethylene, a broadly used hydrocarbon in the chemical industry. The resulting bio-electrochemical hybrid has the potential to produce fuel chemicals with numerous potential advantages over standalone natural and artificial photosynthetic approaches.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Collaborative Research Proposal: Time Resolved Optical Emissions Spectroscopy and Laser Induced Fluorescence Spectroscopy of Nanosecond Pulsed Discharges in a Gas-Liquid Water Film Reactor

Electrical discharge plasma formed in contact with liquid water is of interest for a wide range of applications in chemical, biomedical, agricultural, electrical, and materials science and engineering. Such plasma reactors are of very timely importance since they also have significant disinfection capability by inactivating bacteria, viruses and other pathogens. Many types of plasma sources including those driven by AC, DC, RF, microwave, and pulsed electrical power supplies coupled to a wide range of different electrode configurations and reactor designs have been developed and explored which contact the plasma with liquid water. Recent roadmaps have recommended that further work is needed to develop our understanding of the fundamental chemical and physical process which occur at the interface of non-thermal plasma with liquid water solutions in order to advance this large diversity of applications which ultimately depend upon efficient production of key reactive chemical species. There is a wide range of interacting factors that affect the chemical reactions that occur in the plasma, in the liquid phase, and at the interface. These factors ultimately govern the key reactive chemical species formed and used in the various applications and they include a) the reactor design and input parameters, b) the discharge and transport processes, c) the plasma properties, and d) the resulting chemical reactions. For pulsed discharges, the power supply design and output parameters control the applied voltage, frequency, rise time, and width (duration) of the applied pulses. The reactor design involves specification of the gas-liquid contacting methods, electrode gap distance, reactor volume and shape, and gas and liquid flow rates achievable. The gas and liquid compositions as well as the liquid properties such as pH and conductivity are also of key importance in determination of the resulting chemical reactions. In addition, the important plasma properties include plasma gas temperature, electron density, electron energy (distribution), and size of the plasma channels which are all affected by the discharge and transport properties. Many studies have focused on specific aspects of these various processes. Of particular important and relevance to the proposed work is the utilization of nanosecond pulses to generate plasma in gas-liquid systems, liquid bubbles, underwater, and in gases. Recent advances in nanosecond pulses provide significant advantages in utilization with liquid water. For example, fast rise time and short pulses are less sensitive to water conductivity, such short pulses may provide advantages in fast temporal quenching of the plasma, and fundamental analysis of pulse properties, including pulse shape and width, may be facilitated by investigation of single filamentary fast pulses. Many studies have also dealt with the role of the gas composition on formation of reactive oxygen species (ROS) (i.e., hydroxyl radicals – ·OH, hydrogen peroxide – H 2 O 2 , various atomic oxygen species, ozone-O 3 , hydroperoxyl radicals HO 2 ·) and reactive nitrogen species (RNS) (i.e., nitrogen oxides – NO, NO 2 , N 2 O - collectively termed NO X , nitrite-NO 2 - , nitrate-NO 3 - , peroxynitrite-ONOO - ). The hydroxyl radical is the critical species in many chemical oxidation reactions for chemical degradation of toxic compounds in water and gases and for synthesis of some compounds. The mixture of various nitrogen oxide species is important for many biochemical and biological processes involved in biomedical and agricultural applications including disinfection and fertilizer production. The present proposal focuses on determination of the effects of time resolved electron density and hydroxyl radicals on plasma chemical reactions through collaboration with the Princeton Collaborative Low Temperature Plasma Research Facility (PCRF) at the Princeton Plasma Physics Laboratory (PPPL). In order to further investigate the role of the plasma generated electrons and hydroxyl radicals on the overall formation of the key species including hydrogen peroxide, hydroxyl radicals, and nitrogen oxides, the proposed work, thus seeks to determine high resolution time resolved electron density by optical emissions spectroscopy and time resolved hydroxyl radicals using laser induced fluorescence in the nanosecond discharge reactor. The combination of data on electron density and hydroxyl radical concentration will be utilized in the present work to more fully characterize the chemical reaction processes in this system and to advance the design, development, and operation of such chemical reactors for a wide range of applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗