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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A thermochemical database from high-throughput first-principles calculations and its application to analyzing phase evolution in AM-fabricated IN718

A comprehensive thermochemical database is constructed based on high–throughput first-principles phonon calculations of over 3000 atomic structures in limited concentrations in Ni, Fe, and Co alloys involving a total of 26 elements including Al, B, C, Cr, Cu, Hf, La, Mn, Mo, N, Nb, O, P, Re, Ru, S, Si, Ta, Ti, V, W, Y, and Zr, providing thermochemical data largely unavailable from existing experiments. Here, the database can be employed to predict the equilibrium phase compositions and fractions directly from first-principles by minimizing the chemical potential of a multicomponent system with a fixed overall chemical composition and a fixed temperature. It is applied to the additively manufactured nickel-based IN718 superalloy to analyze the phase evolution with temperature. IN718 is known for its great performance in tensile, fatigue, creep, and rupture strength, combined with easy fabrication and corrosion resistance. In particular, we successfully predicted the formation of L1 0 -FeNi, γ’-Ni 3 (Fe,Al), α-Cr, δ-Ni 3 (Nb,Mo), γ”-Ni 3 Nb, and η-Ni 3 Ti at low temperatures (below 680 K), γ’-Ni 3 Al, δ-Ni 3 Nb, γ”-Ni 3 Nb, α-Cr, and γ-Ni(Fe,Cr,Mo) at intermediate temperatures (between 680 and 1140 K), and δ-Ni 3 Nb and γ-Ni(Fe,Cr,Mo) at high temperatures (above 1140 K) in IN718. These predictions are validated by EDS mapping of compositional distributions and corresponding identifications of phase distributions. The database is expected to be a valuable source for future thermodynamic analysis and microstructure prediction of alloys involving the 26 elements.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Python Group Additivity (pGrAdd) software for estimating species thermochemical properties

ncreasingly complex chemistry models require thermochemical data for many species often estimated from costly first-principles DFT computations. Here we introduce the Python Group Additivity software (pGrAdd) that implements comprehensive group additivity in a simple, modular, lightweight Python package that is extensible and easy to implement. It includes 6 group additivity databases for gas species and Pt(111) adsorbates allowing users to immediately compute thermochemical properties for a wide range of molecules and build new databases.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Active Thermochemical Tables: Enthalpies of Formation of Bromo- and Iodo-Methanes, Ethenes and Ethynes

Here, the thermochemistry of halocarbon species containing iodine and bromine is examined through an extensive interplay between new Feller–Peterson–Dixon (FPD) style composite methods and a detailed analysis of all available experimental and theoretical determinations using the thermochemical network that underlies the Active Thermochemical Tables (ATcT). From the computational viewpoint, a slower convergence of the components of composite thermochemistry methods is observed relative to species that solely contain first row elements, leading to a higher computational expense for achieving comparable levels of accuracy. Potential systematic sources of computational uncertainty are investigated, and, not surprisingly, spin-orbit coupling is found to be a critical component, particularly for iodine containing molecular species. The ATcT analysis of available experimental and theoretical determinations indicates that prior theoretical determinations have significantly larger uncertainties than originally reported, particularly in cases where molecular spin-orbit effects were ignored. Accurate and reliable heats of formation are reported for 38 halogen containing systems, based on combining the current computations with previous experimental and theoretical work via the ATcT approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Solar Thermochemical Redox Cycling Using Ga- and Al-Doped LSM Perovskites for Renewable Hydrogen Production

Solar thermochemical hydrogen production using redox-active metal oxides is a promising pathway for the production of green hydrogen and synthetic fuel precursors. Herein, the perovskite material (La 0.6 Sr 0.4 ) 0.95 Mn 0.8 Ga 0.2 O 3–δ (LSMG6482) is identified as a promising metal oxide for thermochemical water splitting. LSMG6482, along with more-established water splitters ceria and (La 0.6 Sr 0.4 ) 0.95 Mn x Al 1–x O 3–δ (LSMA) perovskites, is experimentally characterized via thermogravimetric (TGA) analysis and high-temperature water splitting in a reactor simulating solar concentrating conditions. TGA analysis demonstrated that LSMG6482 has high and stable oxygen exchange capacity under controlled pO 2 redox cycling, demonstrated by large changes in oxygen nonstoichiometry (δ) relative to ceria. Water splitting experiments using laser heating (T red = 1400 °C, T ox = 1200 °C) resulted in H 2 yields of 165.1 μmol g –1 for the candidate LSMG6482 composition, exceeding that of all benchmark materials tested. Under high conversion oxidation conditions, where H 2 is cointroduced with H 2 O (150 ≤ nH 2 O/nH 2 ≤ 500), H 2 yields were greatest for LSMG6482 and LSMA6482, up to four times that of ceria at the highest nH 2 O/nH 2 conditions. Crystallographic analysis showed that over the course of experimentation, there is some secondary phase growth for all perovskite compositions, except for LSMA6482, but there was no observable degradation in H 2 yields.

08 HYDROGEN↗
DOE OSTI2026

Electrolyte Organization Leads to Potential-Dependence in Thermochemical Catalysis of Nonpolar Reactions

Electrochemical polarization is now known to play a key role in thermochemical catalysis at solid–liquid interfaces. However, existing frameworks cannot account for why even nonpolar, nonfaradaic reactions are sensitive to interfacial polarization. In order to uncover the molecular basis of this phenomenon, we herein study the potential-dependent reaction kinetics of ethylene and trans-2-butene hydrogenation at Pt–liquid interfaces. Measurements were performed in aqueous and ortho-difluorobenzene (o-DFB) solutions, spontaneously polarizing the Pt–liquid interfaces by, respectively, varying the pH or dissolving distinct metallocene redox buffers into solution. Here, we find that at comparable mechanistic regimes, the rates of both ethylene and trans-2-butene hydrogenation are maximized near the same electrochemical potential, E. Moreover, the potential-dependence, defined as $\frac{∂ln 𝑟}{∂𝐸}$, of trans-2-butene hydrogenation is approximately 2.2× greater than that of ethylene hydrogenation across the full potential range studied. These observations are all consistent with a model in which polarization of the Pt surface away from the local potential of zero free charge (E PZFC ) induces electrostatic organization of the polar solvent and charged ions near the interface, which impedes olefin adsorption and surface reaction because these surface reactions induce electrolyte displacement. Accordingly, interfacial polarization alters the free energy landscape and thus the rate of nonpolar heterogeneous catalysis by controlling the degree of electrostatic organization of polar and charged spectators at the interface, which do not in general need to be specifically chemisorbed onto the surface but could simply be close enough to the surface to be perturbed by the olefin adsorption. These results point toward electrochemical design handles, namely, the electrolyte, catalyst potential, and local E PZFC of the catalyst, with which to tune interfacial catalysis of thermochemical organic transformations.

adsorption↗
DOE OSTI2025

Operando Neutron Imaging of Reaction Extent and Particle Swelling Informs Limiting Factors for Salt Hydrate Thermochemical Energy Storage

Salt hydrates are a promising thermochemical energy storage medium that stores heat through the reversible uptake (hydration) and release (dehydration) of water vapor. Our study deploys operando neutron imaging to investigate salt hydrate performance with high spatial resolution (42 μm pixels). For flow over a packed bed with diffusion-driven transport, measurements reveal the formation of a solid diffusion layer due to particle swelling for the pure SrBr2 salt. In contrast, the SrBr2–vermiculite composite exhibits significantly less swelling and more than a 2-fold increase in the apparent water vapor diffusivity. For axial flow through a packed bed, neutron imaging confirms theoretically predicted transitions from a moving reaction front to a homogeneous profile with an increase in humid air flow rate. Our study establishes neutron imaging as a powerful technique to advance fundamental understanding of thermochemical systems and help guide composite material design.

Kinzer, Bryan [ORNL] (ORCID:0000000337804910)↗
DOE OSTI2020

Substituted SrFeO 3 as robust oxygen sorbents for thermochemical air separation: correlating redox performance with compositional and structural properties

Thermochemical air separation via cyclic redox reactions of oxide-based oxygen sorbents has the potential to achieve high energy efficiency. Although a number of promising sorbents have been investigated, further improvements in sorbent performance through a fundamental understanding of the structure–performance relationships are highly desirable. In this study, we systematically investigated the effects of A and B site dopants on the oxygen uptake/release properties (i.e., vacancy formation energy, reduction enthalpy, oxygen release temperature, and oxygen capacity) of the SrFeO 3 family of perovskites as oxygen sorbents. A monotonic correlation between DFT calculated oxygen vacancy formation energy and oxygen release temperature demonstrates the effectiveness of DFT for guiding sorbent selection. Combining vacancy formation energy with stability analysis, dopants such as Ba and Mn have been identified for tuning the redox property of SrFeO 3 sorbents, and increasing the oxygen capacity for temperature and pressure swings when compared to undoped SrFeO 3 . The Mn doped sample proved to be highly stable, with less than a 3% decrease in capacity over 1000 cycles. Although the dynamic nature of the redox process makes it difficult to use a single vacancy formation energy as the descriptor, a systematic approach was developed to correlate the oxygen storage capacities with the sorbents’ compositional properties and vacancy formation energies. The combination of DFT calculations with experimental studies from this study provides a potentially effective strategy for developing improved sorbents for thermochemical air separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The effect of switchgrass plant cell wall properties on its deconstruction by thermochemical pretreatments coupled with fungal enzymatic hydrolysis or Clostridium thermocellum consolidated bioprocessing

A combination of thermochemical pretreatment and biological digestion technologies is usually required to overcome lignocellulosic recalcitrance and accomplish effective biomass deconstruction. In this study, we aimed to understand switchgrass breakdown by hydrothermal, dilute acid, dilute alkali, and co-solvent enhanced lignocellulosic fractionation (CELF) pretreatments followed by application of traditional fungal enzymatic hydrolysis (EH) and Clostridium thermocellum consolidated bioprocessing (CBP) to the resulting solids. Unpretreated and pretreated switchgrass and their EH and CBP residues were characterized by a suite of analytical techniques to understand structural changes that occurred during deconstruction. CELF pretreated solids showed the highest accessibility and digestibility by both EH and CBP followed by dilute alkali and then dilute acid/hydrothermal pretreated solids. Lignin removal from biomass had a more positive impact on substrate accessibility and digestibility than did xylan removal, while xyloglucan removal by pretreatment appeared essential for cellulose digestion by fungal enzymes. The extent of CBP digestion of cellulose and non-cellulosic glycans was larger than that by EH. Unlike dilute alkali pretreatment, cellulose crystallinity increased for acid-based pretreatments in the following order: hydrothermal, dilute acid, and CELF. Acid-based pretreatments also substantially reduced cellulose degree of polymerization. All thermochemical and biological digestion approaches increased syringyl to guaiacyl lignin (S/G) ratio and reduced β-O-4 lignin interunit linkage and hydroxycinnamates content from levels in unpretreated switchgrass. The substantial increase in S/G ratio after hydrothermal and dilute alkali preatreatments suggested that high temperatures or alkali removed a large portion of G lignin from switchgrass.

09 BIOMASS FUELS↗
DOE OSTI2021

Thermochemical Modeling in Molten Fluoride Salts for Radionuclide Speciation

An important aspect of the licensing process for nuclear reactors is providing a reasonable assurance of safety to the general public. This includes modeling potential radionuclide releases from the reactor during normal operations and accident scenarios, which is known as the reactor’s source term. A new class of advanced (non-LWR) reactors are being developed which use molten salts as the coolant fluid. Because the molten salt coolant represents a credited barrier for radionuclide transport between the fuel and the environment, a necessary aspect of mechanistic source term (MST) analysis for the KP-FHR is modeling the thermochemistry of molten salts. Provided here is a review of the theory of the thermodynamic principles governing multicomponent phase equilibria, the background of molten salt thermochemistry research, and a summary of the thermochemical data relevant to the KP-FHR coolant salt, Li 2 BeF 4 , commonly referred to as “FLiBe”. A review of literature is followed by a brief introduction to methods that can be used to model the thermochemical behavior of molten salt mixtures. The methodology outlined is based on the use of a commercial thermodynamic modeling software called FactSage, which is one of only a few available softwares based on the modified quasichemical model(MQM), which is the recommended solution model for molten salts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Solid State Solar Thermochemical Fuel (SoFuel) for Long Duration Storage

Efficient thermal storage systems, when coupled with renewable energy, enable the decarbonization of numerous industrial processes requiring high temperature steam or air, and provide a path for seasonal building heating, especially for colder climates. Existing thermal storage systems face a significant challenge due to losses inherent to all high temperature systems. A viable route to long-term storage is to use thermochemical reactions to convert concentrated solar energy to a fuel that is shelf-stable and can be stored at room temperature, thus eliminating losses associated with high temperature storage. The Solid-State Solar Thermochemical Fuel (SoFuel) technology developed by Michigan State University, Oregon State University, and Mississippi State University provides reactors and processes with minimal sensible heat losses and allows storing solar energy as a solid-state fuel at room temperature for long duration. The production of SoFuel occurs within a cylindrical cavity reduction chemical reactor that captures concentrated solar radiation from a solar field. Reactive magnesium manganese oxide (Mg-Mn-O) resides within the cylindrical cavity chemical reactor and undergoes thermal reduction as the temperature exceeds 1350°C. The thermally reduced Mg-Mn-O pellets (the SoFuel) are cooled down through a recuperative process and stored within a bin until used. The SoFuel can directly supply up to 1100C heat to an adjacent power plant for electricity generation or industrial heating. Oxidation of SoFuel pellets occurs in a counter flow reactor and supplies heat to the user for electricity generation or industrial processing, after which the fuel is returned to the concentrating solar field where it is regenerated for re-use. Both reactors can be controlled well using a variety of strategies. With the low cost of the material, its cyclability, and the possibility of using the pelletized with on-sun reactors, or with electricity that would be curtailed, this project offers a viable option of medium- and long-term thermal energy storage.

25 ENERGY STORAGE↗
DOE OSTI2020

Preservation of Microalgae, Lignocellulosic Biomass Blends by Ensiling to Enable Consistent Year-Round Feedstock Supply for Thermochemical Conversion to Biofuels

Seasonal variation in microalgae productivity is a significant barrier to economical production of algae biofuels and chemicals. Summer production can be 3–5 times higher than in the winter resulting in uneven feedstock supplies at algae biorefineries. A portion of the summer production must be preserved for conversion in the winter in order to maintain a biorefinery running at capacity. Ensiling, a preservation process that utilizes lactic acid fermentation to limit microbial degradation, has been demonstrated to successfully stabilize algae biomass (20% solids) and algae-lignocellulosic blends (40% algae-60% lignocellulosic biomass, dry basis) for over 6 months, resulting in fuel production cost savings with fewer emissions. Preservation of algae as blends could be beneficial to biorefineries that utilize thermochemical approaches to fuel production as co-processing of algae and lignocellulosic biomass has been observed to enhance biocrude yield and improve oil quality. This study conducts a resource assessment of biomass residues in the southern United States to identify materials available during peak algae productivity and in sufficient quantity to meet the algae storage needs of an algae biofuel industry. Eight feedstocks met the quantity threshold but only three, distillers grains, haylage, and yard waste, were also available in season. Storage experiments utilizing both freshwater and marine strains of microalgae – Scenedesmus acutus, Chlorella vulgaris, Chlorella zofingiensis, Nannochloropsis gaditana, and Porphyridium purpureum – and yard waste were conducted for 30 days. Storage losses were less than 10% in all but one case, and the pH of all but one blend was reduced to less than 4.7, indicating that yard waste is a suitable feedstock for blending with algae prior to storage. To better understand whether the benefits to conversion realized by processing blends might be affected by storage, elemental analysis and bomb calorimetry of pre- and post-storage algae-yard waste blends were conducted to characterize changes occurring during storage. Storing algae biomass as blends with lignocellulosic biomass could be an effective method of mitigating seasonal variability in algae biomass production while retaining the synergistic effect of co-processing algae blends in thermochemical conversion.

09 BIOMASS FUELS↗
DOE OSTI2024

Production of sugars from lignocellulosic biomass via biochemical and thermochemical routes

Sugars are precursors to the majority of the world’s biofuels. Most of these come from sugar and starch crops, such as sugarcane and corn grain. Lignocellulosic sugars, although more challenging to extract from biomass, represent a large, untapped, opportunity. In response to the increasing attention to renewable energy, fuels, and chemicals, we review and compare two strategies for extracting sugars from lignocellulosic biomass: biochemical and thermochemical processing. Biochemical processing based on enzymatic hydrolysis has high sugar yield but is relatively slow. Thermochemical processing, which includes fast pyrolysis and solvent liquefaction, offers increased throughput and operability at the expense of low sugar yields.

Energy & Fuels↗
DOE OSTI2024

Applications of Thermochemical Modeling in Molten Salt Reactors

The extensively evaluated and consistent thermodynamic database, the Molten Salt Thermal Properties Database—Thermochemical (MSTDB-TC), was used along with additional thermodynamic values from other sources as examples of ways to examine molten salt reactor (MSR) fuel behavior. Relative stability with respect to halide potential and temperature for likely fuel and fission product components were mapped in Ellingham diagrams for the chloride and fluoride systems. The Ellingham diagrams provide a rich, visual means for identifying halide-forming components in proposed fuel/solvent salt systems. Thermochemical models and values from MSTDB-TC and ancillary sources were used in global equilibrium calculations to provide compositions for a close analysis of the behavior of a possible Molten Chloride Salt Fast Reactor and a Molten Salt Reactor Experiment-type system at high burnup (100 GWd/t). The results illustrated the oxidative nature of burnup in MSRs and provided information about redox behavior and possible control.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Comparative Life Cycle Assessment of Bacterial and Thermochemical Retting of Hemp

The processes of hemp bast fiber retting, forming, and drying offer the opportunity for value-added products such as natural fiber-reinforced composites. A new process for the retting of raw bast fibers through enzyme-triggered self-cultured bacterial retting was developed in the lab-scale setup. This study focused on comparing the energy consumption and environmental impacts of this bacterial retting process with the thermochemical retting process currently widely used to obtain lignocellulosic fibers for composites. The gate-to-gate life cycle assessment (LCA) models of the two retting processes were constructed to run a comparison analysis using the TRACI (the tool for the reduction and assessment of chemical and other environmental impacts) method for environmental impacts and the cumulative energy demand (CED) method for energy consumptions. This work has demonstrated the advantages of the bacterial retting method from an environmental standpoint. The result of our research shows about a 24% gate-to-gate reduction in CED for bacterial retting and 20–25% lower environmental impacts relating to global warming, smog formation, acidification, carcinogenics, non-carcinogenics, respiratory effects, ecotoxicity, and fossil fuel depletion when compared to that of thermochemical retting.

Chemistry↗
DOE OSTI2020

Methods for operating solar-thermochemical processes

Methods for controlling or operating solar thermochemical reactions process that maximize the two-step thermochemical energy cycle efficiency by a combination of pressure and temperature swing are disclosed.

14 SOLAR ENERGY↗
DOE OSTI2024

Accelerating Thermochemical Equilibrium Calculations for Nuclear Reactor Applications

Thermochemical properties play a key role in modeling and simulation of several key phenomena in nuclear reactors. There has been an increasing interest in incorporating CALPHAD-based formulations in multiphysics simulations including for Molten Salt Reactors where knowledge of phase evolution of the salt and the chemical potentials of various elements are of utmost importance in source term analyses and redox control. However, the size of such simulations is often limited by the high computational cost of full thermodynamic equilibrium calculations. This work discusses the current efforts aimed at accelerating thermochemical equilibrium calculations for multiphysics simulations performed using the open-source finite element / finite volume code Multiphysics Object Oriented Simulation Environment (MOOSE) [1]. While several methods have been proposed for accelerating phase equilibrium calculations [2], most focus on relatively small systems and often rely on a- priori knowledge of the state-space of the system. Nuclear materials, however, are often multi-component systems owing to the evolution of composition under irradiation and an approach based on a-priori mapping of phase diagram is often not enough. This work is aimed at demonstrating an on-the-fly surrogate modeling framework that uses active learning to reduce the number of full equilibrium calculations that must be performed. By combining with efficient coupling approaches, the surrogate framework helps in reducing the computational cost of thermodynamic equilibrium informed multiphysics simulations of nuclear materials. The performance is benchmarked against full coupling with the thermochemistry library Thermochimica [3]. This work uses a machine learning based approach for constructing surrogate models to predict the stable phases in a multicomponent system. The surrogates were constructed using neural networks and Gaussian process classification. In this work, we compare the relative performance of the two methods. We also demonstrate the use of caching previous calculations by interpolating the values from nearest neighbors. References [1] Lindsay, A.D., et al. "2.0 – MOOSE: Enabling massively parallel multiphysics simulation", SoftwareX, 20 (2022): 101202. [2] Roos, W.A. and Zietsman J.H. "Accelerating complex chemical equilibrium calculations – A Review", Calphad, 77 (2022): 102380. [3] Piro, M.H.A., et al. "The thermochemistry library Thermochimica", Computational Materials Science, 67 (2013): 266-272.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Non-Electricity Based Renewable Fuels: Theory and Computation for Solar Thermochemical Hydrogen

Dominated by photovoltaics and wind, current renewable energy sources generate mostly electricity, but 80% of the global final energy consumption occurs in form of fuels. Therefore, direct solar fuel generation would be a major breakthrough for the energy transition. Solar thermochemical hydrogen (STCH) is one of the very few potential routes towards scalable renewable fuels, but currently suffers from lack of an oxide working material that could optimally perform energy conversion within the thermodynamic boundary conditions. Theory and computation can contribute in two distinct ways, through materials search and discovery, but also by providing detailed mechanistic models for specific systems so to advance our understanding of possible design strategies. To enable high-throughput materials screening, we developed a defect graph neural network (dGNN) machine learning approach,[1] which accelerates the prediction of defect formation energies by replacing the tedious density functional theory (DFT) supercell calculations for all possible defect sites. This approach enables high-throughput database screening of oxides, which was integrated with thermodynamic modeling to extract the reduction entropies as additional selection criterion for STCH. Once potential candidate materials are identified, detailed models can guide materials design by predicting performance characteristics. One challenge is to quantitatively predict thermochemical equilibria at high concentrations when the redox active defects start to interact with each other, thereby impeding the formation of additional defects. Introducing a model for the free energy of defect interaction, parametrized on the basis of DFT data, we simulated the complete STCH redox cycle for (Sr,Ce)MnO3 alloys, achieving near-quantitative agreement with experimental data.[2] The analysis of these simulations reveals how defect interactions diminish the reduction entropy and H2 yield, suggesting to include these interactions in design considerations. Finally, we revisit the popular van't Hoff method for analyzing reduction enthalpies and entropies. This method is not ideal, as it involves a temperature-dependent convolution of gas-phase and solid-state entropies, causing uncertainties in the same order of magnitude as the physical quantities of interest. To avoid this problem, we suggest a simple alternative approach which can be applied to experimental and simulated data alike.

first-principles calculations↗
DOE OSTI2024

High-temperature thermochemical energy storage materials using doped magnesium-transition metal spinel oxides

High-temperature thermochemical energy storage materials using doped magnesium-transition metal spinel oxides are provided. —transition metal spinel oxides, such as magnesium manganese oxide (MgMn) 3 O 4 , are promising candidates for high-temperature thermochemical energy storage applications. However, the use of these materials has been constrained by the limited extent of their endothermic reaction. Embodiments described herein provide for doping magnesium-transition metal spinel oxides to produce a material of low material costs and with high energy densities, creating an avenue for plausibly sized modules with high energy storing capacities.

Muhich, Christopher↗