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Results for “Enthalpy method”

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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Investigating Fast Scanning Calorimetry and Differential Scanning Calorimetry as Screening Tools for Thermoset Polymer Material Compatibility with Laser-Based Powder Bed Fusion

As additive manufacturing (AM) technology has developed and progressed, a constant topic of research in the area is expanding the library of materials to be used with these techniques. Among AM methods that utilize polymers, laser-based powder bed fusion (PBF-LB) has preferentially used thermoplastic polymers as its starting materials, but the deposition and material joining method employed in PBF-LB may also be compatible with powdered thermoset polymer precursors as feedstocks. To assess the compatibility of candidate thermosetting polymers and PBF-LB, characterization techniques and protocols that link fundamental material behavior to material behavior in the processing environment are needed. Therefore, the objectives of this work are to compare the curing behavior measured with two different calorimetry techniques that can operate in different heating rate regimes, differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC), and to assess the capabilities of these techniques to act as materials screening tools for PBF-LB. A commercial polyester powder coating is used as a model material to evaluate the potential of obtaining complimentary information for material screening through a combination of calorimetry methods, and its non-isothermal curing behavior is measured at heating rates between 5 °C/min and 7500 °C/min. Curing exotherms are observed with both calorimetry techniques, and comparing the enthalpy associated with curing shows that incomplete curing occurs at higher heating rates, with relative conversion values of approximately 30%. The curing data are fit with two isoconversional models, Friedman and Starink, which show a reduced activation energy at higher heating rates as well, signifying a lower barrier to curing at the conditions used in the FSC experiments. Overall, the results of this work indicate that using these two calorimetry techniques as tiered screening tools can provide valuable information about how curing may proceed in PBF-LB and inform materials selection and design activities for additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A Computational Framework to Accelerate the Discovery of Perovskites for Solar Thermochemical Hydrogen Production: Identification of Gd Perovskite Oxide Redox Mediators

A high-throughput computational framework to identify novel multinary perovskite redox mediators is presented, and this framework is applied to discover the Gd-containing perovskite oxide compositions Gd 2 BB'O 6 , GdA'B 2 O 6 , and GdA'BB'O 6 that split water. The computational scheme uses a sequence of empirical approaches to evaluate the stabilities, electronic properties, and oxygen vacancy thermodynamics of these materials, including contributions to the enthalpies and entropies of reduction, ΔH TR and ΔS TR . This scheme uses the machine-learned descriptor τ to identify compositions that are likely stable as perovskites, the bond valence method to estimate the magnitude and phase of BO 6 octahedral tilting and provide accurate initial estimates of perovskite geometries, and density functional theory including magnetic- and defect-sampling to predict STCH-relevant properties. Eighty-three promising STCH candidate perovskite oxides down-selected from 4392 Gd-containing compositions are reported, three of which are referred to experimental collaborators for characterization and exhibit STCH activity. Our results demonstrate that the high-throughput computational scheme described herein—which is used to evaluate Gd-containing compositions but can be applied to any multinary perovskite oxide compositional space(s) of interest—accelerates the discovery of novel STCH active redox mediators with reasonable computational expense.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Room temperature calorimetry methods were developed to describe the energy landscapes of six polyoxometalates (POMs), Li–U 24 , Li–U 28 , K–U 28 , Li/K–U 60 , Mo 132 , and Mo 154 , in terms of three components: enthalpy of dissolution (ΔH diss ), enthalpy of formation of aqueous POMs (ΔH f,(aq) ), and enthalpy of formation of POM crystals (ΔH f,(c) ). ΔH diss is controlled by a combination of cation solvation enthalpy and the favorability of cation interactions with binding sites on the POM. In the case of the four uranyl peroxide POMs studied, clusters with hydroxide bridges have lower ΔH f,(aq) and are more stable than those containing only peroxide bridges. Here, in general for POMs, the combination of calorimetric results and synthetic observations suggest that spherical topologies may be more stable than wheel-like clusters, and ΔH f,(aq) can be accurately estimated using only ΔH f,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.

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

Degree of rate control and De Donder relations – An interpretation based on transition state theory

We describe sensitivities of elementary steps as salient parameters in determining the rate determining character of elementary steps within a reaction network and develop a formalism wherein the overall composite reaction is described by an apparent rate-determining step that is a sensitivity-weighted average of the elementary steps that comprise the reaction. Reaction parameters—apparent reaction orders, apparent enthalpy and entropy of activation—of the composite reaction network are determined within the framework we develop by application of transition state theory to the apparent rate-determining step. From this formalism we develop methods for determination of surface coverages by measuring only reaction orders, novel methods for discrimination between proposed mechanisms, a proof that the kinetic degrees of rate control sum to unity, and a proof for the relationship between fractional coverages and thermodynamic degrees of rate control. Two complementary formalisms for identifying rate-limiting transition states are broadly employed in chemical kinetics—De Donder relations based on measuring the thermodynamic driving forces of elementary steps during reaction and degrees of rate control based on knowledge of the kinetics of elementary reaction steps. Here, the formalism developed herein unifies these two strategies to elucidate in the most general case a relationship between the thermodynamic driving forces of elementary steps captured by the reversibilities and the kinetic and thermodynamic degrees of rate control.

42 ENGINEERING↗
DOE OSTI2023

Superconductivity in the Li-B-C system at 100 GPa

Layer Li-B-C compounds have been shown to have feasible superconductivity. Using the adaptive genetic algorithm, we predict the structures of the Li-B-C system at 100 GPa. Here we identify several low-enthalpy metallic phases with stoichiometries of Li B 2 C, Li B 3 C, Li 2 BC 2 , Li 3 B 2 C 3 , Li 3 BC, and Li 5 BC. Using a fast screening method of electron-phonon interaction, we find that Li B 3 C is a promising candidate for superconductivity. The consecutive calculations using the full Brillouin zone confirm the existence of the strong electron-phonon coupling (EPC) in this system. The anharmonic B-C phonon modes near the zone center provide the major contribution to the EPC. The EPC constant is 1.40, and the estimated critical temperature is 22 K. In this paper, we indicate that superconductivity can also happen without a layered structural motif in the Li-B-C system. We also demonstrate an effective strategy for crystal structure prediction of superconducting materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Improving tropical cyclone rapid intensification forecasts with satellite measurements of sea surface salinity and calibrated machine learning

Forecasting rapid intensification (RI) of tropical cyclones (TC) is a mission known for large errors. One under-researched factor that affects TC intensification is salinity, which is important for density stratification in certain ocean regions and can affect the surface enthalpy flux under a strengthening hurricane. To investigate the impact and efficacy of using salinity information in state-of-the-art forecasting, we use a statistical model consisting of a variety of machine learning (ML) methods. For salinity data, we use satellite measurements of pre-storm sea surface salinity (SSS) as a proxy for the salinity stratification. We train and test the model on various ocean basins, including the Atlantic, eastern North Pacific and western North Pacific. A calibrator is trained on top of the ML models to correct and enhance probability forecasts. The calibrator significantly improves probability forecasts relative to recent works. The ML model performance is improved with the addition of SSS in the Eastern North Pacific, western North Pacific, and the Caribbean subregion of the North Atlantic, and the overall model performance is better than previous studies. SSS decreases model skill for a model trained on the full Atlantic basin. In the Indian Ocean, SSS is also notably correlated with RI occurrence, but the TC samples are not sufficient to train ML models.

hurricane↗
DOE OSTI2023

Uncovering novel liquid organic hydrogen carriers: a systematic exploration of chemical compound space using cheminformatics and quantum chemical methods

We present a comprehensive, in silico-based discovery approach to identifying novel liquid organic hydrogen carrier (LOHC) candidates using cheminformatics methods and quantum chemical calculations. We screened over 160 billion molecules from ZINC15 and GDB-17 chemical databases for structural similarity to known LOHCs and employed a data-driven selection criterion connecting molecular features with dehydrogenation enthalpy. This scoring criterion effectively predicts dehydrogenation enthalpies from SMILES strings, streamlining the LOHC screening process. After rigorous screening and down-selection, we compiled a database of 3000 dehydrogenation reactions for the most promising LOHC candidates, setting the stage for future selection based on kinetics and catalysis. This work demonstrates the significant impact of integrating quantum chemistry and cheminformatics in materials discovery, accelerating the selection process while reducing experimental efforts and time. By proposing new molecules as prospective LOHC candidates, our study provides a valuable resource for researchers and engineers in the development of advanced LOHC systems and showcases a successful approach for high-throughput discovery, contributing to more efficient and sustainable energy storage solutions.

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

Experimental determination of the solubility constant of kurnakovite, MgB3O3(OH)5·5H2O

In this study, I present experimental results on the equilibrium between boracite [Mg 3 B 7 O 13 C1(cr)] and kurnakovite [chemical formula, Mg 2 B 6 O 11 ·15H 2 O(cr); structural formula, MgB 3 O 3 (OH) 5 ·5H 2 O(cr)] at 22.5 ± 0.5 °C from a long-term experiment up to 1629 days, approaching equilibrium from the direction of supersaturation, Mg 3 B 7 O 13 C1(cr) + H + + 2B(OH)$^-_4$ + 18H 2 O(1) ⇌ 3MgB 3 O 3 (OH) 5 ·5H 2 O(cr) + C1 - . Based on solubility measurements, the 10-based logarithm of the equilibrium constant for the above reaction at 25 °C is determined to be 12.83 ± 0.08 (2σ). Based on the equilibrium constant for dissolution of boracite, Mg 3 B 7 O 13 C1(cr) + 15H 2 O(1) = 3Mg 2+ + 7B(OH)$^-_4$ + C1 - + 2H + at 25 °C measured previously (Xiong et al. 2018) and that for the reaction between boracite and kurnakovite determined here, the equilibrium constant for dissolution of kurnakovite, MgB 3 O 3 (OH) 5 ·5H 2 O(cr) = Mg 2+ + 3B(OH)$^-_4$ + H + + H 2 O(1) is derived as -14.11 ± 0.40 (2σ). Using the equilibrium constant for dissolution of kurnakovite obtained in this study and the experimental enthalpy of formation for kurnakovite from the literature, a set of thermodynamic properties for kurnakovite at 25 °C and 1 bar is recommended as follows: Δ H $^0_f$ = -4813.24 ± 4.92 kJ/mol, Δ G$^0_f$ = -4232.0 ± 2.3 kJ/mol, and S 0 = 414.3 ± 0.9 J/(mol·K). Among them, the Gibbs energy of formation is based on the equilibrium constant for kurnakovite determined in this study; the enthalpy of formation is from the literature (Li et al. 1997), and the standard entropy is calculated internally with the Gibbs-Helmholtz equation in this work. The thermodynamic properties of kurnakovite estimated using the group contribution method for borate minerals based on the sums of contributions from the cations, borate polyanions, and structural water to the thermodynamic properties from the literature (Li et al. 2000) are consistent, within their uncertainties, with the values listed above. Since kurnakovite usually forms in salt lakes rich in sulfate, studying the interactions of borate with sulfate is important to modeling kurnakovite in salt lakes. Finally, for this purpose, I have re-calibrated our previous model (Xiong et al. 2013) describing the interactions of borate with sulfate based on the new solubility data for borax in Na 2 SO 4 solutions presented here.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High pressure melt line of nickel using a generalized embedded atomic method potential

As the second most abundant metal in the Earth's core, nickel plays an important role in determining the structure and temperature of the Earth's core. Yet, the melt line of Ni at pressures corresponding to the Earth's core has not been explored in the literature. Many previous experimental and simulation efforts have reported the melting point of Ni at pressures below 100 GPa, but there exist large discrepancies, most of which have persisted due to various experimental and simulation bottlenecks in handling extreme pressure and temperature conditions. We adopted the generalized embedded atom method, which overcomes the limitations of existing interatomic potentials, to probe phase stability and phase boundaries of Ni at pressures between 50 and 500 GPa. Further, the potential was validated by comparing the cold curves, phonon dispersion curves, and enthalpies of fusion with ab initio density functional theory calculations. Our analysis shows that face centered cubic (FCC) is stable, and the hexagonal close packed (HCP) and body centered cubic (BCC) phases are metastable close to the melt line. Melting temperatures at different pressures were obtained from two-phase co-existence simulations and take the following functional form: $T$ m = $1969.23+19.15P-0.012P$ 2 . In contrast to iron, differences between the melting points of the stable and metastable phases of Ni are less than 250 K at 300 GPa, and the difference in melting points of the metastable BCC and HCP phases changes sign at 500 GPa, which implies that the phase transition mechanisms during solidification can be very complex.

36 MATERIALS SCIENCE↗
DOE OSTI2021

DFTTK: Density Functional Theory ToolKit for high-throughput lattice dynamics calculations

In this work, we present a software package in Python for high-throughput first-principles calculations of thermodynamic properties at finite temperatures, which we refer to as DFTTK (Density Functional Theory ToolKit). DFTTK is based on the atomate package and integrates our experiences in the last decades on the development of theoretical methods and computational softwares. It includes task submissions on all major operating systems and task executions on high-performance computing environments. Furthermore, the distribution of the DFTTK package comes with examples of calculations of phonon density of states, heat capacity, entropy, enthalpy, and free energy under the quasi-harmonic phonon scheme for the stoichiometric phases of Al, Ni, Al 3 Ni, AlNi, AlNi 3 , Al 3 Ni 4 , and Al 3 Ni 5 , and the fcc solution phases treated using the special quasirandom structures at the compositions of Al 3 Ni, AlNi, and AlNi 3 .

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

A review of cladding failure thresholds in RIA conditions based on transient reactor test data and the need for continued testing

Transient reactor experiments on light water reactor (LWR) fuel pins had been conducted since the beginning of the nuclear era to help determine core coolability and cladding failure thresholds. During one such test in November of 1993 at the CABRI transient test reactor on a test involving a high burnup fuel rod with a corroded Zircaloy-4 cladding it was first observed that cladding failures could occur prior to a departure from nucleate boiling (pre-DNB) at lower-than-expected peak radial average enthalpies. This paper will present an independent review of the publicly available transient reactor test database on higher burnup LWR pins conducted at the CABRI and NSRR reactors as well as review of a selection of published out of pile mechanical testing methods. The purpose of the review is to determine how well the new regulatory limits are supported by experimental data. The review will identify if additional transient reactor tests could provide additional support for the NRC guidance or identify the need for revisions. The evaluation will consider how far the existing database can be extrapolated when considering low hydrogen zirconium alloy claddings (with and without protective coatings) containing very high burnup (> 70 MWd/kgU) UO2 fuel pellets. Finally, the authors will suggest how out of pile mechanical tests can be used in conjunction with a limited number of transient reactor tests to develop cladding specific failure thresholds in RIA type transients.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Macro-level mechanical interlocking: A rapid joining approach for additively manufactured compression molded composite panels

Composite joining typically involves multiple steps, such as drilling and surface treatment, as part of the manufacturing process, which leads to low throughput and long cycle times. In the present study, we demonstrated a macro-level mechanical interlocking (MI) based, rapid joining technique to assemble additively manufactured compression molded (AMCM) panels, enabling the production of parts larger than the mold dimensions. Composite panels made of 20 wt% short carbon fiber reinforced acrylonitrile butadiene styrene (CF/ABS) were joined using MI features of various geometries, namely tree (TR), dovetail (Dov), rectangle 2 (Rect2), and rectangle 1 (Rect1), and their in-plane strength was evaluated. The resultant strength of the tested MI joints reached up to 74 % of the baseline tensile strength (i.e., the ‘no joint’ case). Observations from optical and scanning electron microscopy revealed inadequate polymer diffusion between the adherends, indicating that the joint strength was primarily derived from mechanical interlocking. Additionally, the fracture surfaces exhibited stress-whitening marks, which were characterized using differential scanning calorimetry (DSC). The increase in melting enthalpy suggested local stretching of polymer chains due to MI. Finite element analysis (FEA) indicated that the Rect1 MI feature, which generated the lowest stress concentration, outperformed the others in terms of joint strength, achieving 42 MPa. As a demonstration of the MI joining method, a battery box tray measuring 108 cm × 34 cm using a mold with an effective dimension of 36 cm × 34 cm successfully manufactured, resulting in a part with an area three times larger than the mold. In conclusion, this study presents a promising approach to improving composite joining techniques while minimizing production complexities.

In-plane joining↗
DOE OSTI2022

Overcoming significant challenges in extracting off-stoichiometric thermodynamics using the compound energy formalism through complementary use of experimental and first principles data: A case study of Ba 1-x Sr x FeO 3-δ

The compound energy formalism (CEF) is a powerful framework to describe the thermodynamics of metal oxides as a function of off-stoichiometry, temperature, and composition. The thermodynamic properties are crucial materials design attributes in metal oxide-based oxygen-exchange chemical processes. Despite the richness of information an accurate CEF model provides, a method to determine a unique and accurate fit for oxygen exchange materials remains elusive. This contribution details a method for fitting the CEF model that overcomes the current fitting challenges through three innovations: 1) the combination of density functional theory calculations with experimental data decorrelates excess terms and delineates the enthalpic/entropic contributions to the Gibbs free energy; 2) a systematic determination of the important CEF model terms, removing thermodynamic predetermining human intervention; 3) a self-consistent solution of the starting oxygen offstoichiometry (δ 0 ) of thermogravimetric measurements. Thus, our method enables the reliable extraction of off-stoichiometric metal oxide thermodynamic properties and facilitates rapid materials compositional screening, and reliable process design of systems dependent on off-stoichiometric redox-active metal oxides. We apply this method to a Ba x Sr 1-x FeO 3-δ test case. We find by systematically examining the performance of the CEF model fit with and without each innovation that all three innovations are necessary for an accurate fit. We determined that reduction enthalpy is higher and more sensitive to off-stoichiometry when the Sr fraction is large (139.5 and 185.3 kJ/mol O 2 for SrFeO 3 at δ = 0 and δ = 0.5, respectively vs. nearly constant 83 kJ/mol O 2 for BaFeO 3 ). However, the reduction entropy is mostly insensitive to Sr fraction, but highly dependent on δ suggesting larger contributions in the non-configurational entropy parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ethylene Hydrogenation Molecular Mechanism on MoC y Nanoparticles

Ethylene hydrogenation catalyzed by MoC y nanoparticles has been studied by means of density functional theory methods and several models. These include MetCar (Mo 8 C 12 ), Nanocube (Mo 14 C 13 ), and Mo 12 C 12 nanoparticles as representatives of experimental MoC y nanostructures. The effect of hydrogen coverage has been studied in detail by considering low-, intermediate-, and high-hydrogen regimes. The calculated enthalpy and energy barriers show that ethylene hydrogenation is feasible on the MetCar, Mo 12 C 12 , and Nanocube but at low, medium, and high hydrogen coverages, respectively. An additional step, related to the H* migration from a Mo to a C site in the nanoparticle, has been found to be the key to establishing the best hydrogenation system. In most cases, the reactions are exothermic, featuring low hydrogenation energy barriers, especially for the Nanocube at high hydrogen coverage. In addition, the calculated adsorption Gibbs free energy shows that, for this system, the C 2 H 4 adsorption is feasible in the 300–400 K temperature range and pressures from 10 –10 to 2 atm. For the hydrogenation steps, calculated transition state theory rates show that the overall process is limited by the first hydrogenation step (C 2 H 4 → C 2 H 5 ) at temperatures of 330–400 K. However, at the lower temperatures of 300–320 K, the reaction rates are comparable for the two steps. The present results indicate that the Mo 14 C 13 Nanocube models of MoC y nanoparticles exhibit appropriate thermodynamic and kinetic features to catalyze ethylene hydrogenation at a high-hydrogen-coverage regime. The present findings provide a basis for understanding the chemistry of active MoC y catalysts, suggest appropriate working conditions for the reaction to proceed, and provide a basis for future experimental studies.

03 NATURAL GAS↗
DOE OSTI2021

Ultrafast conformational dynamics of Rydberg-excited N -methyl piperidine

We have observed the ultrafast conformational dynamics of electronically excited N-methyl piperidine (NMP) using time-resolved Rydberg fingerprint spectroscopy. Optical excitation at various wavelengths ranging from 212 nm to 229 nm leads to the 3s or 3p Rydberg states and induces coherent oscillatory motions with periods of about 700 fs. Furthermore, these coherent motions survive the internal conversion from 3p to 3s but then dephase on a time scale of a few oscillations. Intramolecular vibrational energy redistribution on a picosecond time scale leads to an equilibrium between two conformeric structures that are separated in binding energy by 0.09 eV. Model calculations using the DFT-SIC method are in excellent agreement with the experiments and identify the conformers as the chair and twist structures of NMP. The analysis of the equilibrium parameters at long time delays as a function of excitation wavelength allows for the extraction of thermodynamic parameters for the conformeric transformation. We derive an enthalpy of the chair to twist reaction in the 3s excited state of 62 meV with an entropy of 19.70 J mol –1 K –1 . An activation energy of 276 meV is also obtained with a kinetic model.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

First-principles prediction of incipient order in arbitrary high-entropy alloys: exemplified in Ti 0.25 CrFeNiAl

High-temperature disordered multi-component alloys, including high-entropy alloys, experience either segregation or partially-ordered phases to reach low-temperature phases. For Ti 0.25 CrFeNiAl x (0 ≤ x ≤ 1), experiments suggest a partially-ordered B2 phase, whereas CALculation of PHAse Diagrams (CALPHAD) predicts a region of L21+B2 coexistence. We employ first-principles KKR-CPA to assess stability of phases with arbitrary order and a KKR-CPA linear-response theory to predict atomic short-range order (SRO) in the disorder phase that reveals the competing long-range ordered (LRO) phases in a given Bravais lattice. The favorable SRO provides a specific concentration-waves (site occupation probabilities and partially-ordered unit cells) and estimated energy gains that can then be assess directly by KKR-CPA formation enthalpies. Our results are in good agreement with experiments and CALPHAD in Al-poor regions (x ≤ 0.75) and with CALPHAD in Al-rich region (1≥ x >0.75). Our first-principles KKR-CPA and SRO-based concentration-wave analysis is shown to be a powerful and fast method to assess competing LRO phases in complex solid-solution alloys, and our results suggests more careful experiments in Al-rich region are needed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Accurate Dehydrogenation Enthalpies Dataset for Liquid Organic Hydrogen Carriers

This contribution presents a comprehensive extension of the QM9 dataset (originally at 133 K molecules) with the calculation of G4MP2 enthalpies for 9,841 molecules, featuring up to nine heavy atoms. We present QM9-LOHC, a (de)hydrogenation dataset of 10,373 reactions, including a minimum of 5.5% weight hydrogen storage capacity in line with the Department of Energy standards for Liquid Organic Hydrogen Carriers (LOHC). By utilizing the accurate quantum chemical method G4MP2 we expand the QM9 database and explore new avenues for the exploration of hydrogen storage technologies (electrochemical LOHCs, alkali metal-LOHCs, and mixtures of LOHCs). The QM9-LOHC dataset, with its focus on reactions that vary only by hydrogen saturation levels, provides a needed data resource for advancing the design and optimization of both conventional and innovative LOHC systems, and high-fidelity data for molecular discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗