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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,117 records · Page 62
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Kinetic model development and Bayesian uncertainty quantification for the complete reduction of Fe-based oxygen carriers with CH 4 , CO, and H 2 for chemical looping combustion

In this work, three kinetic models are developed and calibrated for the complete multi-step reduction of an Fe-based oxygen carrier (OC) particle with CH 4 , CO, and H 2 , using data from thermogravimetric analysis. The complete reduction rate profiles exhibit complex dynamics whose trajectory is significantly different depending on the reducing gas. A Bayesian model building and parameter estimation framework is applied for simultaneous parameter and model structure uncertainty quantification. The final models show excellent agreement between model predictions and calibration data, as well as new data not used for calibration (for the reduction of the OC with CH 4 ). Parameter uncertainty is quantified by determining joint posterior distribution, and model structure uncertainty is addressed by incorporating Gaussian process stochastic functions (represented by Bayesian smoothing splines) into the kinetic models. The final kinetic models with discrepancy functions are readily employable in equation-oriented simulation and optimization platforms.

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

A comparative investigation of the effect of gas type on foam strength and flow behavior in tight carbonates

Foam generation technique has been practically applied to overcome gas mobility issue during enhanced oil recovery (EOR) processes. Incorporated with the utilized gas, the capability of foaming agent to generate persistent foam determines the flow performance under reservoir conditions. Here, in this study, we first identified the surfactants with excellent phase behavior and foaming properties and, second, evaluated their bulk foam performance with different gases, including N 2 , CO 2 , and hydrocarbon gas (CH 4 ) under high-pressure and high-temperature conditions. In bulk, the foam generated with the high-density gas, i.e., CO 2 , exhibited the greatest foamability but the lowest foam stability. With amidoamine oxide-based surfactant, CH 4 -foam was found to be more stable than N 2 -foam, while the opposite was observed for sulfobetaine-based surfactant. The most effective surfactant was later used to perform flow experiments on two tight carbonate rocks, including Minnesota Norther Cream Buff and Edwards limestone, with permeabilities of ~0.8 and 16 mD, respectively. The core-flooding experiments showed that the optimum quality of CO 2 -foam was lower than that of N 2 - and CH 4 -foams. For a given flow rate and fixed foam quality, the steady-state strength followed the descending order of CH 4 -, N 2 -, and CO 2 -foam. However, in general, the difference in foam strength between N 2 - and CH 4 -foams was insignificant when the total flow rate was varied. We also found that the variation in rock permeability had a greater effect on the strength of the CO 2 -foam compared to those generated with N 2 and CH 4 . In the presence of oil, the shear-thinning behavior of all foams was found more prominent. The increase in oil saturation had a more adverse effect on the strength of N 2 - and CH 4 -foams, particularly in the higher permeability rock. The results indicated that the foam strength, which is key in the effectiveness of foam EOR applications, is greatly influenced by several factors such as gas density, gas solubility in water, the presence of oil, and rock permeability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Upcycling mixed cathode materials to high-energy-density LiFe 0.75 Mn 0.25 PO 4

To address the demand for next-generation cathode materials with high energy density, upcycling LiFePO 4 into LiFe 0.75 Mn 0.25 PO 4 has attracted considerable attention. Nevertheless, existing strategies have yet to achieve both morphology and full elemental recovery under mild ambient conditions. Here, we report an upcycling route that can address this issue by combining leaching and a high-temperature treatment process. The upcycled LiFe 0.75 Mn 0.25 PO 4 exhibits enlarged lattice spacing and a high discharge plateau, and it delivers an energy density of 563.7 Wh/kg, 40.3 Wh/kg higher than recycled LiFePO 4 , which indicates the high value of the proposed upcycling strategy. At 1 C, LiFe 0.75 Mn 0.25 PO 4 also exhibits excellent cycling stability of 91% over 700 cycles. Techno-economic analysis also indicates impressive economic and environmental benefits, including 10.4% less raw materials usage and 12.2% less energy consumption and wastewater generation. This work demonstrates a scalable and economic upcycling strategy and provides a promising pathway for sustainable battery upcycling compatible with industrial conditions.

LMFP↗
DOE OSTI2021

Experimental and modeling studies of PR and ND oxalate solubility to high ionic strengths: Insight into actinide(III) oxalates

Actinide oxalates are chemical compounds important to nuclear industry, ranging from actinide separation in waste reprocessing, to production of specialty actinides, and to disposal of high level nuclear waste (HLW) and spent nuclear fuel (SNF). In this study, the solubility constants for Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O by performing solubility experiments in HNO 3 and mixtures of HNO 3 and H 2 C 2 O 4 at 23.0 ± 0.2 °C have been determined. The targeted starting materials, Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O, were successfully synthesized at room temperature using PrCl 3 , NdCl 3 and oxalic acid as the source metrials. Then, we utilized the targeted solubility-controlling phases to conduct solubility measurements. There was no phase change over the entire periods of experiments, demonstrating that Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O were the solubility-controlling phases in our respective experiments. Based on our experimental data, we have developed a thermodynamic model for Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O in the mixtures of HNO 3 and H 2 C 2 O 4 to high ionic strengths. The model for Pr 2 (C 2 O 4 ) 3 •10H 2 O reproduces well the reported experimental data for Pu 2 (C 2 O 4 ) 3 •10H 2 O, which are not utilized for the model development, demonstrating that Pr(III) is an excellent analog for Pu(III). Similarly, the model for Nd 2 (C 2 O 4 ) 3 •10H 2 O reproduces the solubility of Am 2 (C 2 O 4 ) 3 •10H 2 O and Cm 2 (C 2 O 4 ) 3 •10H 2 O. The Pitzer model was used for the calculation of activity coefficients. Based on the published, well established model for dissociation constants for oxalic acid and stability constants for actinide-oxalate complexes [i.e., AmC 2 O 4 + , and Am(C 2 O 4 ) 2 - ] to high ionic strengths, we have obtained the solubility constants (log 10 K 0 ) for the following reactions at 25 °C, Pr 2 (C 2 O 4 ) 3 •10H 2 O ⇌ 2Pr 3+ + 3C 2 O 4 2- + 10H 2 O(l). Nd 2 (C 2 O 4 ) 3 •10H 2 O ⇌ 2Nd 3+ + 3C 2 O 4 2- + 10H 2 O(l). to be -30.82 ± 0.30 (2σ), and - 31.14 ± 0.35 (2σ), respectively. These values for can be directly applied to Pu 2 (C 2 O 4 ) 3 •10H 2 O, Am 2 (C 2 O 4 ) 3 •10H 2 O and Cm 2 (C 2 O 4 ) 3 •10H 2 O. The model established for actinide oxalates by this study provides the needed knowledge with regard to solubilities of actinide/REE oxalates at various ionic strengths, and is expected to find applications in many fields, including the geological disposal of nuclear waste and the mobility of REE under the surface conditions, as Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O can be regarded as the pure Pr and Nd end-members of deveroite, a recently discovered natural REE oxalate with the following stoichiometry, (Ce 1.01 Nd 0.33 La 0.32 Pr 0.11 Y 0.11 Sm 0.01 Pb 0.04 U 0.03 Th 0.01 Ca 0.04 ) 2.01 (C 2 O 4 ) 2.99 •9.99H 2 O. Regarding its importance in the geological disposal of nuclear waste, Am 2 (C 2 O 4 ) 3 •10H 2 O/Pu 2 (C 2 O 4 ) 3 •10H 2 O/Cm 2 (C 2 O 4 ) 3 •10H 2 O can be the source-term phase for actinides, as demonstrated by the instance in the disposal in clay/shale formations. This is exemplified by the stability of Am 2 (C 2 O 4 ) 3 •10H 2 O in comparison with Am(OH) 3 (am), Am(OH) 3 (s) and AmCO 3 (OH)(s) under the relevant geological repository conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Lignin as a bioactive polymer and heavy metal absorber- an overview

As a pulping and bio-refinery by-product with phenolic chemical structure, lignin indicated high potential as natural antioxidant activity, UV blocker, antibacterial and toxic material absorbent properties. Presence of phenolic hydroxyl groups in lignin structure plays the main role of its antioxidant activity. However, lignin antioxidant power can change depending on its other structural features and functional groups like ortho-methoxy groups, –OCH 3 groups, the α-CH 2 groups, the aliphatic carbonyl groups, and the size of π-conjugated systems. Lignin in mixture with synthetic polymers, improved their thermal stability. Lignin has high UV light absorbing potential in broad-spectrum (UVA, UVB). Adding 1–5% of lignin into hand cream indicated excellent range of sun protection factor (SPF) with more than 95% UV light absorption. Lignin also indicated strong UV light protection when applied in different transparent film and protect paint, oil, and varnish from UV degradation. Further, lignosulfonate and other modified lignin including chemically modification, nano-particles and lignin hydrogel indicated high potential as heavy metal absorber.

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

A Principle for Highly Active Metal Oxide Catalysts via NaCl-Based Solid Solution

Toward the preparation of industrial metal oxide catalysts, sacrificial organic templates, excessive solvents, complex impregnation, and drying steps are generally required. Here, we report a versatile rule for the simple synthesis of highly porous metal oxides with well-dispersed noble metal species. Porous metal oxides (Co 3 O 4 , Fe x O y , and Cr 2 O 3 ) are obtained with some surface areas (e.g., Cr 2 O3: 224 m 2 ·g -1 ) beyond the record value. Surprisingly, small noble metal nanoparticles (e.g., Pd: 3.1 and Pt: 3.2 nm) could be incorporated by this solid-state process simultaneously. Corresponding Rh-Co 3 O 4 , Pd-Fe x O y , and Pt-Cr 2 O 3 exhibit excellent performance: CH 4 combustion (T90 = ~360°C and thermal stability: >100 h at 680°C), hydrogenation of nitrobenzene and derivatives (turnover number [TON] = 2.49 × 104, 300 mmol per run), and reversed water gas shift (RWGS) reaction (44% CO 2 conversion with ~98% CO selectivity and thermal stability: >100 h at 500°C), respectively. Therefore, current principle via a NaCl-based solid solution could provide a solid-state, fast, and efficient route for processing metal oxide catalysts.

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

Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

Exercising direct control over the unusual electronic structures arising from quantum confinement effects in graphene nanoribbons (GNRs) is intimately linked to geometric boundary conditions imposed by the structure of the ribbon. Besides composition and position of substitutional dopant atoms, the symmetry of the unit cell, width, length, and termination of a GNR govern its electronic structure. Here, we present a rational design that integrates each of these interdependent variables within a modular bottom-up synthesis. Our hybrid chemical approach relies on a catalyst-transfer polymerization that establishes excellent control over length, width, and end groups. Complemented by a surface-assisted cyclodehydrogenation step, uniquely enabled by matrix-assisted direct (MAD) transfer protocols, geometry and functional handles encoded in a polymer template are faithfully mapped onto the structure of the corresponding GNR. Bond-resolved scanning tunneling microscopy (BRSTM) and spectroscopy (STS) validate the robust correlation between polymer template design and GNR electronic structure.

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

Photoelectrocatalytic reduction of CO 2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon

The reduction of carbon dioxide (CO 2 ) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type ( R bpy)Mn(CO) 3 Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiO x -porSi). SiO x -porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiO x -porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO 2 reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm 2 ), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. Here, the applied potential is close to the equilibrium potential for CO 2 reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO 2 reduction to formate and the first on semiconducting silicon.

13 HYDRO ENERGY↗
DOE OSTI2023

Machine learning-based ethylene and carbon monoxide estimation, real-time optimization, and multivariable feedback control of an experimental electrochemical reactor

Electrochemical reduction of CO 2 gas is a novel CO 2 utilization technique that has the potential to mitigate the global climate crisis caused by anthropogenic CO 2 emissions, and enable the large-scale storage of energy generated from renewable sources in the form of carbon-based chemicals and fuels. However, due to the complexity of the electrochemical reactions, the explicit first-principles models for CO2 reduction are not available yet, and there has been a limited effort to develop process modeling, optimization and control of CO 2 electrochemical reactors. To this end, a rotating cylinder electrode (RCE) reactor has been constructed at UCLA to understand the mass transfer and reaction kinetics effects separately on the productivity. In the RCE reactor, the applied potential strongly influences the reaction energetics and the electrode rotation speed affects the hydrodynamic boundary layer and modifies the film mass transfer coefficient, which involves convective and diffusive transport. Further, the present work aims to develop a multi-input multi-output (MIMO) control scheme for the RCE reactor that integrates techniques from artificial and recurrent neural network modeling, nonlinear optimization, and process controller design. Specifically, production rates of two products from the experimental reactor, ethylene and carbon monoxide, are controlled by manipulating two inputs, applied potential and catalyst rotation speed. Process dynamics and controllability are analyzed, a feedback control strategy is designed and the controllers are tuned accordingly. The experimental electrochemical cell is employed to gather data for process modeling and implement the multivariable control system. Finally, the experimental results are presented which demonstrate excellent closed-loop performance by the control system and regulation of the outputs at three different set-points including an economically-optimal set-point.

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

Carbonation reaction of recycled concrete aggregates (RCA): CO 2 mass consumption under various treatment conditions

Concrete is a key building material around the world due to its excellent strength and durability. Recycling demolished concrete for new construction materials may play a significant role in sustainable development. Producing recycled concrete aggregates (RCA) from waste concrete is one approach for such an initiative. However, using RCA may pose challenges, such as reduced density, lower elastic modulus and strength, and increased water absorption. Recently, the carbonation of RCA has emerged as a method to address those concerns. This study explores the carbon sequestration capacity of RCA through carbonation, examining various parametric conditions, including initial CO 2 pressure, relative humidity, temperature, and pre-treatment approach. Both lab-scale and large-scale carbonation tests were conducted. Additionally, a cost analysis and CO 2 footprint assessment were performed. The findings showed that applying higher initial CO 2 pressures (e.g., 40–60 psi) and optimal relative humidity (~55 %) could significantly enhance the carbonation efficiency of RCA. Elevating temperature also led to accelerated CO 2 consumption, being more effective on the lab scale. The economic analysis presented potential cost benefits when substituting natural aggregates with CO 2 -treated RCA. All in all, these results suggest that the carbonation of RCA may provide significant environmental benefits through carbon sequestration, promoting sustainable construction practices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A thermodynamically consistent finite strain phase field approach to ductile fracture considering multi-axial stress states

Phase field models for ductile fracture have gained significant attention in the last two decades due to their ability in implicitly tracking the nucleation and propagation of cracks. However, most crack phase field formulations for elastoplastic solids focus only on the effects of plastic deformation, and do not consider the different multi-axial stress states that may arise in practical designs. In this work, a thermodynamically consistent phase field approach coupled with finite strain plasticity, considering multi-axial stress states is presented. In order to account for the coupling between plasticity and stress states, the Stress-Weighted Ductile Fracture Model (SWDFM) is utilized. The SWDFM represents a criterion for predicting ductile crack initiation under both monotonic and cyclic loadings based on histories of an internal plastic variable, stress triaxiality, and the Lode angle parameter. The excellent performance of the SWDFM for predicting ductile crack initiation motivates for its incorporation into a phase field approach for predicting both crack initiation and propagation through degradation of the fracture toughness. Moreover, based on the second law of thermodynamics, exact requirements are imposed on the rate at which the fracture toughness can evolve. Here, a novel function for degrading the plastic yield surface during the evolution of damage is introduced. This function, in line with experimental observations, leads to an accumulation of plastic deformation in damaged regions of a solid, and avoids numerical instabilities arising from concentrations of large plastic deformations in severely damaged regions. For validating the proposed model, results of computational simulations are compared to data from selected tests considering different multi-axial stress states. Comparisons of the numerical results with data from laboratory experiments demonstrate the capabilities of the proposed framework.

42 ENGINEERING↗
DOE OSTI2023

Relating storm-snow avalanche instabilities to data collected from the Differential Emissivity Imaging Disdrometer (DEID)

Storm-snow avalanches are challenging to forecast due to complex alpine terrain and during rapidly changing weather conditions. They can result in loss of lives and significant economic impact. We describe how a new device that continuously measures with high-frequency snowflake mass, size, density, and type, the Differential Emissivity Imaging Disdrometer (DEID), and show how the DEID can be used to aid avalanche forecasting when coupled with a storm-snow stability model. DEID measurements of snow accumulation, snow water equivalent (SWE), and snow density obtained during seventeen storms taken at the mid-Collins Snow-Study Plot at Alta Ski Area in Utah's Central Wasatch mountain range during winter 2020–2021 show excellent agreement with infrequent manual measurements. Additionally, two new variables, the Shape Density Index (SDI) and Complexity, are proposed and used to classify snowflake habit and estimate storm-snow shear strength. We illustrate how these DEID-derived data can be used to identify layers of concern in the storm snow such as density inversions, in real-time without digging snow pits. Furthermore, the DEID-data are used to run four variations of the SNOw Slope Stability model (SNOSS) for the storms investigated. The results are evaluated with data collected from tilt-board tests, infrasound measurements, and visual observations of avalanches. For a total fourteen storms analyzed, the DEID-driven SNOSS-modeled minimum stability index predicts the general stability of the storm-snow as indicated by observed avalanches, both natural and of unknown cause. Finally, the results provide a promising approach for nowcasting instabilities within storm-snow layers with a single instrument.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Molecular simulation of the structural and thermodynamic properties of n-alkane/brine interfacial systems with nonionic surfactants

All-atom molecular dynamics (MD) simulations are used to study the structural and thermodynamic properties of water + n-heptane interfacial systems in the presence of salinity (NaCl, NaI, KCl, and KI) and two different nonionic surfactants. Excellent qualitative and quantitative agreement with interfacial tension experimental data is obtained, but this requires applying a charge scaling factor to the ionic species, suggesting the likely role of polarizability effects. Tensoactive behavior is observed for the NaI and KI systems, coinciding with layering of the iodide species near the interface. Further, there are significant interaction differences between the surfactants and the different ionic species, but the structural and thermodynamic behavior of the surfactant molecules is relatively unaffected by the specific salt species. Our analysis suggest that the surfactant-surfactant interactions play a critical role in determining the interfacial behavior, with a much smaller impact associated with the composition of the brine phase.

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

An experimental investigation of flame and autoignition behavior of propane

We report autoignition delay time data are one important means to develop, quantify, and validate fundamental understanding of combustion chemistry at low temperatures (T<1200 K). However, low-temperature chemistry often has higher uncertainties and scatter in the experimental data compared with high-temperature ignition data (T>1200 K). In this study, autoignition properties of propane and oxygen mixtures were investigated using the University of Michigan rapid compression facility in order to understand the effects of ignition regimes on low-temperature ignition data. For the first time for propane, autoignition delay times were determined from pressure histories, and autoignition characteristics were simultaneously recorded using highspeed imaging of the test section through a transparent end-wall. Propane mixtures with fuel-to-O 2 equivalence ratios of φ = 0.25 and φ = 0.5 and O 2 -to-inert gas molar ratios of 1:3.76 were studied over the pressure range of 8.9 to 11.3 atm and the temperature range of 930 – 1070 K. The results showed homogeneous or strong autoignition occurred for all φ = 0.25 experiments, and inhomogeneous or mixed autoignition occurred for all φ = 0.5 experiments. While a limited temperature range is covered in the study, importantly the data span predicted transitions in autoignition behavior, allowing validation of autoignition regime hypotheses. Specifically, the results agree well with strong-autoignition limits proposed based on the Sankaran Criterion. The autoignition delay time data at the strong-ignition conditions are in excellent agreement with predictions using a well-validated detailed reaction mechanism from the literature and a zerodimensional modeling assumption. However, the experimental data at the mixed autoignition conditions were systematically faster than the model predictions, particularly at lower temperatures (T< ~970 K). The results are an important addition to the growing body of data in the literature that show mixed autoignition phenomena are important sources of the higher scatter observed in the low-temperature autoignition data for propane and other fuels. The results are discussed in terms of different methods to capture the effects of pre-autoignition heat release associated with mixed autoignition conditions and thereby address some of the discrepancies between kinetic modeling and experimental measurements.

42 ENGINEERING↗
DOE OSTI2021

Machine learning assisted modeling of mixing timescale for LES/PDF of high-Karlovitz turbulent premixed combustion

Accurate modeling of mixing in the transported probability density function (PDF) method remains a great challenge, especially for turbulent premixed combustion under extreme conditions such as high Karlovitz number Ka. Recently, a power-law based mixing timescale model was developed for the large-eddy simulations (LES)/PDF modeling of high-Ka number turbulent premixed flames. It is found in this work that the power-law mixing timescale model is highly sensitive to the model parameters. It is thus critically needed to develop accurate calibration of these model parameters. The empirical specification of the model parameters developed in Zhang et. al. is found to be inadequate for accurate modeling of the mixing timescale. Here, machine learning is introduced as an attractive alternative in this work for the specification of the model parameters. A high-Ka number DNS jet flame is used as the training and validation of the machine learning models. The choices of the input parameters are discussed and compared for the machine learning models. The effect of differential molecular diffusion on mixing is examined by including the effect of the Lewis number in the training of the machine learning models. The performance of different machine learning algorithms is compared for the specification of the mixing model parameters. Overall, excellent performance of the machine learning models is observed for assisting the mixing modeling. The feasibility, interpretability, applicability, generality, and portability of using machine learning are discussed in general to provide a perspective on applying data-driven machine learning for turbulent combustion modeling studies.

42 ENGINEERING↗
DOE OSTI2022

Group additivity values for the heat of formation of C 2 –C 8 alkanes, alkyl hydroperoxides, and their radicals

A set of 58 group additivity values (GAV) for the calculation of the heat of formation is derived from an extensive and accurate database of 192 ab initio heats of formation. The ab initio values are from companion calculations at the CCSD(T)–F12/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ level of theory employing second order connectivity based hierarchy reference reactions with ANL energies for the reference species. This database of 192 species consists of alkanes (RH), alkyl radicals ($\dot{\text {R}}$), alkyl hydroperoxides (RO 2 H), alkyl-peroxy (R$\dot{\text {O}}$ 2 ) radicals, and hydroperoxy-alkyl ($\dot{\text {Q}}$OOH) radicals of all of the isomers of C 2 –C 5 alkane fuels and a select set of C 6 –C 8 isomers. The GAV and ab initio based enthalpies for this dataset show excellent agreement, with an estimated 2σ uncertainty of 0.9 kcal mol –1 . Among the 58 GAV terms, 40 are refinements of previously reported terms, while 18 are newly developed. These new GAV terms are mainly non-next-nearest neighbor interactions (NNI) and β-corrections. The inclusion of these new groups significantly improves the accuracy of the GAV estimates of the heats of formation. Finally, the updated GAVs can be used with increased confidence to estimate the heats of formation of combustion relevant hydrocarbons and oxygenated hydrocarbons and their corresponding radicals, which are important in predicting low-temperature chemistry and are critical in the development of accurate chemical kinetic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Temperature measurements in heavily-sooting ethylene/air flames using synchrotron x-ray fluorescence of krypton

High-fidelity temperature field measurements have been made for several heavily-sooting ethylene/air flames that have historically been challenging environments for conventional optical diagnostics. These challenges have largely been overcome here, in this study, by conducting x-ray fluorescence (XRF) measurements of a Kr fluorescent agent in the hard x-ray regime (15 keV). The current methodology presents a more economical diagnostic than a previously reported implementation of the Kr-XRF method, by limiting seeding of the expensive fluorescent agent to only the fuel stream flows. Detailed reacting flow simulations have been used to interpret experimental signals by tracking the mole fraction of the fluorescent agent in the flow field. Simulated Kr densities are in excellent agreement with measurements throughout the flow field. Temperature measurements of the flow field also agree well with simulations and recent literature studies. However, uncertainties in the measurements become increasingly large downstream of the burner surface as the krypton fraction drops due to mixing of the fuel and co-flow streams. Additionally, we demonstrate that soot particles in the heavily sooting flames studied do not impede the Kr-XRF measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗