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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Safely probing the chemistry of Chernobyl nuclear fuel using micro-focus X-ray analysis

Detailed chemical analysis of the solidified molten fuel still residing in the stricken Chernobyl reactor unit 4 are inferred using multi-modal micro-focus X-ray analysis of a low-radioactivity proxy. A fascinating mixture of molten UO 2 , nuclear fuel cladding, concrete, stainless steel and other nuclear reactor components, these materials behaved like lava, solidifying to form a complex, highly radioactive glass-ceramic. Using element-specific chemical probes (micro-X-ray fluorescence and X-ray absorption spectroscopy), coupled with micro-diffraction analysis, the crystalline phase assemblage of simulants of these heterogeneous materials was established, which included “chernobylite” and a range of compositions in the (U 1-x Zr x )O 2 solid solution. Novel insight to nuclear accident fuel chemistry was obtained by establishing the oxidation state and local coordination of uranium not only in these crystalline phases, but uniquely in the amorphous fraction of the material, which varied depending on the history of the nuclear lava as it flowed through the reactor. This study demonstrates that micro-focus X-ray analysis of very small fractions of material can yield rich chemical information, which can be applied to nuclear-melt down materials to aid decommissioning and nuclear fuel management at nuclear accident sites.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Autothermal Chemical Looping Oxidative Dehydrogenation of Ethane: Redox Catalyst Performance, Longevity, and Process Analysis

Energy-efficient upgrading of stranded ethane from shale gas to olefins holds the promise of increasing the supply of useful chemical feedstocks while reducing flaring-based CO 2 emissions. Previously, we reported a modular ethane-to-liquids (M-ETL) system based on a chemical looping oxidative dehydrogenation (CL-ODH) scheme. In this article, we present long-term (>1200 h) results of Li 2 CO 3 -promoted La 0.8 Sr 0.2 FeO 3 corresponding to ~4125 CL-ODH cycles in a large laboratory-scale packed bed reactor. Temperature monitoring along the bed length confirmed the exothermicity of both the oxidative dehydrogenation and regeneration steps, enabling an autothermal operation. Product gas analysis indicated that the redox catalyst maintains a high C 2+ selectivity (~90%) and ethane conversion (~67%) at 735 °C after continuous cycling of >1000 h. As a result, product distributions and heats of reactions were used to update our M-ETL process model for revised techno-economic analysis, demonstrating that the current system is economically viable with relatively low required selling prices across a wide range of operating scenarios.

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

Introductory guide to backgrounds in XPS spectra and their impact on determining peak intensities

Photoelectron and Auger peaks are central to most of the important uses of x-ray photoelectron spectroscopy (XPS), and thus, they receive the most attention in many types of analysis. Quantitative chemical analysis using XPS requires the assessment of the intensities of the photoemission peaks of the elements detected. Determination of peak intensities requires separation of the photoelectron peak signals from the background on which the peaks rest. For the determination of peak area intensities, the background is subtracted from overall signal intensity. The spectral background is also critical when peak fitting is used to determine intensities of overlapping peaks, and the model of background used in this process can impact the results. In addition to the impact on quantitative analysis, information about the depth distribution of elements in the near surface region can often be obtained by visual inspection of the background and quantified using appropriate modeling. Here, this introductory guide provides some basic information about backgrounds in the XPS analysis, describes the types of background models that are commonly used, suggests some of their strengths and weaknesses, and provides examples of their use and misuse. Although the fundamental nature of some components of the background signals in XPS is not understood, indicating that none of the models in use are fully correct and the area is subject to active research, appropriate good practices have been established for most routine analysis. The guide describes good practices, identifies errors that frequently appear in the literature, and uses examples to demonstrate the impacts of background selections on determinations of peak intensities.

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

Characterization of DWPF Melter Primary Off-Gas Line Pluggage Deposits

This report details results from characterization of the Defense Waste Processing Facility (DWPF) melter off-gas pluggage deposits collected in late calendar year 2021 from the outlet of the jumper immediately preceding the quencher. DWPF requested through a technical assistance request characterization of the melter off-gas deposits by X-Ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDAX), chemical analysis and both aqueous and organic leaching of the solids.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

The Open Cluster Chemical Abundances and Mapping Survey. VI. Galactic Chemical Gradient Analysis from APOGEE DR17

The goal of the Open Cluster Chemical Abundances and Mapping (OCCAM) survey is to constrain key Galactic dynamic and chemical evolution parameters by the construction and analysis of a large, comprehensive, uniform data set of infrared spectra for stars in hundreds of open clusters. This sixth contribution from the OCCAM survey presents analysis of SDSS/APOGEE Data Release 17 (DR17) results for a sample of stars in 150 open clusters, 94 of which we designate to be "high-quality" based on the appearance of their color–magnitude diagram. We find the APOGEE DR17-derived [Fe/H] values to be in good agreement with those from previous high-resolution spectroscopic open cluster abundance studies. Using a subset of the high-quality sample, the Galactic abundance gradients were measured for 16 chemical elements, including [Fe/H], for both Galactocentric radius ($R$ GC ) and guiding center radius ($R$ guide ). We find an overall Galactic [Fe/H] versus RGC gradient of -0.073 ± 0.002 dex kpc -1 over the range of 6 > $R$ GC < 11.5 kpc, and a similar gradient is found for [Fe/H] versus $R$ guide . Significant Galactic abundance gradients are also noted for O, Mg, S, Ca, Mn, Na, Al, K, and Ce. Our large sample additionally allows us to explore the evolution of the gradients in four age bins for the remaining 15 elements.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Characterization of Hanford LAW Phase 3 Glasses

This report provides analyses of glass compositions, wash solution compositions, and Product Consistency Test (PCT) leachate compositions for a series of simulated low-activity waste (LAW) glasses fabricated at the Pacific Northwest National Laboratory (PNNL). These data will be used in the development of improved property/composition models for LAW glass at Hanford. Chemical analyses were performed on a representative sample of each of the quenched and sulfur saturated glasses to allow for comparisons with the targeted compositions. For some of the quenched glasses, measured concentrations of Cr₂O₃, K₂O, Na₂O, P₂O₅, and ZrO₂ were below the targeted values. For some of the sulfur saturated glasses, the measured concentrations of Al₂O₃, Cl⁻, Cr₂O₃, F⁻, K₂O, Na₂O, P₂O₅, V₂O₅, and ZrO₂ were generally low relative to the targeted values. A comparison of the measured compositions of the quenched and sulfur saturated versions of the study glasses showed that the measured concentrations of Al₂O₃, Cl⁻, and F⁻ were lower for most of the sulfur saturated glasses. The measured Cr₂O₃ and K₂O concentrations were markedly lower for the sulfur saturated versions of the glasses as compared to the quenched versions, which may indicate that these elements partitioned to the soluble sulfur salts. A set of modified glasses was received from PNNL later in this study. Chemical analysis showed that these glasses generally met their targeted compositions. The measured SO₃ concentrations were higher for most of the sulfur saturated glasses relative to those of the quenched versions, as expected. Chemical analysis of the wash solutions that resulted from preparation of the sulfur saturated melts identified Cr, K, Na, P, S, and V as the major elements in solution. With the exception of sulfur, this may explain why the measured concentrations of these components in the study glasses were generally below the targeted values. PNNL performed PCTs on quenched and canister centerline cooled (CCC) versions of the study glasses, as well as the modified glasses. The leachates were sent to SRNL for chemical analysis. Minor scatter in the measured values among the triplicate samples for each glass was noted. Several of the study glasses, both quenched and CCC, have NCi values that are greater than the immobilized LAW constraint of 4 g/L for B, Na, and Si.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Colloidal State Machines as Smart Tracers for Chemical Reactor Analysis

A widely utilized tool in reactor analysis is passive tracers that report the residence time distribution, allowing estimation of the conversion and other properties of the system. Recently, advances in microrobotics have introduced powered and functional entities with sizes comparable to some traditional tracers. This has motivated the concept of Smart Tracers that could record the local chemical concentrations, temperature, or other conditions as they progress through reactors. Herein, the design constraints and advantages of Smart Tracers by simulating their operation in a laminar flow reactor model conducting chemical reactions of various orders are analyzed. It is noted that far fewer particles are necessary to completely map even the most complex concentration gradients compared with their conventional counterparts. Design criteria explored herein include sampling frequency, memory storage capacity, and ensemble number necessary to achieve the required accuracy to inform a reactor model. Cases of severe particle diffusion and sensor noise appear to bind the functional upper limit of such probes and require consideration for future design. The results of the study provide a starting framework for applying the new technology of microrobotics to the broad and impactful set of problems classified as chemical reactor analysis.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

A comprehensive chemical abundance analysis of the extremely metal poor Leoncino Dwarf galaxy (AGC 198691)

ABSTRACT We re-examine the extremely metal-poor dwarf galaxy AGC 198691 using a high quality spectrum obtained by the LBT’s MODS instrument. Previous spectral observations obtained from KOSMOS on the Mayall 4-m and the Blue channel spectrograph on the MMT 6.5-m telescope did not allow for the determination of sulfur, argon, or helium abundances. We report an updated and full chemical abundance analysis for AGC 198691, including confirmation of the extremely low “direct” oxygen abundance with a value of 12 + log (O/H) = 7.06 ± 0.03. AGC 198691’s low metallicity potentially makes it a high value target for helping determine the primordial helium abundance (Yp). Though complicated by a Na i night sky line partially overlaying the He i λ5876 emission line, the LBT/MODS spectrum proved adequate for determining AGC 198691’s helium abundance. We employ the recently expanded and improved model of Aver et al., incorporating higher Balmer and Paschen lines, augmented by the observation of the infrared helium emission line He i λ10830 obtained by Hsyu et al. Applying our full model produced a reliable helium abundance determination, consistent with the expectation for its metallicity. Although this is the lowest metallicity object with a detailed helium abundance, unfortunately, due to its faintness [EW(Hβ) < 100 Å] and the compromised He i λ5876, the resultant uncertainty on the helium abundance is too large to allow a significant improvement on the measurement of Yp.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

The Critical Role of Process Analysis in Chemical Recycling and Upcycling of Waste Plastics

There is an urgent need for new technologies to enable circularity for synthetic polymers, spurred by the accumulation of waste plastics in landfills and the environment and the contributions of plastics manufacturing to climate change. Chemical recycling is a promising means to convert waste plastics into molecular intermediates that can be remanufactured into new products. Given the growing interest in the development of new chemical recycling approaches, it is critical to evaluate the economics, energy use, greenhouse gas emissions, and other life cycle inventory metrics for emerging processes, relative to the incumbent, linear manufacturing practices employed today. Here we offer specific definitions for classes of chemical recycling and upcycling and describe general process concepts for the chemical recycling of mixed plastics waste. We present a framework for techno-economic analysis and life cycle assessment for both closed- and open-loop chemical recycling. Rigorous application of these process analysis tools will be required to enable impactful solutions for the plastics waste problem.

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

HPTLC Analysis and Chemical Composition of Selected Melaleuca Essential Oils

Tea tree oil (TTO) is a volatile essential oil obtained by distillation, mainly from the Australian native plant Melaleuca alternifolia (Maiden & Betche) Cheel (Myrtaceae). In this study, a comparative analysis of the chemical constituents of seven tea tree oils (M. alternifolia) and four other Melaleuca spp. oils (M. cajuputi, (M Ca ), two chemotypes of M. quinquenervia, (M Ne and M Ni ), and M. ericifolia (M Ro )) was carried out using gas chromatography–mass spectrometry (GC-MS) and high-performance thin-layer chromatography (HPTLC). Among the seven TTOs, terpinen-4-ol (37.66–44.28%), γ-terpinene (16.42–20.75%), α-terpinene (3.47–12.62%), α-terpineol (3.11–4.66%), and terpinolene (2.75–4.19%) were the most abundant compounds. On the other hand, the most abundant compounds of the other Melaleuca oils varied, such as 1,8-cineole (64.63%) in M Ca oil, (E)-nerolidol (48.40%) and linalool (33.30%) in M Ne oil, 1,8-cineole (52.20%) in M Ni oil, and linalool (38.19%) and 1,8-cineole (27.57%) in M Ro oil. HPTLC fingerprinting of Melaleuca oils enabled the discrimination of TTO oils from other Melaleuca spp. oils. Variation was observed in the profile of the R f values among EOs. The present study shows that HPTLC is one of the best ways to identify and evaluate the quality control in authenticating TTOs, other Melaleuca EOs, or EOs from other species within the Myrtaceae.

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

Identification of combustion mode under MILD conditions using Chemical Explosive Mode Analysis

Direct Numerical Simulations (DNS) data of Moderate or Intense Low-oxygen Dilution (MILD) combustion are analysed in this paper to identify the contributions of the autoignition and flame modes. This is performed using an extended Chemical Explosive Mode Analysis (CEMA) which accounts for diffusion effects allowing it to discriminate between deflagration and autoignition. This analysis indicates that in premixed MILD combustion conditions, the main combustion mode is ignition for all dilution and turbulence levels and for the two reactant temperature conditions considered. In non-premixed conditions, the preponderance of the ignition mode was observed to depend on the axial location and mixture fraction stratification. With a large mixture fraction lengthscale, ignition is more preponderant in the early part of the domain while the deflagrative mode increases further downstream. On the other hand, when the mixture fraction lengthscale is small, sequential autoignition is observed. Finally, the various combustion modes are observed to correlate strongly with mixture fraction where lean mixtures are more likely to autoignite while stoichiometric and rich mixtures are more likely to react as deflagrative structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Techno-Economic Analysis of Chemical Precipitation Followed by Low Hydraulic Residence Time Biological Treatment, Including Ultrafiltration

This National Energy Technology Laboratory (NETL) analysis is a techno-economic evaluation of chemical precipitation followed by low hydraulic residence time biological treatment, which was identified as Best Available Technology for treatment and control of selenium emissions from wet flue gas desulfurization wastewater streams.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Tutorial on Chemical Pressure Analysis: How Atomic Packing Drives Laves/Zintl Intergrowth in K3Au5Tl

The tight atomic packing generally exhibited by alloys and intermetallics can create the impression of their being composed of hard spheres arranged to maximize their density. As such, the atomic size factor has historically been central to explanations of the structural chemistry of these systems. However, the role atomic size plays structurally has traditionally been inferred from empirical considerations. The recently developed DFT-Chemical Pressure (CP) analysis has opened a path to investigating these effects with theory. In this article, we provide a step-by-step tutorial on the DFT-CP method for non-specialists, along with advances in the approach that broaden its applicability. A new version of the CP software package is introduced, which features an interactive system that guides the user in preparing the necessary electronic structure data and generating the CP scheme, with the results being readily visualized with a web browser (and easily incorporated into websites). For demonstration purposes, we investigate the origins of the crystal structure of K3Au5Tl, which represents an intergrowth of Laves and Zintl phase domains. Here, CP analysis reveals that the intergrowth is supported by complementary CP features of NaTl-type KTl and MgCu2-type KAu2 phases. In this way, K3Au5Tl exemplifies how CP effects can drive the merging for geometrical motifs derived from different families of intermetallics through a mechanism referred to as epitaxial stabilization.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Comparability of Liquid Chromatography Tandem Mass Spectrometry Analysis of Dissolved Organic Matter across Laboratories

Non-targeted liquid chromatography tandem highresolution mass spectrometry (LC−MS/MS) is increasingly applied for the structure-resolved chemical analysis of dissolved organic matter (DOM). With new developments in MS instrumentation and analysis software, the approach has gained substantial momentum over the past decade. However, achieving high-quality analytical data that is reproducible and comparable across laboratories can be a bottleneck in non-targeted metabolomics and organic matter chemical analysis, especially for data reuse in repository-scale analyses. Understanding the capabilities as well as challenges of comparing LC−MS/MS data from different laboratories is necessary for inferring global trends from public data sets. To illuminate instrumentation factors that drive differences and variability, we used a standardized data analysis pipeline, including classical (CMN) and featurebased molecular networking (FBMN), to analyze data from a ring trial by 24 laboratories on identical sample sets of algal and DOM extracts that were mixed in predefined concentrations and spiked with standards. Our results showed that data sets from similar mass spectrometer types with unified instrument parameters were qualitatively comparable, resolving the same general trends and shared mass spectral features. Interlaboratory comparability was best for high-intensity features, while low-intensity features showed greater detection variability. Our analysis also highlights challenges when comparing data from instruments with different acquisition rates or operating with less standardized methods. Lastly, we provide recommendations for data integration, public data sharing, standardization, and best practices for standardized LC−MS/MS data acquisition, which will be critical for long-term time series and intercomparability of DOM chemical analyses.

DOM↗
DOE OSTI2020

High-Throughput Analysis of Materials for Chemical Looping Processes

Chemical looping is a promising approach for improving the energy efficiency of many industrial chemical processes. However, a major limitation of modern chemical looping technologies is the lack of suitable active materials to mediate the involved subreactions. Identification of suitable materials has been historically limited by the scarcity of high-temperature (>600 °C) thermochemical data to evaluate candidate materials. An accuratethermodynamic approach is demonstrated here to rapidly identify active materials which is applicable to a wide variety of chemical looping chemistries. Application of this analysis to chemical looping combustion correctly classifies 17/17 experimentally studied redox materials by their viability and identifies over 1300 promising yet previously unstudied active materials. This approach is further demonstrated by analyzing redox pairs for mediating a novel chemical looping process for producing pure SO2 from raw sulfur and air which could provide a more efficient and lower emission route to sulfuric acid. 12 promising redox materials for this process are identified, two of which are supported by previous experimental studies of their individual oxidation and reduction reactions. This approach provides the necessary foundation for connecting process design with high-throughput material discovery to accelerate the innovation and development of a wide range of chemical looping technologies.

chemical looping↗
DOE OSTI2021

Specialty chemicals production case study: Economic analysis of modular chemical process intensification versus conventional stick‐built approaches

Abstract The beneficial synergies of chemical process intensification and plant modularization present a unique step‐wise advancement opportunity for many chemical manufacturers, but economic case studies are needed to raise awareness of such opportunities. The primary objective of this case study is to better understand the business case economics of a specialty chemical plant using modular chemical process intensification (MCPI), by comparing it with that of a conventional stick‐built (CSB) plant that produces the same product at the same production capacity. When comparing MCPI against CSB approaches for a plant project strategy decision, analysts should thoroughly understand and model the differences and similarities in scope bases. The MCPI approach for this case study benefitted from dramatic reductions in capital expenditures (CAPEX). A sizeable reduction in plant spatial volume likely explains some of these reductions. Sizeable operational expenditure (OPEX) reductions with the MCPI plant appear to be associated with the reduced operator staffing required from converting a labor‐intensive batch process into an automated, continuous flow process. Traditional project investment economic measures strongly favored the MCPI case for the design, construction, and operation of the specialty chemical plant. The net present value for the MCPI case was nearly twice that for the CSB case over a ten‐year period, and the payback period for the CSB case was nearly five times longer than that of the MCPI case. The opinion‐based perspective of the study participant identified significant contributors to superior MCPI economic performance for this case study. With the two conditions of low MCPI CAPEX and high product profit margin, economic analysis indicates that incorporation of a backup MCPI train, for operational redundancy when downtime occurs, is a very beneficial strategy.

O'Connor, James T.↗
DOE OSTI2024

Exploring constituent redistribution in irradiated U-19Pu-14Zr fuel via electron probe microanalysis

Here, the phenomena of constituent redistribution, wherein a previously homogeneous metallic fuel forms discrete, radially concentric compositional zones upon irradiation was investigated by examining an irradiated U-19Pu-14Zr fuel (where numbers represent wt. %) with a burnup of 11.5 at.% with electron probe microanalysis (EPMA) and quadruple inductively coupled plasma mass spectroscopy (Q-ICP-MS). EPMA-generated U, Pu, and Zr compositional data obtained from a diameter traverse of the sample was converted to mass and was used to: 1) compare the overall fuel element analysis results between the two methods, 2) determine the number of compositionally distinct zones forming as a result of constituent redistribution; and 3) quantify the post-irradiation loss or gain of U, Pu, and Zr atoms in each distinct compositional zone. Weight percent concentrations of U, Pu, and Zr for the overall cross section compare favorably between the two analytical methods, suggesting that the spatially resolved EPMA analysis complements bulk chemical analysis. Among the four identified compositional zones, post-irradiation quantification of U, Pu, and Zr elemental atom content changes shows that the quantity of U atoms lost from the innermost zone is slightly less than the quantity of U atoms gained by the middle two zones, and the quantity of Zr atoms lost from the high-U third zone is slightly less than is gained by the two innermost zones. Pu is lost from all four zones, although the innermost zone and the high-U third zone lose a significantly higher percentage (> 22 %) of their initial Pu atoms than the other two zones. For all three elements, EPMA cannot distinguish between atoms lost due to transport to a different zone from atoms lost due to nuclear processes; however, the insight gained from using this process can be used to experiment with new modeling techniques to predict constituent redistribution in U-Pu-Zr fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Characterization of the Sulfur Saturated Versions of the High-Chromium Matrix Glasses

In this report, the Savannah River National Laboratory provides chemical analysis of a series of sulfur saturated melt versions of simulated nuclear waste glasses, and chemical analysis of the wash solutions resulting from the preparation of these glasses. The glasses were selected and fabricated by the Pacific Northwest National Laboratory as part of a broader study of the influence of glass composition on chemical durability, sulfur retention, and other properties. The resulting data will be used in the development of improved property/composition models to support operation of the Hanford Tank Waste Treatment and Immobilization Plant. Some degree of scatter among the Al₂O₃, B₂O₃, CaO, K₂O, Na₂O, and SiO₂ measurements was noted for the study glasses. The measured concentrations of B₂O₃, chlorine, and fluorine were below the targeted values for most of the study glasses, likely because of volatility during the multiple melting steps. The measured concentrations of Cr₂O₃ and K₂O were generally low relative to the targeted values. These components were identified in the wash solutions, indicating partitioning to the excess sulfate phase that was washed from the glasses prior to analyses. As expected, the measured concentrations of SO₃ in the glasses were higher than targeted due to the use of the sulfur saturation method in fabricating these glasses. Minor scatter among the triplicate measurements of some of the analytes of the wash solutions was noted. The wash solutions contained mainly sulfur and sodium, with moderate concentrations of chromium and potassium. Revision 1 of this report corrects the omission of Al₂O₃ values from Table A-4 in Appendix A.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗