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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Additional considerations in analytical solution for time-dependent heat conduction in a three-dimensional multilayer sphere

This work presents an analytical method to solve the heat conduction equation in three dimensions for problems consisting of multilayer concentric spheres. The method can be used to treat time-varying heat conduction problems where the heat source that drives the transient is time-invariant. Equally applicable to all Poisson-type problems with concentric spherical geometry, the method consists of representing the solution as a summation of weighted eigenfunctions. The weights for each eigenfunction are computed algebraically. Previous work has already established the core constituents of the methodology. The current work augments the existing methods by including consideration of nonzero interface resistance between layers and explicit discussion on the boundary condition homogenization required to treat inhomogeneous problems. Also, two demonstration problems are presented. One demonstration problem is based on the method of manufactured solutions and therefore allows for comparison with exact expressions for the solution temperature distribution. The second, more complex, demonstration problem relies on the finite element method for comparisons. The expected convergence behavior is observed for both demonstration problems.

97 - MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Extreme Molecular Complexity Resulting in a Continuum of Carbonaceous Species in Biomass Burning Tar Balls from Wildfire Smoke

Biomass burning emits a wide range of carbonaceous particles into the atmosphere and has negative impacts on human health and the Earth’s radiative balance. Nonvolatile spherical organic aerosol particles, commonly known as tar balls, represent one of the most abundant particles in aged biomass burning smoke. However, the detailed molecular-level composition of ambient tar balls is largely unknown but critical to access their environmental impacts. Ambient aerosol samples collected during a wildfire event, which were ~90% tar balls by number fraction, were analyzed using ultrahigh resolution Orbitrap Elite mass spectrometry with four complementary ionization modes. Our results show the molecular composition of tar balls to be complex, composed of over 10,000 molecular formulas. Model estimated saturation mass concentrations and relative humidity dependent glass transition temperatures were consistent with low volatility and solid morphology as expected for tar balls. Room-temperature evaporation kinetics showed that these particles were composed of ~90% non-volatile species. The molecular complexity detected here signifies a continuum of carbonaceous species, ranging from C3 to C45 with continuous ranges of oxygenation and hydrogen saturation for each Cn. Approximately 24% of molecular formulas were estimated the be highly aromatic, which could indicate chemical compounds with negative health effects, and which may contribute to visible light absorption. The carbon continuum observed here has significant implications for the molecular characterization of atmospheric organic matter. The level of complexity detected here should not be ignored in future studies and we demonstrate that multiple analytical methods may be required to suitably interpret this complexity on a molecular level.

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

Agilent AgileBioFoundry CRADA (Final Report)

The mission of this CRADA with Agilent was to couple powerful MS platforms (QQQ, IM-QTOF-MS) with Agilent’s novel Ultra-High-Performance Liquid Chromatography (UHPLC) fast metabolomic workflows and perform ABF Machine Learning (ML) to generated datasets. Agilent transferred UHPLC methods to PNNL and LBNL and methods were implemented and demonstrated in both labs, achieving total acquisition times of < 10 min. Metabolites analyzed using Agilent’s shared methods included metabolites from central carbon metabolism, common across hosts, and metabolites unique to engineered strains. Standards were acquired in an UHPLC-Drift Tube Ion Mobility Mass Spectrometer (DTIMS) system for the first time within the context of ABF and methods were optimized based on Agilent’s protocols. Samples from ABF hosts Pseudomonas putida, Aspergillus pseudoterreus, Aspergillus niger and Rhodosporidium toruloides were analyzed using the UHPLC-DTIMS platform for a total of 276 runs. A data analysis workflow compatible with the Experimental Data Depot (EDD) and completely shareable was developed for the acquired UHPLC-DTIMS data. Samples were analyzed using a Data Independent Acquisition Approach (DIA), which for most of the standards provided more transitions therefore increasing detection confidence. Using the data acquired by PNNL, LBNL, and Agilent’s specifications from previous ML projects, SNL applied an ensemble ML strategy to pick the best performing model for automated LC-method selection. Finally, with the contribution of the participant labs and Agilent, SNL developed an Automated Method Selection (AMS) software tool to predict the best liquid chromatography method for analysis of any new molecules of interest. Samples with novel pathways and new metabolite targets of interest are generated at a high pace in the ABF. Therefore, our accomplishment in this CRADA improved the efficiency and accuracy of strain testing by developing and implementing fast analytical methods, robust processing tools, and software for predicting the best methods for UHPLC analysis.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Comparison of vapour pressure osmometry, freezing point osmometry and direct membrane osmometry for determining the osmotic pressure of concentrated solutions

Osmometry is the analytical method of measuring osmotic pressure ($π$) and related colligative properties. Accurately measuring $π$ is essential for applications that use osmosis, including drug delivery systems and water filtration methods such as forward osmosis. The three most common forms of directly or indirectly measuring $π$ are vapour pressure osmometry (VPO), freezing point osmometry (FPO), and direct membrane osmometry (DMO). In this report, the performance of VPO, FPO, and DMO are compared for various aqueous solutions, including small molecule and polymer solutes, and potentially more difficult samples such as concentrated, carbonated, or viscous solutions. Furthermore, potential problems with each of the three methods are examined. Good practices can avoid inaccuracies in DMO due to external concentration polarization and solute diffusion through the membrane. Similarly, it is important to be aware of and avoid weaknesses in VPO and FPO in order to obtain reliable results. Even with care, however, the three methods still give different values of $π$ for concentrated aqueous solutions.

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

Raman spectroscopy coupled with ambient ionization mass spectrometry: A forensic laboratory investigation into rapid and simple dual instrumental analysis techniques

We present a laboratory experiment, developed around a pair of instrumental analysis techniques, Raman spectroscopy and ambient ionization mass spectrometry (MS), conducted by senior chemistry undergraduate students for bulk analysis of over-the-counter drugs using benchtop versions of the two instruments, as well as trace analysis of illicit drugs utilizing the corresponding portable instruments. The identification and confirmation of seized drugs is a routine operation in forensic laboratories that can be simplified using these two instrumental techniques in tandem. Bulk samples are readily analyzed using conventional Raman spectroscopy followed by paper cone spray ionization (PCSI) MS, while trace analysis is allowed by a simple single-substrate dual-analyzer method using surface enhanced Raman spectroscopy (SERS) from paper followed by paper spray ionization (PSI) MS. The introduction of these novel strategies to the students exposed them to potential career paths in forensic science by means of a hands-on experience that provided fundamental knowledge about this set of analytical methods, including intercomparisons of their performance, as well as practical issues like costs, regulations and databases. The use of portable instrumentation represents an additional learning experience for the students, considering that it is cutting-edge technology that is just now being transferred from academic to industrial labs and that it allows a valuable discussion of the advantages and disadvantages of bringing the laboratory to the field.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Active oxygen species in heterogeneously catalyzed oxidation reactions

Active oxygen species generation in heterogeneously catalyzed hydrocarbon oxidation reactions have not been fully characterized. There is little consensus as to which the most active or selective species are. However, electron localization at a single oxygen atom—rather than shared over several—is necessary to activate very stable hydrocarbons like methane. This paper presents an overview of oxygen species formed on various catalytic surfaces and their role in hydrocarbon oxidation reactions. Since limitations of analytical methods are a significant bottleneck for understanding and engineering active oxygen species, approaches for characterizing and quantifying active oxygen are discussed. While several methods are effective for describing certain oxygen species, there is no method that comprehensively characterizes all active oxygen species. Here, the most promising approach is oxygen isotope exchange coupled with infrared spectrometry and inline mass spectrometry.

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

Selecting Suitable Near-Native Lignins for Research

There are several methods to isolate near-native lignins, including milled-wood lignin, enzymatic lignin, cellulolytic enzyme lignin, and enzymatic mild-acidolysis lignin. Which one is the most representative of the native lignin? Herein, near-native lignins were isolated from different plant groups and structurally analyzed to determine how well these lignins represented their native lignin counterparts. Analytical methods were applied to understand the molecular weight, monomer composition, and distribution of interunit linkages in the structure of the lignins. The results indicated that either enzymatic lignin or cellulolytic enzyme lignin may be used to represent native lignin in softwoods and hardwoods. None of the lignins, however, appeared to represent native lignins in grasses (monocot plants) because of substantial syringyl/guaiacyl differences. Furthermore, complicating the understanding of grass lignin structure, large amounts of hydroxycinnamates acylate their polysaccharides and, when released, are often conflated with actual lignin monomers.

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

Quantification of Native Lignin Structural Features with Gel–Phase 2D–HSQC 0 Reveals Lignin Structural Changes During Extraction

Our ability to study and valorize the lignin fraction of biomass is hampered by the fundamental and still unmet challenge of precisely quantifying native lignin's structural features. Here, we developed a rapid elevated-temperature 1 H– 13 C Heteronuclear Single-Quantum Coherence Zero (HSQC 0 ) NMR method that enables this precise quantification of native lignin structural characteristics even with whole plant cell wall (WPCW) NMR spectroscopy, overcoming fast spin relaxation in the gel phase. We also formulated a Gaussian fitting algorithm to perform automatic and reliable spectral integration. By combining HSQC 0 measurements with yield measurements following depolymerisation, we can confirm the combinatorial nature of radical coupling reactions during biosynthesis leading to a random sequential organization of linkages within a largely linear lignin chain. Such analyses illustrate how this analytical method can greatly facilitate the study of native lignin structure, which can then be used for fundamental studies or to understand lignin depolymerization methods like reductive catalytic fractionation or aldehyde-assisted fractionation.

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

Production and Evaluation of Fluorophore-Doped Polymer Substrates to Screen for Plastic-Degrading Enzymes

Fast and sensitive analytical methods are the key to efficient screening of plastic-degrading enzymes. Here, we present a streamlined and affordable approach to assess the enzymatic deconstruction of insoluble synthetic polymers by blending them with a fluorescent dye, rhodamine 6G, and we evaluate this screening method using poly(ethylene terephthalate) (PET) as a model material. Our results indicate that enzymatic depolymerization of the rhodamine-doped PET can be observed in a high-throughput fashion by following release of the fluorophore. The fluorescence data obtained during the hydrolysis of rhodamine-doped PET by 14 PET hydrolases, produced with a robotic platform, correlated with the quantitative chromatographic analysis of PET degradation products. Remarkably, the use of the rhodamine-loaded PET substrate resulted in negligibly low background signals even when detecting PETase activity in crude cell lysates, suggesting suitability for screening of a wide variety of samples. Encouraged by these results, we next produced a selection of polyethylene- and nylon-based materials loaded with rhodamine 6G. While rapid leaching of fluorophore observed with nylon substrates limits the utility of the method for detecting nylonase activity, the rhodamine-loaded polyethylene showed promising performance in passive diffusion tests, indicating that this latter substrate may be used to screen for polyolefin-degrading enzymes.

09 BIOMASS FUELS↗
DOE OSTI2025

Ionic Liquids in Analytical Chemistry: Fundamentals, Technological Advances, and Future Outlook

The development of new analytical methods most often focus on novel materials used to impart selectivity or sensitivity to the protocol. Ionic liquids (ILs) are a class of solvents that have been extensively explored as promising materials for various applications and continue to be explored due to their tunable physicochemical properties. These materials possess melting temperatures below 100 °C and can interact with analytes through a multitude of interactions afforded by their readily tunable chemical structure. These interactions include electrostatic, dispersive, hydrogen bonding, π–π, and dipolar interactions and can be modulated or strengthened based on the functional groups present within the chemical structure. ILs consist predominately of organic cations and either inorganic or organic anions, both of which can be functionalized with desired moieties. Common cation and anions found in IL chemical structures are presented in Figure 1. The unique polarity afforded by the ionic structure has also led to their increasing use in areas including sample preparation, chemical separations, electrochemistry, mass spectrometry, and spectroscopy.

Zeger, Victoria R. [Iowa State Univ., Ames, IA (Un↗
DOE OSTI2024

Quantification of Native Lignin Structural Features with Gel–Phase 2D–HSQC 0 Reveals Lignin Structural Changes During Extraction

Our ability to study and valorize the lignin fraction of biomass is hampered by the fundamental and still unmet challenge of precisely quantifying native lignin's structural features. Here, we developed a rapid elevated-temperature 1 H– 13 C Heteronuclear Single-Quantum Coherence Zero (HSQC 0 ) NMR method that enables this precise quantification of native lignin structural characteristics even with whole plant cell wall (WPCW) NMR spectroscopy, overcoming fast spin relaxation in the gel phase. We also formulated a Gaussian fitting algorithm to perform automatic and reliable spectral integration. By combining HSQC 0 measurements with yield measurements following depolymerisation, we can confirm the combinatorial nature of radical coupling reactions during biosynthesis leading to a random sequential organization of linkages within a largely linear lignin chain. Such analyses illustrate how this analytical method can greatly facilitate the study of native lignin structure, which can then be used for fundamental studies or to understand lignin depolymerization methods like reductive catalytic fractionation or aldehyde-assisted fractionation.

09 BIOMASS FUELS↗
DOE OSTI2022

Defect and satellite characteristics of additive manufacturing metal powders

Metal additive manufacturing (AM) requires high-quality metal powders to three-dimensionally (3D) print metallic components with complex and customizable geometries. The lack of quantification of AM metal powders creates quality control challenges for 3D printed components, increases the uncertainty of printing reliability and net cost of inspected and certified printed components, and reduces the recyclability of used powders. However, critical characteristics of AM metal powders that are decisive factors for the 3D printing process, such as internal porosity, contamination, and satellite feature, remain ambiguous. In this work, we developed a novel approach to 3D quantify key characteristics of AM metal powders down to individual particles by using high-resolution synchrotron x-ray computed tomography. Empowered by the penetrative capability of high-energy x-ray, internal porosity and contamination within as-atomized metal powders from high-entropy alloys to nickel-based superalloys were evaluated. Additionally, the newly-developed dispersion method enables the homogeneous separation of individual particles, and consequently, results in the implementation of 3D particle shape analysis. To resolve a major challenge of identification and quantification of satellite-feature particles in as-atomized AM metal powders, the satellite features were quantitated by modeling and analyzing the shape parameter of local thickness variance. Furthermore, the 3D analytical methods of particle assessment in this study can be applied to other materials systems like rock, food, and pharmaceutical particles, and provide insights for process optimization across powder metallurgy, concrete, food and pharmaceutical manufacturing, and AM industries.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Determination of a suitable molar absorption coefficient (ε) for lignin analysis of fibrous plants using the CASA method

In this study, the benchmarking and applicability of the CASA method for the analysis of fibrous plants, such as flax, hemp, and jute, is evaluated. Lignin is a phenolic biopolymer present in plant cell walls and is composed of three primary monomeric units, designated G, S, and H. Various factors, such as the genetic variability, influence the relative proportions of these units in plant samples. Recently, the cysteine-assisted sulfuric acid (CASA) method has been introduced as a rapid method for the quantification of lignin in wood samples. The aim of this study is to establish a suitable molar absorption coefficient (ε, L·g –1 ·cm –1 ) to adapt the CASA method for use with annual plant fibers. This investigation was motivated by the technical advantages of the CASA method, including higher throughput, lower reaction temperatures, and ecological benefits due to the absence of carcinogenic, mutagenic, or reprotoxic (CMR) substances and the need for minimal sample quantities. In this method, lignin solubilization is facilitated by cysteine, which is an amino acid that enhances the reaction kinetics, using a one-hour incubation period. However, as with any spectrophotometric technique, the CASA method depends on a molar absorption coefficient (ε) that varies according to the ratio of the aromatic units within the polymer. To evaluate the suitability of CASA for quantifying lignin in economically significant plant fibers, we investigate the impact of the unit ratios on the accuracy of ε. The results are compared with those of two widely recognized lignin analytical methods: the Klason method, which is a gravimetric reference method, and the acetyl bromide soluble lignin method, which is the most commonly used spectrophotometric approach. The final ε obtained in this study reveals a relative difference in lignin content ranging from –8 % to +9 % based on a comparison between the CASA and Klason methods across different industrial hemp varieties. As a result, using known G:S ratios in annual fibrous plants, ε can be estimated from our results.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Dislocation dynamics in polycrystalline materials

An extension of the dislocation dynamics method to polycrystalline materials is presented with emphasis on handling interactions between dislocations and grain boundaries. The key new features of the method include: (1) a grain boundary detection algorithm, (2) new dislocation emission criteria based on power dissipation and area growth, (3) mobility of dislocations at grain boundaries, and (4) extension of topological operations e.g. mesh adaption, collision, and dissociation to handle dislocations interacting with grain boundaries. Furthermore, verification and validation examples are executed to compare our calculations with existing analytic methods, molecular dynamics simulations, and experimental observations.

36 MATERIALS SCIENCE↗