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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

Oxidative Catalytic Fractionation of Lignocellulosic Biomass Using a Co-N-P-C Catalyst and One-Step Isolation of Aromatic Monomers via Centrifugal Partition Chromatography

Methods for catalytic fractionation of biomass provide a means to convert lignin directly into monomers while generating a high-quality cellulosic stream, contrasting conventional biomass pretreatment strategies that prioritize the cellulosic fraction. Here, a nonprecious-metal Co-N-P-C catalyst is identified for aerobic oxidative catalytic fractionation (OCF) of poplar feedstock in dimethyl carbonate that achieves significantly higher yields of aromatic monomers (24 wt %) relative to those obtained with a recently reported Co-N-C catalyst in acetone solvent (15 wt %). Mechanistic studies indicate that the acidic properties of the catalyst contribute to its improved performance by promoting extraction of lignin from insoluble polysaccharides. This OCF process is complemented by the development of a new centrifugal partition chromatography (CPC) method that supports isolation of all five major aromatic monomers (syringic acid, syringaldehyde, vanillic acid, vanillin, and para-hydroxybenzoic acid) in a single liquid–liquid extraction purification step. Furthermore, this OCF/CPC sequence has important implications for future lignin valorization efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast and Controllable Phase Evolution by Flash Joule Heating

Flash Joule heating (FJH), an advanced material synthesis technique, has been used for the production of high-quality carbon materials. Direct current discharge through the precursors by large capacitors has successfully converted carbon-based starting materials into bulk quantities of turbostratic graphene by the FJH process. However, the formation of other carbon allotropes, such as nanodiamonds and concentric carbon materials, as well as the covalent functionalization of different carbon allotropes by the FJH process, remains challenging. Here, we report the solvent-free FJH synthesis of three different fluorinated carbon allotropes: fluorinated nanodiamonds, fluorinated turbostratic graphene and fluorinated concentric carbon. This is done by millisecond flashing of organic fluorine compounds and fluoride precursors. Spectroscopic analysis confirms the modification of the electronic states and the existence of various short-range and long-range orders in the different fluorinated carbon allotropes. As a result, the flash time-dependent relationship is further demonstrated to control the phase evolution and product compositions.

01 COAL, LIGNITE, AND PEAT↗

Data from : "Warming promotes loss of subsoil carbon through accelerated degradation of plant-derived organic matter". Blodgett warming experiment

This dataset contains data used for the paper: Warming promotes loss of subsoil carbon through accelerated degradation of plant-derived organic matter. Soil Biology and Biochemistry 156, 108185. doi:10.1016/j.soilbio.2021.108185On April 2018 (after 4.5 years of warming), we collected O-horizon (organic horizon) material and soil core down to 90 cm depth from a whole-soil warming experiment in a mixed-coniferous temperate forest, located at the University of California Blodgett experimental forest in the foothills of the Sierra Nevada, CA USA. The goal was to assess how 4.5 years of +4 °C whole-soil warming affected the quantity and quality of soil organic matter. Cores were collected from 6 experimental plots (three replicated blocks); samples were collected in 10 cm increments from 0 to 90 cm depth.This dataset contains a compressed (.zip) archive of the data used for this manuscript. The dataset includes files in .xlsx format, which can be accessed and processed using MS Excel or R. Carbon and nitrogen concentrations, as well as stable carbon isotope composition ((δ13C) and solvent extractable lipid biomarker (alkanoic acids and alkanes) data are provided as processed data files. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy data are provided as raw output and processed data files.The dataset files "Blodgett_warming_Data" and "Blodgett_warming_raw_data.xlsx" were updated on July 7, 2021. The following updates were made: (1) specification of the units of measurements in the dataset (the unit of measurement was missing in some parameters) and (2) the column name "pulled depth" was changed to "pooled depth" in the updated data files.

54 ENVIRONMENTAL SCIENCES↗

Double-Crucible Vertical Bridgman Technique for Stoichiometry-Controlled Chalcogenide Crystal Growth

Precise stoichiometry control in single-crystal growth is essential for both technological applications and fundamental research. However, conventional growth methods often face challenges such as non-stoichiometry, compositional gradients, and phase impurities, particularly in non-congruent melting systems. Even in congruent melting systems like Bi₂Se₃, deviations from the ideal stoichiometric composition can lead to significant property degradation, such as excessive bulk conductivity, which limits its topological applications. In this study, we introduce the double-crucible vertical Bridgman (DCVB) method, a novel approach that enhances stoichiometry control through the combined use of continuous source material feeding, traveling-solvent growth, and liquid encapsulation, which suppresses volatile element loss under high pressure. Using Bi₂Se₃ as a model system, we demonstrate that crystals grown via DCVB exhibit enhanced stoichiometric control, significantly reducing defect density and achieving much lower carrier concentrations compared to those produced by conventional Bridgman techniques. Moreover, the continuous feeding of source material enables the growth of large crystals. As a result, this approach presents a promising strategy for synthesizing high-quality, large-scale crystals, particularly for metal chalcogenides and pnictides that exhibit challenging non-congruent melting behaviors.

Crystal structure↗

Realistic Ion Dynamics through Charge Renormalization in Nonaqueous Electrolytes

While many practically important electrolytes contain lithium ions, interactions of these ions are particularly difficult to probe experimentally because of their small X-ray and neutron scattering cross sections and large neutron absorption cross sections. Molecular dynamics (MD) is a powerful tool for understanding the properties of nonaqueous electrolyte solutions from the atomic level, but the accuracy of this computational method crucially depends on the physics built into the classical force field. In this study, we demonstrate that several force fields for lithium bistriflimide (LiTFSI) in acetonitrile yield a solution structure that is consistent with the neutron scattering experiments, yet these models produce dramatically different ion dynamics in solution. Such glaring discrepancies indicate that inadequate representation of long-range interactions leads to excessive ionic association and ion-pair clustering. We show that reasonable agreement with the experimental observations can be achieved by renormalization of the ion charges using a “titration” method suggested herewith. This simple modification produces realistic concentration dependencies for ionic diffusion and conductivity in <2 M solutions, without loss in quality for simulation of the structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microsecond Molecular Dynamics Simulations of Proteins Using a Quasi-Equilibrium Solvation Shell Model

In this work, we describe the development and implementation of a quasi-equilibrium hydration shell model of biomolecular solvation with adaptive boundaries. Applying the model to microsecond-long molecular dynamics simulations of several protein systems of varying complexity, we find that the model simulation results are of comparable quality to those obtained from simulations of fully solvated systems, but at a reduced computational cost. We discuss the dominant sources of error in the model and outline directions for future improvements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rice Bran Stabilisation and Oil Extraction Using the Microwave-Assisted Method and Its Effects on GABA and Gamma-Oryzanol Compounds

Rice bran oil (RBO) is a valuable ingredient extracted from rice bran (RB), a side stream of polishing rice grain in the milling process. RBO is rich in bioactive ingredients with potential health benefits, such as gamma-oryzanol (GO) and gamma-aminobutyric acid (GABA). Despite its benefits, the quality of RBO depends on the degree of stabilisation of the RB, which is easily affected by lipase enzymes, and thus needs an effective treatment prior to RBO production. To assess the potential of the microwave-assisted method for RB stabilisation and RBO extraction, three Carolino rice varieties (Ariete, Teti, Luna) were tested. The effect of RB stabilisation was evaluated via acid value, water absorption, and GO and GABA levels. The RBO yield was optimised by solvent, temperature, and solvent-to-sample ratio, and the GO and fatty acid levels were determined. The RB stabilisation for the Luna variety did not affect the GO and GABA; for the Ariete and Teti varieties, the GO decreased by 34.4% and 24.2%, and the GABA increased by 26.5% and 47.0%, respectively. The GO levels in RBO samples were not affected by RB stabilisation. The RBO nutritional value was confirmed by the suitable ratio (>2) between polyunsaturated (PUFA) and saturated fatty acids (SFA), with the Teti variety presenting the highest ratio.

Reis, Núria (ORCID:0000000194339109)↗

Assembly of Arbitrary Designer Heterostructures with Atomically Clean Interfaces

Van der Waals heterostructures are an excellent platform for studying intriguing interface phenomena, such as moiré and proximity effects. Many of these phenomena occurring in such heterostructures' interfaces and surfaces have so far been hampered because of their high sensitivity to disorder and interface contamination. Here, it reports a dry polymer-based assembly technique to fabricate arbitrary designer van der Waals heterostructures with atomically clean surfaces. The key features of the suspended dry pick-up and flip-over assembly technique are: 1) the heterostructure surface never comes into contact with polymers, 2) the assemble is entirely solvent-free, 3) it is entirely performed in a glovebox, and 4) it only requires temperatures below 130 °C. By performing ambient atomic force microscopy and atomically-resolved scanning tunneling microscopy on example heterostructures, it demonstrates the fabrication of air-sensitive heterostructures with ultra-clean interfaces and surfaces. It envisions that, due to the avoidance of polymer melting, this technique is potentially compatible with heterostructure assembly under ultra-high vacuum conditions, which promises ultimate heterostructure quality.

2D materials↗

Filer City Biomass Carbon Removal and Storage (BiCRS) Net-Negative Study

NorthStar Clean Energy Company (NorthStar) conducted the Filer City Biomass Carbon Removal and Storage (BiCRS) Net-Negative Study to develop a conceptual design and cost estimate for retrofitting the TES Filer City Station with post-combustion carbon capture technology in Mainstee Michigan. The Filer City BiCRS Net-Negative Study allowed NorthStar and team to confirm the commercial feasibility of a post-combustion carbon capture system applied to biomass-fired boilers. At the time of the study, there were no operating facilities in the world with carbon capture applied to flue gas from woody biomass as proposed for Filer City. Due to the solvent-agnostic nature of B&W’s SolveBright™ technology, the team determined that multiple amines, both traditional and proprietary, would be capable of 95% CO 2 capture efficiency with the steam available from Filer City’s existing boilers after modifications to burn 100% biomass. Based on the cost estimates produced, NorthStar can now confirm the Filer City BiCRS Project is economically viable with a combination of tax credits available from the Inflation Reduction Act of 2022 and high-quality Carbon Dioxide Removal Credits sold on the Voluntary Carbon Market. The Filer City BiCRS project is uniquely positioned to become one of the first projects to capture and sequester large volumes of CO 2 from a biogenic source, removing existing CO 2 from the atmosphere. The unlimited version of the Filer City Biomass Carbon Removal and Storage (BiCRS) Net-Negative Study Final Technical Report is attached.

01 COAL, LIGNITE, AND PEAT↗

Analysis of edible oil processing options for the BIO-Plex advanced life support system

Edible oil is a critical component of the proposed plant-based Advanced Life Support (ALS) diet. Soybean, peanut, and single-cell oil are the oil source options to date. In terrestrial manufacture, oil is ordinarily extracted with hexane, an organic solvent. However, exposed solvents are not permitted in the spacecraft environment or in enclosed human tests by National Aeronautics and Space Administration due to their potential danger and handling difficulty. As a result, alternative oil-processing methods will need to be utilized. Preparation and recovery options include traditional dehulling, crushing, conditioning, and flaking, extrusion, pressing, water extraction, and supercritical extraction. These processing options were evaluated on criteria appropriate to the Advanced Life Support System and BIO-Plex application including: product quality, product stability, waste production, risk, energy needs, labor requirements, utilization of nonrenewable resources, usefulness of by-products, and versatility and mass of equipment to determine the most appropriate ALS edible oil-processing operation.

NASA Discipline Life Support Systems↗

Automated Counting of Particles To Quantify Cleanliness

A machine vision system, similar to systems used in microbiological laboratories to count cultured microbes, has been proposed for quantifying the cleanliness of nominally precisely cleaned hardware by counting residual contaminant particles. The system would include a microscope equipped with an electronic camera and circuitry to digitize the camera output, a personal computer programmed with machine-vision and interface software, and digital storage media. A filter pad, through which had been aspirated solvent from rinsing the hardware in question, would be placed on the microscope stage. A high-resolution image of the filter pad would be recorded. The computer would analyze the image and present a histogram of sizes of particles on the filter. On the basis of the histogram and a measure of the desired level of cleanliness, the hardware would be accepted or rejected. If the hardware were accepted, the image would be saved, along with other information, as a quality record. If the hardware were rejected, the histogram and ancillary information would be recorded for analysis of trends. The software would perceive particles that are too large or too numerous to meet a specified particle-distribution profile. Anomalous particles or fibrous material would be flagged for inspection.

Rhode, James↗

Heteroatom-Doped Flash Graphene

Heteroatom doping can effectively tailor the local structures and electronic states of intrinsic two-dimensional materials, and endow them with modified optical, electrical, and mechanical properties. Recent studies have shown the feasibility of preparing doped graphene from graphene oxide and its derivatives via some post-treatments, including solid-state and solvothermal methods, but they require reactive and harsh reagents. However, direct synthesis of various heteroatom-doped graphene in larger quantities and high purity through bottom-up methods remains challenging. Here, we report catalyst-free and solvent-free direct synthesis of graphene doped with various heteroatoms in bulk via flash Joule heating (FJH). Seven types of heteroatom-doped flash graphene (FG) are synthesized through millisecond flashing, including single-element-doped FG (boron, nitrogen, oxygen, phosphorus, sulfur), two-element-co-doped FG (boron and nitrogen), as well as three-element-co-doped FG (boron, nitrogen, and sulfur). Here, a variety of low-cost dopants, such as elements, oxides, and organic compounds are used. The graphene quality of heteroatom-doped FG is high, and similar to intrinsic FG, the material exhibits turbostraticity, increased interlayer spacing, and superior dispersibility. Electrochemical oxygen reduction reaction of different heteroatom-doped FG is tested, and sulfur-doped FG shows the best performance. Lithium metal battery tests demonstrate that nitrogen-doped FG exhibits a smaller nucleation overpotential compared to Cu or undoped FG. The electrical energy cost for the synthesis of heteroatom-doped FG synthesis is only 1.2 to 10.7 kJ g –1 , which could render the FJH method suitable for low-cost mass production of heteroatom-doped graphene.

01 COAL, LIGNITE, AND PEAT↗

Improved lipid analysis using a 2D-LC-MS system with a novel injection procedure

The aim of this study was to improve analysis of nonpolar lipidomics sample extracts using reversed phase (RP) chromatography. A 4/3/3 (v/v/v) mixture of methanol/methyl tert-butyl ether/chloroform (MeOH/MTBE/CHCl 3 , MMC) was chosen for sample extraction solvent based on its proven extraction capability for several lipid classes. To avoid carry over, loss of analytes and peak distortion the loops and all capillaries of the presented LC system were flushed and filled up with methanol until the analytical column. Here, the choice of methanol was due to its weak elution strength and being infinitely miscible with MMC and several other nonpolar solvents. This allowed injection of a 100 μl sample that was 20 μl nonpolar extraction solvent diluted fivefold with methanol. All lipids of 25 lipid classes were transferred quantitatively to the column head where the online dilution of methanol was carried out with aqueous eluent for focusing the lipid analytes. The weak elution strength of methanol prevented peak distortions. The consecutive reversed phase elution resulted in remarkably narrow peaks (full width at half maximum was 0.07–0.08 min typically) and enhanced sensitivity (limit of detection usually in sub nM region) because of increased sample injection volume and narrow peaks. Calibration and quality control samples made by diluting commercial lipid standards 200–50000 times confirmed the applicability of this approach both for targeted lipid quantification and for untargeted quantitative comparison of lipids from different sources.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration (FY2020 Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Established methods that typify R2R processing include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating, and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier and membrane materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, the means must be available to enable manufacture of these products in a cost-competitive manner that is affordable. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations and the coating and drying processes to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product. To solve the problems associated with these challenges, the R2R Collaboration is executing a research program with outcomes that will ultimately link modeling, processing, metrology and defect detection tools, thereby directly relating the properties of constituent particles and processing conditions to the performance of final devices. This collaborative approach was designed to foster identification and development of materials and processes related to R2R for clean-energy materials development. Using computational and experimental capabilities by acknowledged subject matter experts within the supported National Laboratory system, this project leverages the capabilities and expertise at each of five National Laboratories to further the development of multilayer technologies that will enable high-volume, cost-competitive platforms. A typical R2R process has three steps: (1) mixing of particles and various constituents in a slurry, (2) coating of the ink/slurry mixture on a substrate, and (3) drying/curing and processing of the coating. Final performance of devices made via R2R processes is dependent on the active materials (e.g., electrochemical particles in battery or fuel cell electrodes) and the device structure that stems from the governing component interactions within the various steps. However, a fundamental understanding of the underlying mechanisms and phenomena is still lacking, which is why industrial-scale R2R process development and manufacturing is still largely empirical in nature. The FY 2019 through FY 2021 program addresses aspects of the following two targets from the AMO Multi-Year Program Plan: (1) Target 8.1 Develop technologies to reduce the cost per manufactured throughput of continuous R2R manufacturing processes. (A) Increasing throughput of R2R processes by 5 times for batteries (to 50 square feet per minute (50 ft 2 /min)) and capacitors and 10 times for printed electronics and the manufacture of other substrates and MEs used in support of these products. (B) Developing resolution capabilities to enable registration and alignment that will detect, align, and co-deposit multiple layers of coatings and print < 1-micron (1 µm) features using continuous process scalable for commercial production. (C) Developing scalable and reliable R2R processes for solution deposition of ultra-thin (<10 nm) films for active and passive materials. (D) Develop in-line multilayer coating technology on thin films with yields greater than 95%. (2) Target 8.2 Develop in-line instrumentation tools that will evaluate the quality of single and multilayer materials in-process. (A) Developing in-line QC technologies and methodologies for real-time identification of defects and expected product properties “in-use/application” during continuous processing at all size-scales with a focus on the “micro” and “nano” scale traces, lines, and devices, i.e., <1 μm at 300 ft./min for R2R processing in air and <10 nm at 20 ft./min for vacuum (B) Developing technologies to increase the measurement frequency of surface rheology without significant cost increases with a goal of a 10-nanometer in-line profilometry at a production rate of 100,000 square millimeters per minute (100,000 mm 2 /min).

42 ENGINEERING↗

Abstract for CRADA between National Energy Technology Laboratory and Western Michigan University

NETL will team up with Western Michigan University (WMU) on designing, developing, and testing the integration of enzyme/Deep Eutectic Solvent (DES) treatment with kraft pulping with a focus on optimizing kraft pulp conditions and testing pulp strength, and optical, and barrier properties. NETL will perform pulping experiments by combining Kraft pulping with DES to allow lower temperature, and reduced chemical use thus improved yield. The main purpose of this study is to investigate different heating methods during chlorine dioxide bleaching of kraft pulps. This study also compares the methods with one another with respect to pulp properties and fiber morphologies. In addition, the energy consumption and quality of bleached pulps under different bleaching conditions are going to be analyzed to provide a solid basis for scale up microwave bleaching process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energy Emissions Accounting Methods Can Determine Whether Direct Air Capture with Storage Achieves Net Removal

The voluntary carbon market within the United States has expanded rapidly in recent years and enabled private companies and other organizations to provide revenue streams to carbon dioxide removal (CDR) technologies. For a CDR technology to participate in the voluntary carbon market (VCM), the emissions associated with constructing and operating the technology must be less than the CO 2 captured from the atmosphere. Assessing the extent to which this is true for direct air capture with storage (DACS), a relatively energy-intensive CDR technology, strongly depends on the accounting method used to assess the emissions intensity of purchased energy. We simulate the hourly weather-dependent operation of sorbent- and solvent-based DACS in California, Louisiana, Texas, and Wyoming, representing a wide range of local weather and electric and natural gas grid compositions. In all cases, the single most important emissions accounting decision is the method used to estimate the emissions intensity of purchased grid electricity, which varies the calculated net removal by −1049% to +108%. All other factors influencing net removal introduce a variation of at most ±14%. No electricity emissions accounting method is universally conservative across all scenarios, and none is objectively more accurate. High-spatiotemporal-resolution, high-quality, publicly available data sets and models for electricity emissions accounting do not currently exist and are urgently needed to enable standardization of emissions accounting methods to more accurately determine the true emissions impacts of DACS and other energy-intensive facilities.

54 ENVIRONMENTAL SCIENCES↗

Improvements in Production of Single-Walled Carbon Nanotubes

A continuing program of research and development has been directed toward improvement of a prior batch process in which single-walled carbon nanotubes are formed by catalytic disproportionation of carbon monoxide in a fluidized-bed reactor. The overall effect of the improvements has been to make progress toward converting the process from a batch mode to a continuous mode and to scaling of production to larger quantities. Efforts have also been made to optimize associated purification and dispersion post processes to make them effective at large scales and to investigate means of incorporating the purified products into composite materials. The ultimate purpose of the program is to enable the production of high-quality single-walled carbon nanotubes in quantities large enough and at costs low enough to foster the further development of practical applications. The fluidized bed used in this process contains mixed-metal catalyst particles. The choice of the catalyst and the operating conditions is such that the yield of single-walled carbon nanotubes, relative to all forms of carbon (including carbon fibers, multi-walled carbon nanotubes, and graphite) produced in the disproportionation reaction is more than 90 weight percent. After the reaction, the nanotubes are dispersed in various solvents in preparation for end use, which typically involves blending into a plastic, ceramic, or other matrix to form a composite material. Notwithstanding the batch nature of the unmodified prior fluidized-bed process, the fluidized-bed reactor operates in a continuous mode during the process. The operation is almost entirely automated, utilizing mass flow controllers, a control computer running software specific to the process, and other equipment. Moreover, an important inherent advantage of fluidized- bed reactors in general is that solid particles can be added to and removed from fluidized beds during operation. For these reasons, the process and equipment were amenable to modification for conversion from batch to continuous production.

Balzano, Leandro↗

Bona fide upcycling strategy of anhydride cured epoxy and reutilization of decomposed dual monomers into multipurpose applications

Waste epoxy materials become an enormous problem to society and the environment. The advantages of epoxy resins derive from their rigid and chemically stable networks, but these qualities also make them difficult to dispose of or recycle. In this work, we demonstrated an efficient degradation of anhydride cured epoxy resin by aminolysis in aminoethanol without using any catalysts. The epoxy resin was fully decomposed at 160 °C in 4 h, resulting in two distinct high purity monomers (HHPA-OH and BPA-OH). To fully realize this upcycling approach, The BPA-OH was used to synthesize a polyurethane coating with an excellent glass transition temperature (88.9 °C), scratch hardness (8H), gouge hardness (6H), adhesive strength (5B), and strong solvent resistance. The HHPA-OH with two hydroxyl groups was reacted with methacrylic anhydride to form a dimethacrylate monomer which was then used as a viable crosslinker for photo-curable 3D printing thermosetting polymer with tensile strength as high as 64 MPa and impact strength of 4.86 kJ/m 2 . This work demonstrates a feasible pathway to convert anhydride cured epoxy waste to new monomeric recyclates for superior polymer products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗