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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 127 records · Page 7

The role of biochar in the degradation of sugars during fast pyrolysis of biomass

With appropriate pretreatment, sugars can be a major product from fast pyrolysis of lignocellulosic biomass. Analytical pyrolysis of pure cellulose can produce up to 60 wt% yield of levoglucosan although yields are significantly lower in continuous pyrolysis at larger scales. Secondary reactions of vaporized levoglucosan are thought to be responsible for this loss of sugar yield, suggesting changes in the design and operation of pyrolysis reactors to minimize these reactions. Micropyrolysis experiments were performed to better understand the mechanism of sugar degradation in the presence of biochar. A 57% loss in levoglucosan yield was observed for cellulose overlain with untreated biochar powder compared to the pure cellulose control sample. The addition of biochar derived from pyrolysis of untreated corn stover to a fluidized bed pyrolyzer reduced sugar yields from cellulose from 61.3 wt% to 21.3 wt% and 41.5–11.6 wt% for conventional and autothermal operation, respectively. The significant drop in sugar yield due to biochar interaction inspired change in feeder configuration for the fluidized bed pyrolyzer to reduce vapor-char interactions. Biomass feeding was changed from in-bed to above-bed injection, which allowed significant devolatilization to occur above the layer of biochar that exists at the surface of the bed. Finally, by reducing secondary reactions, bio-oil and sugar yields increased by 7.9% and 14%, respectively, for autothermal pyrolysis.

09 BIOMASS FUELS↗

Co-depolymerization of lignin and plastic waste using hydrothermal liquefaction process

Sustainable valorization of underutilized lignin and plastic waste beyond incineration is critical for producing renewable fuels. Hydrothermal liquefaction (HTL) provides a promising approach to convert wet lignin and plastics into high-quality oils without the need for prior drying of wet lignin. Here, this study examines the effects of temperature (300–400 °C), residence time, and polymer molecular weight on product yield and composition during HTL of polyethylene (PE), polypropylene (PP), and lignin under subcritical and supercritical water conditions. For PE, oil yields increased with temperature, with low molecular weight (LMW) PE achieving a maximum of ∼93 % at 400 °C for 30 min, while high molecular weight (HMW) PE reached ∼86 % at 400 °C for 1 h. Lignin and PP exhibited optimal oil yields at intermediate temperatures, decreasing at higher temperatures due to secondary reactions and char formation. Lignin yielded a maximum of ∼22 % oil at 300 °C for 30 min, LMW PP ∼88 % at 375 °C for 1 h, and HMW PP ∼83 % at 400 °C for 1 h. GC–MS analysis revealed that lignin oils were rich in phenols and alkylphenols, while PE and PP oils were dominated by paraffins and olefins. Oxygenated compounds in PE decreased at higher temperatures, improving oil quality. Co-liquefaction of lignin with plastics enhanced oil yields and energy content under specific conditions, demonstrating synergistic effects dependent on plastic type, molecular weight, and HTL conditions. These findings highlight the potential of HTL to produce high-energy, value-added fuels from lignin–plastic mixtures.

09 - BIOMASS FUELS↗

The evolution of coal porosity during pyrolysis

Gasification of coal, municipal waste, or other organic materials is a potential hydrogen source that entails complex thermal decomposition and transport processes. This study provides a multiscale analysis of these processes for sub-bituminous (Usibelli, Healy, Alaska) and lignite (Center, North Dakota) coals and provides data useful for process design. The chemistry, mineralogy, and pore structures of pyrolyzed coal and their evolution with thermal decomposition are discussed. Samples pyrolyzed at 200–1000 °C were analyzed by small-angle neutron scattering; ultra-small, small-, and wide-angle X-ray scattering; and other complementary techniques. Scanning electron microscopy showed new pores in the high-temperature-pyrolyzed material. Upon heating, the coals became progressively denser, and the concentration of hydrogen decreased. Changes in pore volume fell into three temperature ranges: an initial, low-temperature range that, for the Usibelli coal, involved an increase in overall porosity; a mid-temperature range associated with pore volume loss; and a high-temperature range associated with significant porosity increase and char formation. This transformation was paralleled by changes in fractal dimension and correlation length. The higher the pyrolysis temperature the greater the small-pore-volume fraction and overall surface area became. Pyrolysis increased the lateral size of coal crystallites, decreased the amorphous fraction, and increased the aromatics fraction and overall coal rank. Comparisons of neutron and X-ray scattering data and subsequent water uptake studies showed that pre-dried coals can re-hydrate relatively rapidly upon exposure to air, which can significantly affect the porosity calculated from small-angle-scattering data. Fits to the cumulative porosity curves provide a method for modeling the physical and chemical transformation of hydrogen-containing feedstock during gasification.

Anovitz, Lawrence {Larry} [ORNL] (ORCID:0000000226↗

Process intensification in hydrothermal liquefaction of biomass: A review

Hydrothermal liquefaction (HTL) presents a promising pathway for converting wet biomass resources into biofuels, offering significant advantages over conventional methods. However, numerous challenges must be addressed for HTL scale-up, including energy provision for the endothermic process, heat and mass transfer limitations, slurry concentration and pumpability challenges, char and coke formation, and continuous phase separation. This review explores key strategies such as autothermal HTL, which improves process efficiency and reduces external energy requirements by coupling exothermic and endothermic reactions within the same reactor, thereby simplifying reactor design and reducing operational costs. Additionally, multistage HTL processes are highlighted for their ability to optimize biocrude quality and yield by fractionating biomass conversion stages, resulting in higher energy returns on investment and better-quality biocrude. Solvothermal HTL and integration techniques for aqueous phase are also discussed. Furthermore, the HTL patent landscape is discussed to provide insights into current technological advancements. This review aims to offer a comprehensive understanding of process intensification in HTL, highlighting innovative solutions to enhance the efficiency and scalability of the process for sustainable biofuel production.

Biocrude oil↗

Highly thermally stable copolymers of epoxy and trifunctional polybenzoxazine

Here, in this work, we report the copolymerization of a triamine-based benzoxazine and a commercial difunctional epoxy resin, and investigate their synergistic effect on improved thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Results showed that a glass transition temperature increase of up to 268 °C was obtained for the copolymer with as low as 25 wt% epoxy. A higher thermal performance was also achieved with an onset degradation of nearly 400 °C and char yield of 39 wt% at 800 °C for the copolymer with 52 wt% epoxy. The behavior was compared to previously reported benzoxazine/epoxy combinations and was found to be advantageous. The curing behavior of different copolymer compositions was also investigated via DSC and a methodology for matching each peak with its corresponding reaction was developed. Results showed that the alternating favorability of the reactions was dependent on the benzoxazine/epoxy ratio. Overall, the prepared PBZ/epoxy copolymers displayed higher thermal stability than their individual components, indicating suitability for a number of potential extended uses including utility in higher temperature applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub-volt conversion of activated biochar and water for H 2 production near equilibrium via biochar-assisted water electrolysis

Sluggish water oxidation reactions limit water electrolysis for H 2 production, which can be alleviated by the use of carbon-based ma- terials like agricultural wastes as reducing agents. Biochar from such biomass can reduce equilibrium cell potentials at standard condi- tions from 1.23 V to 0.21 V by avoiding direct water splitting at the anode. However, some challenges hinder biochar oxidation, including poor biochar binding, electrode caking, and surface passivation. We find that enhanced C/O ratio, crystallinity, and negative zeta potential improve biochar oxidation kinetics at mod- erate temperatures. Smaller particle sizes and better mixing pre- vent electrode caking, enhancing biochar stability. Here, we report sub-volt biochar-coupled H 2 production, often referred to as a bio- char-assisted water electrolysis (BAWE), yielding 250 mA/g cat H 2 current at 100% Faradaic efficiency. Over 1 mA current was observed at a near-equilibrium cell potential of 0.2 V cell potential. Using a single-junction solar cell-powered BAWE, 15 mA H 2 is generated at 1 Sun, resulting in 4.8% solar-to-hydrogen efficiency, equivalent to 35% when the energy of H 2 relative to H 2 O (without biochar) is assumed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Donor–Acceptor Conjugated Copolymers Containing Transition-Metal Complex: Intrachain Magnetic Exchange Interactions and Magneto-Optical Activity

A donor-acceptor conjugated copolymer containing thienothiophene (TT) (Donor) units and Co(II) complexes (Acceptor) has been synthesized and characterized. The studies of magnetic properties of the polymers by SQUID and EPR measurements showed antiferromagnetic exchange interaction between neighboring spin centers along with the polymer backbone through intrachain in-teractions. It is the first time that D-A conjugated polymer backbone serving as bridging ligands for magnetic couplings, making this type of polymers promising as magnetic materials. Moreover, the magneto-optical activity (MOA) of polymer LCP1 was char-acterized using magnetic circular dichroism (MCD) spectroscopy. It was found that the material exhibits a large magneto-optic rotation with a peak Verdet constant of 2980 deg*T -1 *m -1 at 590 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing Hidden Quinones Through Diagnostic MS² Fragmentation of Peptide–Quinone Adducts

Quinones are redox-active components of natural organic matter that mediate electron transfer and influence biogeochemical processes, but many quinones in pyrogenic organic matter (PyOM) remain unresolved because they ionize poorly by mass spectrometry. Here, we present a peptide-tagging approach to improve detection of cysteine-reactive electrophiles in PyOM, with quinones expected to be a dominant subset based on reaction chemistry and selectivity experiments. A cysteine-containing peptide was used to form Michael-addition adducts, enhancing electrospray ionization and enabling untargeted screening by high-performance liquid chromatography-high-resolution tandem mass spectrometry. The method was benchmarked with five quinone standards and applied to extracts from charred plant material as a discovery-level screen for cysteine-reactive targets. We identified 98 quinone-candidate adducts (mean neutral mass ~603 Da), of which more than 70% were not detectable in native MS1 data. Among formula-assigned features, hidden quinone candidates had median (O+N)/C of 0.391 and normalized oxidation state of carbon of -0.281, consistent with relatively low polarity and low oxidation state. These results reveal a previously inaccessible pool of hidden redox-active compounds in PyOM and provide a framework for prioritizing quinone-like electrophiles for confirmation and incorporation into models of fire-driven biogeochemical cycling.

LC-MS/MS↗

Understanding and Mitigating Stickiness in Biochar Produced through Acid Hydrolysis and Dehydration

Levulinic acid is a platform chemical with significant potential for conversion into a wide range of biobased chemicals and fuels. A common process for producing levulinic acid from lignocellulosic feedstocks involves acid hydrolysis and dehydration (AHDH), where hexose polymers are hydrolyzed into monomeric sugars and subsequently dehydrated to levulinic acid and formic acid in the presence of dilute sulfuric acid. However, scaling the AHDH process is challenging because of the formation of byproducts such as sticky biochar, which accumulates in continuous-flow reactors, reducing effective reaction volume and increasing process downtime. This study investigates the effect of a chemical preconditioning step on mitigating sticky biochar formation. Woody biomass was preconditioned at 170 °C with 0.26 wt % sulfuric acid for 30 min, resulting in substantial removal of hemicellulose and acid-soluble lignin. AHDH of these preconditioned solids produced biochar that did not adhere to reactor surfaces. TGA analysis confirmed that the chemical preconditioning step minimized interactions between hemicellulose-derived degradation products and lignin side chains, reducing sticky char formation. Additionally, the study observed a 6% higher yield of organic acids from softwood species compared to hardwoods, with bark content shown to negatively impact yield. These findings suggest that targeted preconditioning of lignocellulosic biomass can enhance reactor operability and improve organic acid production efficiency in AHDH processes.

biopolymers↗

High-Temperature-Performance Cyanate Ester Composites with Carboranes

Cyanate ester (CE) is an important class of materials among high-temperature performance thermosets. It is used in aerospace launch vehicles, heat sinks, booms, and trusses of satellites etc. due to its high glass transition temperatures (>220°C), excellent thermal stability, and low flammability. Current approaches to improve the thermal stability of CE include incorporation of siloxanes or phosphorus- based flame retardants (PFRs). In this work, we have explored boron-based hydroxy (PD) and epoxy (EP) functionalized carborane additives to improve the thermal properties of CE. Carborane fillers were solvent blended at various mass loadings in the resin and cured to study their effect on thermal properties. PD and EP carboranes react with CE to form iminocarbonate and oxazolidinone linkages respectively. Cure kinetics studies at different wt% loadings explained that carboranes catalyze the curing reaction by reducing curing activation energy by about 54% and 26% for 10 wt% loadings of PD and EP carboranes respectively. In addition, carborane-filled cyanate ester (CE) nanocomposites demonstrate an exceptionally high thermal stability as compared to the pristine resin in air and inert environment. Our thermogravimetric analysis (TGA) experiments show that the ultimate char yield of the resin can be increased from 0% to as high as 76% and 82% with 30 wt% PD and EP carborane loading respectively at 1000 °C in air. The initial degradation temperature T d;5 of the composites decreased with increasing carborane loadings in both air and argon. For instance, T d;5 for CE was 465 and 471.6 °C in argon and air while that for P20 was 437.4 and 452.1 °C. Modulated TGA studies gave evidence of the effect of carboranes on degradation kinetics and the mechanism of the resin in air and inert environment. The effect of bonding between carboranes and CE at various loadings on the thermal expansion of the matrix was also studied using Thermomechanical Analyzer (TMA). PD carborane reduced the T g for P20 to about 225 °C while CE had T g >350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emergent Chemical Behavior in Mixed Food and Lignocellulosic Green Waste Hydrothermal Liquefaction

Hydrothermal liquefaction (HTL) is a promising strategy for the conversion of energy-dense waste streams to fuels. Mixed-feed HTL aggregates multiple feed streams to achieve greater scales that capitalize on local resources, hence lowering costs. The potential for new pathways and products upon feedstock blending becomes a compounding level of complexity when unlocking emergent chemistries. Here, food and green waste streams were evaluated under HTL conditions (300 °C, 1 h) to understand the effect of feed molecular composition on product distributions and mechanisms. Thousands of emergent chemical compounds were detected via Fourier transform ion cyclotron resonance mass spectrometry, ultimately leading to the emergence of two dominant outcomes. First, the presence of small amounts of food waste into green waste results in substantial decarboxylation and subsequent polymerization to biocrude than chars. Second, in the other limit, small amounts of green waste promote the capping of oxygenates into the biodiesel range, such as with the emergence of fatty acid methyl esters.

09 BIOMASS FUELS↗

Bioenabled Platform to Access Polyamides with Built-In Target Properties

The diversification of platform chemicals is key to today’s petroleum industry. Likewise, the flourishing of tomorrow’s biorefineries will rely on molecules with next-generation properties from biomass. Herein, we explore this opportunity with a novel approach to monomers with custom property enhancements. Cyclic diacids with alkyl and aromatic decorations were synthesized from muconic acid by Diels-Alder cycloaddition and copolymerized with hexamethylenediamine and adipic acid to yield polyamides with built-in hydrophobicity and flame retardancy. Testing shows a 70% reduction in water uptake and doubling of char production while largely retaining other key properties of the parent Nylon-6,6. In conclusion, the present approach can be generalized to access a wide range of performance-advantaged polyamides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analyzing Wildland Fire Smoke Emissions Data Using Compositional Data Techniques

By conservation of mass, the mass of wildland fuel that is pyrolyzed and combusted must equal the mass of smoke emissions, residual char and ash. For a given set of conditions, these amounts are fixed. This places a constraint on smoke emissions data which violates statistical assumptions for many of the methods currently used to analyze these data such as linear regression, analysis of variance, and t-tests. These data are inherently multivariate and non-negative parts of a whole. This paper introduces the field of compositional data analysis to the emissions community and provides examples of appropriate statistical treatment of emissions data. It is shown that modified combustion efficiency should not be used as a predictor variable for other smoke emissions because it is not an independent variable. An alternative method based on compositional linear trends to estimate trace gas composition using CO and CO2 is presented. The data used in this paper resulted from projects the DOD/DOE/EPA Strategic 586 Environmental Research and Development Program projects RC-1648 and 1649. The senior 587 author appreciates the guidance and R scripts provided by Prof. Girty at San Diego State 588 University to estimate linear trends by perturbation. J. P.-A. was supported by the Spanish 589 Ministry of Science, Innovation and Universities under the project CODAMET (RTI2018-590 095518-B-C21, 2019-2021). The data used in this study have been previously published and are 591 available in the original publications. DRW conceived the initial manuscript (70 percent) and 592 performed the bulk of the data analysis. JPA provided statistical guidance and compositional data 593 expertise and contributed 20 percent of the manuscript. TJJ and HJ were extensively involved in 594 the study that provided the data. TJJ provide smoke emissions expertise and HJ provided 595 combustion expertise. The authors declare that they have no conflict of interest. The use of trade 596 or firm names in this publication is for reader information and does not imply endorsement by 597 the U.S. Department of Agriculture of any product or service.

simplex, compositional data analysis, balance, log↗

Constraints and Drivers of Dissolved Fluxes of Pyrogenic Carbon in Soil and Freshwater Systems: A Global Review and Meta‐Analysis

Abstract Pyrogenic carbon (PyC) is a significant component of the global soil carbon pool due to its longer environmental persistence than other soil organic matter components. Despite PyC's persistence in soil, recent work has indicated that it is susceptible to loss processes such as mineralization and leaching, with the significance and magnitude of these largely unknown at the hillslope and watershed scales. We present a review of the work concerning dissolved PyC transport in soil and freshwater. Our analysis found that the primary environmental controls on dissolved PyC (dPyC) transport are the formation conditions and quality of the PyC itself, with longer and higher temperature charring conditions leading to less transport of dPyC. While correlations between dPyC and dissolved organic carbon in rivers and other pools are frequently reported, the slope of these correlations was pool‐dependent (i.e., soil‐water, precipitation, lakes, streams, rivers), suggesting site‐specific environmental controls. However, the lack of consistency in analytical techniques and sample preparation remains a major challenge to quantifying environmental controls on dPyC fluxes. We propose that future research should focus on the following: (a) consistency in methodological approaches, (b) more quantitative measures of dPyC in pools and fluxes from soils to streams, (c) turnover times of dPyC in soils and aquatic systems, and (d) improved understanding of how mechanisms controlling the fate of dPyC in dynamic post‐fire landscapes interact. With more refined quantitative information about the controls on dPyC transport at the hillslope and landscape scale, we can increase the accuracy and utility of global carbon models.

58 GEOSCIENCES↗

Dimensionality crossover to a two-dimensional vestigial nematic state from a three-dimensional antiferromagnet in a honeycomb van der Waals magnet

The effects of fluctuations and disorder, which are substantially enhanced in reduced dimensional-ities, can play a crucial role in producing nontrivial phases of matter such as vestigial orders char-acterized by a composite order parameter. However, fluctuation-driven magnetic phases in low dimensions have remained relatively unexplored. Here we demonstrate a phase transition from the zigzag antiferromagnetic order in the three-dimensional bulk to a Z 3 vestigial Potts-nematicity in two-dimensional few-layer samples of van der Waals magnet NiPS 3 . Our spin relaxometry and op-tical spectroscopy measurements reveal that the spin fluctuations are enhanced over the gigahertz to terahertz range as the layer number of NiPS 3 reduces. Monte Carlo simulations corroborate the experimental finding of 3-fold rotational symmetry breaking, but show that translational symmetry is restored in thin layers of NiPS 3 . Furthermore, our results show that strong quantum fluctuations can stabilize an unconventional magnetic phase after destroying a more conventional one.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The Effects of Polyolefin Structure and Source on Pyrolysis-Derived Plastic Oil Composition

Seven types of plastics were pyrolyzed in a fluidized bed reactor: post-consumer recycled (PCR) high-density polyethylene (HDPE), PCR polypropylene (PP), virgin resins of varying molecular weights of HDPE, virgin resins of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and (PP). Pyrolysis produced non-condensable gases (C1-C3), liquid phase products (C4-C40), and solids (C40+ and chars), with alkane, alkene, alkadiene, aromatic, and multi-cycloaromatics as the predominant compounds. Polymer structure had the greatest impact on product distribution, with minimal influence from molecular weight. Branches in polyethylene (PE) acted as thermal defects initiating degradation. Higher branch density in PE led to increased concentrations of aromatics, branched alkanes, and internal alkenes. PP and PE exhibited distinct degradation mechanisms, with PP requiring less energy for decomposition and yielding more oil. Here, pyrolysis oil from PCR HDPE and PCR PP contained a higher proportion of branched compounds. Additives in PCR plastics may promote isomerization during pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plastic waste gasification for low-carbon hydrogen production: a comprehensive review

Hydrogen is one of the most important feedstocks for the chemical industry, power production, and the decarbonization of other sectors that rely on natural gas. The production of hydrogen from plastics enables sustainable use of plastic waste and offers significant environmental benefits. Gasification emerges as a promising route for chemical recycling, converting plastic into hydrogen and other valuable chemicals. Although the gasification of plastic waste has recently gained attention, the number of studies regarding low-carbon hydrogen production is still limited. The effective integration of carbon capture, utilization, and storage (CCUS) is essential for achieving low-carbon hydrogen production via gasification, which enables the efficient capture and storage of CO 2 emissions. Incorporating coal waste and biomass into plastic gasification can synergistically enhance reforming reactions for hydrogen production, reduce tar content, and resolve feeding issues caused by plastic stickiness. Based on the previous studies, this paper briefly reviews the mechanisms of plastic gasification including plastic depolymerization, reforming, tar and char formation, and gasification; the discussions on feedstocks and effects of operating conditions on H 2 production including plastic-type, temperature, steam/carbon ratio, equivalence ratio, and catalysts; and the integration of CCUS and alternative recovery processes in plastic gasification for low-carbon hydrogen.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface-active antibiotic production as a multifunctional adaptation for postfire microorganisms

Abstract Wildfires affect soils in multiple ways, leading to numerous challenges for colonizing microorganisms. Although it is thought that fire-adapted microorganisms lie at the forefront of postfire ecosystem recovery, the specific strategies that these organisms use to thrive in burned soils remain largely unknown. Through bioactivity screening of bacterial isolates from burned soils, we discovered that several Paraburkholderia spp. isolates produced a set of unusual rhamnolipid surfactants with a natural methyl ester modification. These rhamnolipid methyl esters (RLMEs) exhibited enhanced antimicrobial activity against other postfire microbial isolates, including pyrophilous Pyronema fungi and Amycolatopsis bacteria, compared to the typical rhamnolipids made by organisms such as Pseudomonas spp. RLMEs also showed enhanced surfactant properties and facilitated bacterial motility on agar surfaces. In vitro assays further demonstrated that RLMEs improved aqueous solubilization of polycyclic aromatic hydrocarbons, which are potential carbon sources found in char. Identification of the rhamnolipid biosynthesis genes in the postfire isolate, Paraburkholderia kirstenboschensis str. F3, led to the discovery of rhlM, whose gene product is responsible for the unique methylation of rhamnolipid substrates. RhlM is the first characterized bacterial representative of a large class of integral membrane methyltransferases that are widespread in bacteria. These results indicate multiple roles for RLMEs in the postfire lifestyle of Paraburkholderia isolates, including enhanced dispersal, solubilization of potential nutrients, and inhibition of competitors. Our findings shed new light on the chemical adaptations that bacteria employ to navigate, grow, and outcompete other soil community members in postfire environments.

59 BASIC BIOLOGICAL SCIENCES↗