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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Pyromellitic diimide based bipolar molecule for total organic symmetric redox flow battery

Non-aqueous redox flow batteries based on total organic electrolytes, consisting of earth-abundant elements, i.e., C, H, N, O, are regarded as a promising technology for sustainable and large-scale energy storage. In particular, bipolar redox-active organic materials (BROMs) are distinctly fascinating as electroactive species because they have multiple oxidation states and can undergo multiple redox processes. By virtue of this unique characteristic, BROMs can be utilized as both anolyte and catholyte in symmetric flow batteries, consequently, helping alleviate cross-contamination issues. Here, in this paper, we report an all-organic symmetric redox flow battery based on diimide molecule as a bipolar electroactive material. The potential interval between the cathodic peak and the inner and outer anodic peaks led to a promising cell voltage of 2.22 V. The symmetric battery can be operated at a current density of 20 mA cm -2 , with a coulombic efficiency of 90% for over 100 cycles. This work proposes an alternative approach to designing multi-electron organic redox active materials to facilitate the advancement of high-density symmetric flow batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

High-Fidelity and High-Performance Computational Simulations for Rapid Design Optimization of Sulfur Thermal Energy Storage

Industrial process heating (IPH) accounts for approximately 70% of US manufacturing energy use and is primarily produced by fossil fuel combustion. Approximately 1500 TWht (approximately 60%) of IPH demand is in the temperature range of 100-300. Industrial applications in this temperature range include drying, hydrothermal processing, thermal enhanced oil recovery, food and beverage, bioethanol production, etc. Cost-effective thermal energy storage (TES) that increases the utilization of waste and renewable heat (solar, geothermal, etc.) could provide significant energy savings and reliable heat sources, decrease emissions, and increase US manufacturing competitiveness through reductions in fuel consumption. TES development has historically been dominated by technologies suitable for deployment with concentrating solar power (CSP). State-of-the-art thermal storage deployed commercially with power tower CSP plants uses a 60%/40% NaNO3/KNO3 molten salt and operates between temperatures of approximately 280 degrees Celsius and 570 degrees Celsius using a two-tank configuration. However, these nitrate salts are unsuitable for operation outside of this temperature range due to a high freezing point of approximately 220 degrees Celsius, and limits on high-temperature salt stability and corrosion resistance of containment alloys. Other materials being investigated for TES include those based on: (1) sensible energy storage (various molten salt compositions, inert solid particles, rocks or pebble beds, sulfur, water, concrete, graphite, etc.), (2) latent energy storage in materials that undergo solid-liquid phase change at relevant temperatures (organic materials for low-temperature applications, inorganic salts and/or metals for high-temperature applications), or (3) thermochemical energy storage (hydrides, hydroxides, carbonates, metal oxides, etc.). The application temperature and challenges pertaining to storage material and/or containment cost, energy density, long-term thermal and cyclic stability, and charge/discharge heat transfer effectiveness drive material selection for a given IPH or electricity generation application. Sulfur is a cheap commodity at $80/ton compared to $1100 - 1300/ton for conventional salts. When using a metric of storage cost per kWh, sulfur costs around 2-3 $/kWh. Previous sulfur TES development focused on high temperature (>600 degrees) concentrated solar power applications with sulfur encapsulated in pipes and flow of gaseous HTF (air) in the shell side. However, for lower-temperature IPH applications in the range of approximately 100-300 degrees Celsius Element 16 adopted a compact and scalable TES design with molten sulfur in the shell and HTF pipes submerged in the molten sulfur bath. The low-cost molten sulfur TES for dispatchable IPH has deployment potential for broad applications. The spatial and temporal evolution of the HTF and sulfur temperature is critical to the TES system performance, and thus detailed modeling can improve understanding of the performance and facilitate design improvements. Using high performance computing and computational fluid dynamics (CFD) a low-cost molten sulfur thermal energy storage (TES) system for industrial process heating (IPH) applications was developed. The unique challenges in CFD modeling of sulfur TES are the sharp property changes of sulfur relevant to the working temperatures. Above 159, liquid sulfur undergoes polymerization, and the viscosity of sulfur rapidly increases by several orders of magnitude between 159 degrees Celsius and 188 degrees Celsius, followed by a decrease in viscosity beyond 188 degrees Celsius due to thermal bound dissociation. In addition, various concentrations of H2S impurities can also modify sulfur viscosity. This numerical challenge is especially relevant to transient simulation of the sulfur TES charging and discharging processes as the extreme property variations limit the applicability of traditional heat transfer correlations. Transient CFD simulations including the temperature-dependent sulfur properties and geometric complexity of the TES design were used to predict the effect of natural convection during charging and discharging on the heat transfer process, sulfur temperature uniformity, charge/discharge rates, and performance of the storage devices. The CFD model was validated with experimental results for a full charge and discharge cycle. The work will show 3D and 2D simulation comparisons aimed to facilitate rapid design iterations and a machine learning based design optimization approach.

CFD↗
DOE OSTI2021

Partial substitution of rice husks for manure in greenhouse vegetable fields: Insight from soil carbon stock and aggregate stability

Abstract Soil aggregate stability and C stock are key factors in greenhouse vegetable production, which are influenced by the application of different organic materials. However, the responses of soil aggregate stability and C stock to organic amendment in greenhouse vegetable fields are not well understood. A 5‐year study was carried out in greenhouse vegetable fields to investigate the effect of partial substitution of rice husks for manure on soil aggregate stability, C compositions, and their relationships. Four treatments included: (a) no organic fertilization (control), (b) 30 t ha −1 chicken manure (CM), (c) 30 t ha −1 rice husks (RH), and (d) 10 t ha −1 chicken manure plus 20 t ha −1 rice husks (MR). Rice husks addition significantly increased the proportion of >2 mm aggregates and mean weight diameter (MWD), while manure addition showed no difference with control. Polysaccharide and humin (HM) were increased with rice husks addition (RH and MR) compared with that in CM treatment. Polysaccharide and HM caused 86.03% variation of soil aggregate, in which polysaccharide and HM contributed 76.3 and 9.7%, respectively. The soil C stock in CM, RH, and MR treatments was increased by 146, 175, and 164% compared with control, respectively. Aliphatic‐C and amorphous Fe‐oxides (Fe‐ox) content were as higher in MR added soil than those in RH treatment. Partial substitution of rice husk for manure improved soil aggregation stability and thus enhanced C stock by suppling more polysaccharide, HM and liberated soil minerals, which was conducive to the sustainable development in greenhouse vegetable production.

Fei, Chao↗
DOE OSTI2020

Hydrogen Transport in a Model 9979 Shipping Package with Inner Convenience Cans

Radiolytic hydrogen production and accumulation inside containment packages is a concern at any facility responsible for their packaging, storage, transportation, and/or disposal. When hydrogen gas accumulates to concentrations above the Lower Flammability Limit (LFL) which is 4% or 40,000 ppm in air, the possibility of a deflagration or explosion increases. This concern persists over the course of the package lifetime which is unlimited when disposed of by burial or in permanent repositories. Here, we report on a numerical model used to predict the concentration of hydrogen within each layer of a Model 9979 package containing a convenience can assembly. Simulations show the hydrogen concentration to always be highest in the inner convenience can containing the radioactive source. When the radioactive source is within the Los Alamos National Laboratory (LANL) Packaging Limits, the hydrogen concentration is shown to remain well below the LFL at all times including packaging, storage, transportation, and disposal. A hydrogen transport model is presented for a Model 9979 package system containing a nested arrangement of convenience cans, which are tin oxide coated steel cans of various sizes with a slip-lid assembly. The inner convenience can contains the radioactive source material along with an unknown quantity of incidental water acquired from humid air or processing. While visible organic materials such as paper and plastics were purposely excluded from the inner can, it is not possible to claim the wastes are entirely organic free. The inner convenience can is tape sealed and placed into a plastic bag which is horsetail closed (i.e., twisted and taped). The bagged can is placed into an outer convenience can that is also tape sealed. The can assembly is then placed into the 30 gallon drum and subsequently placed inside the 55 gallon drum in the 9979 package. Here we assume hydrogen gas is produced in the inner convenience can from alpha radiolysis of water at a rate dependent on the quantity of uranium isotopes and water present. The hydrogen transport model was used to calculate hydrogen accumulations within the package’s five layers at different times and conditions. These simulations serve two purposes; (i) to build confidence in the model by comparing predicted values to measured values, and (ii) to check the steady state hydrogen concentrations that are approached at long times in the package’s lifetime. Model simulations were compared to gas samples taken from the 30 gallon drum after storage at LANL’s Chemistry and Metallurgy Research (CMR) building for around 500 days. Hydrogen concentration calculations over much longer periods (i.e., more than 270 years) included extreme storage durations, transportation at extreme cold temperatures, and disposal of packages assuming different average temperatures.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Structure and Dispersion of Free and Grafted Polymer in Nanoparticle Organic Hybrid Materials-Based Solutions by Small-Angle Neutron Scattering

Liquid-like Nanoscale Organic Hybrid Materials or NOHMs consisting of polymer grafted nanoparticles have shown great promise in applications, such as electrochemistry and gas separation, due to their enhanced conductivity, tunability, and negligible vapor pressure. Recently, NOHMs are considered to be used as novel electrolytes in Redox Flow Batteries (RFBs). However, to employ NOHMs in redox flow batteries as electrolytes, it is important to understand the conformation and dispersion of NOHMs in the electrochemical milieu. In this work, we report the use of small-angle neutron scattering to probe the structure and dispersion of Jeffamine M2070 polymer grafted to a SiO 2 nanoparticle in an aqueous solution with and without the presence of a supporting electrolyte. Our results indicate that, in the aqueous environment, there exists a large amount of free polymer in the solution that is not grafted to the functionalized nanoparticles. These protonated free polymers, dispersed in the aqueous solvent, may also strongly interact with the grafted polymer layer and greatly affect the neat structure of NOHMs. Thus, there also exist polymers identified as “interacting” polymers to distinguish them from tethered or truly free polymers in the fluid system. The presence of supporting electrolyte shows a greater effect on the structure of NOHMs-based fluid as it not only alters the structure of the free polymer but also hinders the interaction of the polymer with the functionalized nanoparticles. Moreover, the change in the interaction of the Jeffamine M2070 with the functionalized nanoparticles due to the addition of supporting electrolyte has revealed a drastic change in the viscosities of NOHM solutions. Overall, the dispersion of the free polymer, the interaction of the interacting polymer with grafted polymer, and the change in conformation of free polymer and grafted layers with the addition of supporting electrolyte provide valuable insight into the overall scenario of the electrochemical environment of NOHMs. These results can be applied to fine-tune the structure of liquid-like NOHMs and will aid in a better understanding of their performance as potential electrolytes in RFBs.

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

Review: Recent advances of ToF-SIMS for environmental analysis and imaging

Background: Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful surface analysis technique, initially developed and applied in inorganic materials and semiconductors. In past decades, ToF-SIMS has attracted more attention in its analysis capabilities of organic materials, with increased applications in biology, medical, and health development. It has also become a versatile and effective tool in environmental analysis due to its high mass resolution, mass accuracy, and depth profiling. Results: In this review, we first give an overview of the principle of ToF-SIMS and follow with recent ToF-SIMS applications in exemplary environmental study cases, including atmospheric aerosol, soil, water, plant, and organic solvent analysis. Moreover, sample preparation techniques are summarized in relation to corresponding environmental applications. Specifically, we call attention to ToF-SIMS investigations showcasing studies in surface chemical compositions, images, and depth profile analysis. These findings emphasize the important role of interfacial chemistry in environmental processes and provide valuable insights into dynamic processes, such as chemical transformation, particle formation, plant biology, and microbial inspired biotechnology development. The mass spectral imaging results acquired by ToF-SIMS offer a deeper understanding of intermediate stages and transient phases for environmental specimens. Significance: In situ and operando imaging offer new possibilities in studying phenomena in real time with high spatial resolution. Furthermore, it is anticipated that more research groups will use ToF-SIMS in environmental research given recent advances in measurement capabilities and surging needs in chemical mapping of complex analytes and systems.

Aerosol↗
DOE OSTI2025

Non-traditional stable isotope measurements using laser desorption Orbitrap mass spectrometry: Implications for planetary missions.

Isotopic fractionation recorded in planetary materials provides insights into physical, chemical, and/or potential biological processes occurring on Solar System bodies. As we enter into the next decades of planetary exploration, the crucial information revealed by isotopic compositions of rocky and icy samples mandates that next generation spaceflight instrumentation possess the capability to measure isotope ratios in situ with sufficient precision/accuracy to distinguish between such processes. Here, in addition to identifying and fingerprinting complex organic materials with high accuracy and ultrahigh mass resolutions, laser desorption Orbitrap™ mass spectrometry (LD-O-MS) has the capability to determine the elemental and isotopic composition of solid planetary materials such as rock, regolith, organics, ice, etc. Here, we use a space-qualified LD-O-MS instrument comprising a 266 nm ultraviolet (UV) laser and Orbitrap mass analyzer ruggedized for planetary applications to investigate the stable isotopic composition of Ti and Zn metal plates. Based on the isotopic analyses, we constrain the performance of the CORALS instrument to sub per mille (‰) level accuracy and precision for Ti and at the per mille (‰) level for Zn. An LD-O-MS instrument is a versatile instrument capable of measuring isotopic composition of a variety of planetary samples and would constitute a critical instrument in the exploration of various planetary bodies including but not limited to Moon, Mars, Enceladus and other ocean or icy worlds, Ceres and other asteroids, and comets, thereby answering several high-priority questions pertaining to the formation and evolution of our Solar System.

58 GEOSCIENCES↗
DOE OSTI2024

Solvation and oxidation effects on the crystal structure and morphology of tetraoxolene-based materials

Owing to their rich redox behavior and strong metal chelating ability, tetraoxolene ligands have been established as one of the foundational building blocks for multifunctional metal–organic materials. Here, we show how simple and often overlooked synthetic parameters can be used to control the structures of transition metal and lanthanide-based metal–tetraoxolene materials across multiple length scales. Through the synthesis of twelve new compounds, we provide a comprehensive survey detailing how the choice of solvent, initial ligand redox state, and in situ oxidant impact the local coordination geometry and chain architecture, as well as the crystal size and shape (e.g., rods vs. platelets). This work represents an important step towards the synthesis of new metal–tetraoxolene materials with predictable architectures and, therefore, targeted functionality.

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

Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

Materials combining an asymmetric pore structure with mesopores everywhere enable high surface area accessibility and fast transport, making them attractive for e.g., energy conversion and storage applications. Block copolymer (BCP)/inorganic precursor co-assembly combined with non-solvent induced phase separation (NIPS) provides a route to materials in which a mesoporous top surface layer merges into an asymmetric support with graded porosity along the film normal and mesopores throughout. Here, the co-assembly and non-solvent-induced phase separation (CNIPS) of poly(isoprene)-b-poly(styrene)-b-poly(4-vinylpyridine) (ISV) triblock terpolymer and titanium dioxide (TiO 2 ) sol-gel nanoparticlesare reported. Heat-treatment in air results in free-standing asymmetric porous TiO 2 . Further thermal processing in ammonia results in free-standing asymmetric porous titanium nitride (TiN). processing changes alter structural membrane characteristics is demonstrated. Changing the CNIPS evaporation time results in various membrane cross-sections ( finger-like to sponge-like). Further, oxide and nitride material composition, crystallinity, and porosity are tuned by varying thermal processing conditions. Finally, thermal processing condition effects are probed on phase-pure asymmetric nitride membrane behavior using cyclic voltammetry to elucidate their influence, e.g., on specific capacitance. Results provide further insights into improving asymmetric and porous materials for applications including energy conversion and storage, separation, and catalysis and motivate a further expansion of CNIPS to other (in)organic materials.

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

Dynamic structural and microstructural responses of a metal–organic framework type material to carbon dioxide under dual gas flow and supercritical conditions

The structural and microstructural responses of a model metal–organic framework material, Ni(3-methyl-4,4'-bipyridine)[Ni(CN) 4 ] (Ni-BpyMe or PICNIC-21), to CO 2 adsorption and desorption are reported for in situ small-angle X-ray scattering and X-ray diffraction measurements under different gas pressure conditions for two technologically important cases. These conditions are single or dual gas flow (CO 2 with N 2 , CH 4 or H 2 at sub-critical CO 2 partial pressures and ambient temperatures) and supercritical CO 2 (with static pressures and temperatures adjusted to explore the gas, liquid and supercritical fluid regimes on the CO 2 phase diagram). The experimental results are compared with density functional theory calculations that seek to predict where CO 2 and other gas molecules are accommodated within the sorbent structure as a function of gas pressure conditions, and hence the degree of swelling and contraction in the associated structure spacings and void spaces. Furthermore, these predictions illustrate the insights that can be gained concerning how such sorbents can be designed or modified to optimize the desired gas sorption properties relevant to enhanced gas recovery or to addressing carbon dioxide reduction through carbon mitigation, or even direct air capture of CO 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2023

Hierarchical Cellulose Superinsulation Membrane

The environment-friendly components coupled with the ability to mimic the simplicity and originality of nature necessitate advanced sustainable materials with structural capabilities for energy-efficient applications. The use of feedstock deriving from plant-based, renewable organic material to produce nanofibril that embodies enhanced insulating properties and high mechanical strength constitutes an efficient development strategy. In this work, a free-standing, hierarchical superinsulation membrane by leveraging the principle of the bottom-up method is reported. The electrospun cellulose nanofibrils/aerogel-based core layer provides exceptional thermal properties with its thermal conductivity of 10.2 mW m –1 K –1 . The lightweight, flexible, and durable paper-like membrane features a tensile strength of 11.3 MPa and a bending rigidity in the order of 4.6 cN mm –1 . The hydrophobic superinsulation membrane material also exhibits a ΔT of ≈25 °C under continuous sunlight illumination and allows thermal runaway mitigation of rechargeable lithium-ion batteries. All the aforementioned properties position this hybrid superinsulation membrane as a promising material for energy-saving thermal management applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Excitonic Shockley-Read-Hall recombination in organic semiconductors

Trap-mediated recombination influences the performance of a wide range of electronic devices. The well-known Shockley-Read-Hall (SRH) expression for inorganic semiconductors is often invoked to describe the recombination rate in organic materials, although without a clear understanding of how its parameters relate to the underlying material properties or how it should be modified to account for the finite lifetime of exciton intermediates in, for example, the doped emissive layer of an organic light-emitting diode (OLED). Here, we formalize SRH recombination for organic semiconductors based on diffusive trapping and Langevin recombination. We show that including the exciton state suppresses the recombination rate in host-guest systems with type II energy level alignment whenever the interfacial gap between the host and guest molecular orbitals is comparable to the exciton energy. Furthermore, these results quantify the balance between bimolecular and trap-mediated recombination in doped OLED emissive layers, and indicate that devices with type II host-guest pairings can, in principle, beat the thermodynamic limit of their neat guest counterparts.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Many-body reactive force field development for carbon condensation in C/O systems under extreme conditions

In this paper, we describe the development of a reactive force field for C/O systems under extreme temperatures and pressures, based on the many-body Chebyshev Interaction Model for Efficient Simulation (ChIMES). The resulting model, which targets carbon condensation under thermodynamic conditions of 6500 K and 2.5 g cm –3 , affords a balance between model accuracy, complexity, and training set generation expense. We show that the model recovers much of the accuracy of density functional theory for the prediction of structure, dynamics, and chemistry when applied to dissociative condensed phase systems at 1:1 and 1:2 C:O ratios, as well as molten carbon. Our C/O modeling approach exhibits a 104 increase in efficiency for the same system size (i.e., 128 atoms) and a linear system size scalability over standard quantum molecular dynamics methods, allowing the simulation of significantly larger systems than previously possible. We find that the model captures the condensed-phase reaction-coupled formation of carbon clusters implied by recent experiments, and that this process is susceptible to strong finite size effects. Overall, we find the present ChIMES model to be well suited for studying chemical processes and cluster formation at pressures and temperatures typical of shock waves. We expect that the present C/O modeling paradigm can serve as a template for the development of a broader high pressure–high temperature force-field for condensed phase chemistry in organic materials.

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

Aircraft Measurements from a U.S. Western Wildfire Demonstrating Day and Night Differences in the Chemical Composition and Optical Properties of Biomass Burning Aerosols and Their Atmospheric Evolution

The composition and transformations of biomass burning aerosols (BBA) have been measured onboard the NOAA Twin Otter research aircraft during the Fire Influence on Regional to Global Environments and Air Quality field study. Here, we analyze real-time aerosol mass spectrometry measurements across three flights during the afternoon, late afternoon, and night of August 28, 2019, for one midsized wildfire. Analysis of several metrics showed that the aerosol composition and optical properties varied depending on the burning conditions at the fire zone and the time of day the BBA was emitted, with substantial variations in the available sunlight. The total aerosol mass loadings were dominated by organic components with a much smaller contribution from inorganic species. A gradual buildup of organic material was observed during the afternoon as the plume aged, indicating the condensation of photochemically formed low-volatility oxidized organic compounds. Highly hygroscopic ammonium nitrate was the main inorganic component, suggesting potential water content in BBA particles and the likelihood of their aqueous-phase reactivity. Depletions of particle-phase NO 3 – and Cl – relative to carbon monoxide were observed in the late afternoon and nighttime plumes, respectively, aligning with known gas-particle partitioning thermodynamics and the heterogeneous chemistry of dissolved nitrate and chloride. The wavelength-dependent light absorption by aerosol species was higher for the plume sampled at night and showed no significant changes with plume age, despite observed trends in composition and mass downwind. These differences in particle composition and optical properties demonstrate that the processes involved in BBA aging are not uniform for the same wildfire over the course of the day and depend highly on when the BBA was emitted, as well as the burning phase at the emissions source.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Low-Temperature Plasma Treatment for Enhanced Recovery of Highly Valued Critical REEs from Coal (Final Report)

The principle objective of this project was to develop a novel process flowsheet using low-temperature plasma treatment (LTP) integrated with conventional hydrometallurgical processes to recover rare earth elements (REEs), especially highly valued REEs (i.e. scandium and critical REEs), from coal and coal byproducts. LTP treatment was used to pretreat the solid feed material prior to leaching in an effort to improve the leaching characteristics of the REEs and potentially reduce acid consumption. Initially, a detailed experimental program was performed on a laboratory LTP furnace to identify a set of process parameter values to be used for assessing the enhanced leaching performance achieved on four specific gravity fractions of West Kentucky No. 13 and Fire Clay coarse coal refuse materials. High-temperature oxidation (HTO)) was also evaluated as a means for improving REE leachability on the same fractions of both coal sources. The lixiviants used to assess leachability improvements included: i) untreated water, ii) 0.1 M ammonium sulfate solution and iii) 1.2 M sulfuric acid solution at a temperature of 75°C. The laboratory data was used to develop multiple process flow sheets using HTO only to produce a rare earth oxide mix concentrate or utilizing both LTP and HTO treatment processes to generate a high purity heavy REO mix concentrate and a light REO mix concentrate. A techno-economic analysis was performed on each circuit. Low-temperature plasma oxidation was found to enhance REE leaching characteristics for all specific gravity (SG) fractions of the West Kentucky No. 13 coarse refuse material. The leaching recovery improvement was preferentially achieved for the heavy REEs with higher values obtained when treating the lower density fraction material. For example, the leaching recovery for the heavy REEs in the untreated 1.6 SG Float fraction material was 8% in a 0.1 M ammonium sulfate solution. After LTP treatment for 32 hours, heavy REE recovery increased to 33%. The corresponding recovery value for the light REEs was 10%. These findings indicate a strong affinity of the heavy REEs with the organic material, which is the component being reduced in content during the LTP treatment. Scanning electron micrographs showed the development of a honeycomb structure with increased LTP treatment with higher surface area as confirmed from BET measurements. Higher surface area promotes improved leaching efficiency due to enhance chemical interactions. When using 1.2 M sulfuric acid, the LTP treatment was found to provide a heavy REE recovery increase from 23% to 53% for the 1.6 SG Float fraction which corresponded to an ash content increase from around 20% to 35%. However, LTP treatment provided no improvement in leaching characteristic for the 2.2 SG sink material in the acid solution, which was likely due to the low organic content. The LTP treatment of the Fire Clay SG fractions provided no improvement in REE leaching characteristic, which may be due to the association with REE minerals such as monazite and REE-associated mineral matter such as clays. High temperature oxidation using temperatures in the range of 600-750OC was found to significantly enhance the leaching characteristics of both the light and heavy REEs for all density fractions in both coarse coal refuse materials. Generally, the increase in light REE recovery for the West Kentucky material was from 15% for the untreated material to 90% for the HTO treated material at 600°C. Recovery values dropped significantly when using temperatures below 600°C and above 750°C. The impact of the excessive temperatures was most likely a result of sintering. For the heavy REEs, HTO significantly improved recovery in the lighter SG fractions, which may be due to an affinity with the organic content. Only limited heavy REE recovery improvement was obtained for the denser SG fractions. Another benefit of HTO is the conversion of calcium-based minerals to a very soluble calcium oxide, which is removable using a mild acid solution, and the conversion of Fe minerals to relatively insoluble minerals such as hematite and magnetite. The pregnant leaching solution produced from the leaching of all SG fractions obtained from both coal sources was treated using two stages of solvent extraction procedurally modeling a rougher-cleaner circuit followed by oxalic acid precipitation. Rare earth oxide products having a purity greater than 97% was produced from nearly all of the SG fractions. A novel process flowsheet was developed based on the selective leaching of heavy REEs that was made possible through LTP treatment of West Kentucky No. 13 coarse refuse followed by salt leaching. In the flowsheet, coal refuse material is ground to a top size of 1mm and then treated by LTP. The treated material is mixed into a 0.1 M ammonium sulfate solution and then filtered to produce a heavy REE enriched pregnant leach solution. The heavy REEs are concentrated by two stages of selective precipitation to produce a heavy REE mix oxalate and then roasted to obtain a heavy REO mix concentrate. The solid residues remaining after salt leaching is dried and then subjected to HTO treatment followed by concentration using selective precipitation and roasting to produce a light REO mix concentrate. An alternative circuit was developed using HTO treatment only to treat 100% of the coarse refuse material followed by selective precipitation and roasting to generate a high purity REO mix product. A techno-economic analysis performed for the treatment of West Kentucky No. 13 and Fire Clay coarse refuse based on a hypothetical 500-tph plant revealed that the net present value for all scenarios was significantly negative. Primary reasons include: i) a substantial decrease in the basket value of the final product relative to the feed and ii) high chemical costs relative to the amount of product generated. The basket value reduction was primarily due to little to no scandium recovery due to poor leaching characteristics when using low acid concentrations as necessitated by the low feed grades. Operating costs were primarily influenced by the chemical costs relative to the kilograms of concentrate produced and feed grade. For the Fire Clay coarse refuse material, the total operating cost was estimated to be $354 per kg of REO produced which was higher than the basket value of the REO product ($276/kg). Approximately 37% of the total cost was the sulfuric acid used during the leaching process. A comparative analysis performed to assess the economic viability of using low-temperature plasma furnaces found that market value enhancement for the generation of both heavy REO and light REO concentrates will be needed in addition to significant technology advancements to reduce the cost of plasma furnaces.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

Controlling the Manifold of Polariton States Through Molecular Disorder

Exciton polaritons, arising from the interaction of electronic transitions with confined electromagnetic fields, have emerged as a powerful tool to manipulate the properties of organic materials. However, standard experimental and theoretical approaches overlook the significant energetic disorder present in most materials now studied. Using the conjugated polymer P3HT as a model platform, the degree of energetic disorder is systematically tuned and a corresponding redistribution of photonic character within the polariton manifold is observed. Based on these subtle spectral features, a more generalized approach is developed to describe strong light–matter coupling in disordered systems that captures the key spectroscopic observables and provides a description of the rich manifold of states intermediate between bright and dark. Finally, applied to a wide range of organic systems, the method challenges prevailing notions about ultrastrong coupling and whether it can be achieved with broad, disordered absorbers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phonon-engineered extreme thermal conductivity materials

Materials with ultrahigh or low thermal conductivity are desirable for many technological applications, such as thermal management of electronic and photonic devices, heat exchangers, energy converters and thermal insulation. Recent advances in simulation tools (first principles, the atomistic Green’s function and molecular dynamics) and experimental techniques (pump–probe techniques and microfabricated platforms) have led to new insights on phonon transport and scattering in materials and the discovery of new thermal materials, and are enabling the engineering of phonons towards desired thermal properties. Here, we review recent discoveries of both inorganic and organic materials with ultrahigh and low thermal conductivity, highlighting heat-conduction physics, strategies used to change thermal conductivity, and future directions to achieve extreme thermal conductivities in solid-state materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Charge Transport in Solvated Donor–Acceptor Functionalized Peptoids: Molecular Dynamics and Rate Theory

Scalable solar-energy conversion requires photoactive materials that combine the efficiency of natural photosynthetic systems with the stability and processability needed for practical applications. Achieving reliable charge transport in soft, self-assembled organic materials remains challenging, as structural fluctuations and environmental effects strongly influence charge-transfer (CT) rates. Here, we present a broadly applicable computational framework for evaluating CT rates in the condensed phase, combining Fermi’s golden rule rate theory with inputs from all-atom molecular dynamics (MD) simulations and first-principles electronic-structure calculations. The approach does not rely on system-specific parametrization and is applicable to a wide range of soft and disordered materials. We demonstrate the applicability and usefulness of the framework on redox-active peptoids functionalized with iron–porphyrin (Fe–P) complexes, a bioinspired platform with programmable donor–acceptor units and tunable three-dimensional organization. The calculated CT rates exhibit strong sensitivity to molecular conformation, with variations spanning several orders of magnitude. This dependence is shown to arise from the pronounced variation in diabatic electronic coupling with the relative orientations and separations of the Fe–P complexes across the conformational ensemble. The framework provides a consistent route for connecting atomistic structure to CT kinetics in the condensed phase and enables analysis of structure–rate relations in organic semiconducting systems.

Charge transfer↗