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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Magnetic Field Directed Rare‐Earth Separations

Abstract The separation of rare‐earth ions from one another is challenging due to their chemical and physical similarities. Nearly all rare‐earth separations rely upon small changes in ionic radii to direct speciation or reactivity. Herein, we show that the intrinsic magnetic properties of the rare‐earth ions impact the separations of light/heavy and selected heavy/heavy binary mixtures. Using TriNOx 3− ([{(2‐ t BuNO)C 6 H 4 CH 2 } 3 N] 3− ) rare‐earth complexes, we efficiently and selectively crystallized heavy rare earths (Tb–Yb) from a mixture with light rare earths (La and Nd) in the presence of an external Fe 14 Nd 2 B magnet, concomitant with the introduction of a concentration gradient (decrease in temperature). The optimal separation was observed for an equimolar mixture of La:Dy, which gave an enrichment factor of EF La:Dy =297±31 for the solid fraction, compared to EF La:Dy =159±22 in the absence of the field, and achieving a 99.7 % pure Dy sample in one step. These results indicate that the application of a magnetic field can improve performance in a molecular separation system for paramagnetic rare‐earth cations.

Higgins, Robert F.↗
DOE OSTI2023

Understanding the performance of membrane for direct air capture of CO 2

Abstract Direct air capture (DAC) of CO 2 is becoming increasingly important for reducing greenhouse gas concentrations in the atmosphere. However, the cost and energy requirements associated with DAC make it less economically feasible than carbon capture from flue gases. While various methods like solid sorbents and gas–liquid absorption have been explored for DAC, membrane processes have only recently been investigated. The objective of this study is to examine the separation performance of a membrane unit for capturing CO 2 from ambient air. The performance of a membrane depends on several factors, including the composition of the feed gas, pressure ratio, material selectivity, and membrane area. The single‐stage separation process with the co‐current flow and constant permeability flux model is evaluated using a commercial module integrated with a process simulator to separate a binary mixture of carbon dioxide and nitrogen to assess the sensitivity of selectivity on purity and recovery of CO 2 in permeate, and power requirement. Additionally, three levels of CO 2 reduction from the feed stream to the retentate stream (25%, 50%, and 75%) are studied. A trade‐off between purity and recovery factor is observed, and achieving high purity in permeate requires high concentration in the retentate.

Panja, Palash↗
DOE OSTI2025

Thermodynamic Water Activity Explains the Unusual Electrochemical Stability of Aqueous Deep Eutectic Solvents

The presence of water in nonaqueous deep eutectic solvent (DES) electrolytes has been debated in recent years, with efforts ranging from its complete removal to willful addition. It was shown that controlled amounts of water can be beneficial, as it not only enhances the physicochemical properties of these electrolytes but also has no significant detrimental effects on their electrochemical stability. Despite these advantages, there is still limited understanding of how water interacts with DES systems at the molecular level. This study examines the water activity in ethylene glycol and glycerol, as well as their binary mixtures with choline chloride to form the DESs ethaline and glyceline, respectively. In this work, we show that the high electrochemical stability of glyceline is related to its lower water activity compared to ethaline and can be attributed to the robust H-bonding network formed by the three hydroxyl groups of glycerol. Its 3D H-bond network effectively integrates water molecules within its solvent structure, reducing degradation and maintaining stability at higher water contents. The deviations from the ideal Raoult's law behavior are reflected in the water activity and activity coefficients, which highlight the intricate H-bond interactions within DES-water mixtures. Water acts like a lubricant within the more viscous DES mixtures without being detrimental to their electrochemical performance. The presented results emphasize the necessity of customizing DES-water compositions to enhance their performance as electrolytes, especially in flow battery applications where electrochemical stability, ionic conductivity, and fluidity are of utmost importance.

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

Thermodynamic modeling of aqueous acetic acid, butyric acid, and lactic acid solutions

Based on the activity coefficient – fugacity coefficient approach, a rigorous thermodynamic modeling study is presented for accurate correlation of vapor-liquid equilibrium data of aqueous solutions of acetic acid (293 to 391 K), butyric acid (325 to 436 K), lactic acid (378 to 409 K), and acetic acid + butyric acid binary mixture (358 to 421 K). In addition, the pH data of the three aqueous, single carboxylic acid solutions were measured at 298 to 328 K and successfully correlated. Given that these aqueous carboxylic acid solutions exhibit various degrees of association behavior in both vapor and liquid phases, the thermodynamic models considered for this study include the Redlich-Kwong equation of state (RK-EoS) and the Hayden-O’Connell equation of state (HOC-EoS) for the vapor phase fugacity coefficients and the electrolyte non-random two-liquid model (eNRTL) and the association electrolyte non-random two-liquid model (AeNRTL) for the liquid phase activity coefficients. The combination of the HOC-EoS for the vapor phase and the AeNRTL model for the liquid phase is found to provide the best correlation results, consistent with the fact that the HOC-EoS and the AeNRTL model explicitly account for association behaviors in the vapor phase and the liquid phase, respectively.

09 BIOMASS FUELS↗
DOE OSTI2020

ReaxFF-based molecular dynamics study of bio-derived polycyclic alkanes as potential alternative jet fuels

This work investigates the initial stages of the pyrolysis of HtH-1 (C 18 H 32 ; 2,2,7,7,8a,8b-hexamethyl-dodecahydrobiphenylene) and HtH-2 (C 18 H 34 ; 1,1',3,3,3',3'-hexamethyl-1,1'-bi(cyclohexane)), which are bio-derived polycyclic alkanes and potential jet fuels, using ReaxFF force field based molecular dynamics (MD) simulations. Global Arrhenius parameters, such as activation energies and pre-exponential factors, are calculated and used to analyze the overall decomposition kinetics of the fuels. HtH-1 decomposes faster than HtH-2 at the same temperature and density conditions, and they have a faster decomposition rate compared to some existing jet-fuels, such as JP-10. A systematic reaction analysis framework developed in this work is applied to determine a temperature-dependent decomposition mechanism. At lower temperature, the central C-C bond connecting the two cyclohexane rings is dominantly broken in both HtH-1 and HtH-2. However, C-CH 3 bond breaking becomes dominant with increasing temperature due to the large increase in entropy during this reaction. Major products from HtH-1 are C 5 H 8 and C 4 H 8 , and those from HtH-2 are C 4 H 8 and C 2 H 4 . The major products predict that HtH-1 has a higher sooting tendency than HtH-2, which is consistent with measurements. The impact of HtH-2 on the pyrolysis of HtH-1 is also investigated in their binary mixtures. HtH-1 and HtH-2 decompose by unimolecular reactions, and they rarely interact with each other during the pyrolysis of the mixtures. Furthermore, this work demonstrates that ReaxFF can be used to investigate pyrolysis and combustion chemistry of existing or future fuels and to contribute to the development of their chemical kinetic models without any a priori input and chemical intuition.

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

The intrinsic value of bioblendstocks: Prenol as a case study

Decarbonizing the transportation sector is likely to require both electrification and increased incorporation of biofuels and/or bioblendstocks. While the social and environmental benefits of bioblendstocks are well understood, their real value for the fuel producers has not been established. As such, this work considers prenol as a bioblendstock case study to identify sources of intrinsic value to fuel blenders by studying the properties of binary mixtures with gasoline components. The considered refinery blendstocks were samples of full range naphthas from the distillation, fluidized catalytic cracking, isomerization, alkylation, and reforming units. Octane numbers, Reid vapor pressure, distillation curves, and sulfur content were evaluated. Our results indicate the need for adjusting the formulation of the base fuel, depending on the interplay among the properties of the bioblendstock and those of the base fuel. Prenol increased research octane number (RON) and octane sensitivity (OS) of the base fuel, by up to 25 and 10 octane numbers, respectively. Additionally, 10 vol% prenol reduced RVP up to 2.2 psi, for the more volatile blendstock. Thus, considering prenol as a low volatility, RON/OS boosting bioblendstock, the composition of the preferred base fuel was proposed as containing reduced olefins and aromatics, and increase light fractions. The potential impact of this new gasoline formulation on refining processes and products gives rise to direct sources of value to the refiners, such as exporting products to the chemicals market, increasing the value of intermediate refinery streams, decreasing operating severity of certain refinery units, and broadening of the product suite.

09 BIOMASS FUELS↗
DOE OSTI2021

Phase diagrams and microstructures of aqueous short alkyl chain polyethylene glycol ether carboxylate and carboxylic acid triblock surfactant solutions

The surfactant C 8 Eo 8 CH 2 COOH (Akypo LF2) and its salts have a small hydrophobic and a significantly longer hydrophilic part. As a consequence, there must be a significant steric constraint, once these surfactant molecules form micelles. In addition, the partially charged headgroups should bring some additional fine-tuning via electrostatic interactions to this "essentially non-ionic" surfactant. Experiments: Phase diagrams of binary mixtures of water and C 8 Eo 8 CH 2 COOH are established over large concentration and temperature ranges, also at different pHs and in the presence of sodium and calcium ions. Surface tensions and osmotic pressures are measured to understand the systems. To evaluate the microstructures, also Dynamic Light Scattering and Small-Angle X-ray Scattering are performed.

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

Influence of solvents on electrochemical stability window of ionic liquid solutions

The electrochemical stability window (ESW) defines the voltage range within which an electrolyte remains stable against oxidation and reduction, serving as a key descriptor for ionic liquid (IL)-based systems. The ESWs of 15 ILs with diverse cation-anion combinations were systematically investigated, both in their neat forms and as binary mixtures with three representative solvents, i.e., propylene carbonate (PC), ethylene glycol (EG), and tetrahydrofuran (THF). Cyclic voltammetry on a glassy carbon electrode determined anodic and cathodic stability limits, revealing that ESW protection in IL-solvent mixtures strongly depends on solvent polarity, proticity, and IL compatibility. PC, with a high dielectric constant and aprotic character, broadened anodic limits and moderately stabilized cathodic limits. THF maintained compact interfacial structure, offering additional cathodic protection, whereas EG, being protic, reduced ESWs via proton-coupled electron transfer and hydrogen evolution. The solvent protection trend followed by PC > THF > EG, with bulky, hydrophobic cations ([HMIM] + , [BMPYRR] + ) and weakly coordinating anions ([NTF 2 ] - , [DCA] - , [DEP] - ) showing the highest ESW protection for 50 mol% IL in these solvents. Among the neat ILs, [EMIM][DEP], [HMIM][PF 6 ], and [BMPYRR][DCA] showed wide ESWs of ∼5.5 V. These results provide valuable insight into solvent-modulated electrochemical stability, enabling rational design of IL-based electrolytes for energy storage and electrosynthesis.

25 ENERGY STORAGE↗
DOE OSTI2026

Solidification cracking of refractory alloys: a computational and machine learning study to investigate composition-dependence for improved weldability and additive manufacturability

Large-batch numerical, CALculation of PHAse Diagrams (CALPHAD)-based solidification cracking calculations are performed and then analyzed with machine learning methods to generate models that relate chemistry of refractory alloys to cracking susceptibility. Kou’s solidification cracking index is used to study the refractory alloys including O, N, C binary mixtures with Mo, Ta, Nb, and W, the molybdenum-based TZM, Niobium-based C103, and Tantalum-based T111 and Ta-10 W, as well as hypothetical refractory ternary alloys. Findings strongly validate Kou’s Crack Susceptibility Index (CSI) against Varestraint test data for Nb- and Ta-based alloys, establishing CSI thresholds where refractory alloys with CSI < 15,000 K are likely weldable, CSI > 15,000 K are prone to cracking, and CSI > 25,000 K are likely unweldable (or unprintable). Furthermore, interstitial elements C, N, and O significantly increase crack susceptibility, with some existing material specifications coinciding with peak cracking susceptibility concentrations. Finally, machine learning-derived elemental potency factors enable rapid prediction of CSI from alloy chemistry for C103, TZM, Ta-10 W, and T-111 alloys. These results provide practical guidance for feedstock selection, powder reuse limits, and alloy specification amendments for welding and additive manufacturing applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Open-air spray deposition of PCBM/BCP electron transport layer for inverted perovskite solar cells

A [6,6]-phenyl C61 butyric acid methyl ester (PCBM) and bathocuproine (BCP) electron transport layer (ETL) is spray deposited in open air directly on top of a perovskite at linear speeds of 9 m/min. The PCBM precursor ink contains a binary mixture of 1:1 chlorobenzene:chloroform, which optimizes spray wettability on the perovskite surface and allows quick solvent evaporation. A near-infrared heating module additionally provides a flash cure (<5 s) for the formation of smooth, large-area PCBM films (∼20 cm 2 ). A BCP solution in isopropanol is subsequently sprayed to form an ultrathin (<5 nm) film and characterized with a suite of high-resolution metrologies. The spray-deposition processing and near-infrared treatment do not damage the underlying perovskite. Inverted architecture devices containing the sprayed ETL achieve a champion efficiency of 20.3% and demonstrate stable performance without additional interlayers or surface treatments. Here, the technoeconomic cost of the open-air spray process is compared against traditional vacuum-based evaporation, resulting in a decrease in manufacturing costs by 26%.

14 SOLAR ENERGY↗
DOE OSTI2021

Fine-tuned thermally cross-linkable 6FDA-based polyimide membranes for aggressive natural gas separation

Glassy 6FDA-based polyimides are attractive membrane materials for many industrially important gas separations; however, plasticization in aggressive natural gas often causes significant loss in CO 2 /CH 4 selectivity. In this study, a family of thermally cross-linkable 6FDA-based polyimides containing carboxyl groups were synthesized and cross-linked as dense films via decarboxylation-induced thermal crosslinking. As well as chemical structure, crosslinking temperatures above and below T g are shown to be synergistic tools. Our results demonstrate that structure evolution during the decarboxylation-induced crosslinking process is affected significantly by the 3,5-diaminobenzoic acid (DABA) content in the polymer backbone. Even for a 50/50 CO 2 /CH 4 binary mixture with feed pressure up to 800 psia, decarboxylation-induced crosslinking provides attractive gas separation performance and plasticization resistance. Combined facile structure tunability, crosslinkability and high asymmetric fiber spinnability make the cross-linkable 6FDA-based polyimides a versatile platform for diverse aggressive natural gas feeds encountered in practice. Finally, our study provides insights into material design of thermally cross-linkable polymer membranes for such a broad spectrum of aggressive gas separations.

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

The chemical and physical origin of incineration ash reactivity in cementitious systems

Incorporating industrial byproducts and waste in concrete is the key to reducing landfill usage as well as lowering the environmental footprint of cement industry. An emerging industrial byproduct which can partly replace cement is the Municipal Solid Waste Incinerator Ash (MSWI ash: residue that is left after incineration of municipal solid waste in a Waste-to-Energy facility). These ashes are predominantly calcium-rich; however, they also contain additional elements whose speciation is not known. These elements can significantly alter the hydration characteristics of a cementitious system. Here, our results suggest these ashes can accelerate as well as retard cement hydration. Specifically, Pb, Br, S, Ca, and Cl appear to accelerate cement hydration, whereas Cu, Fe, Al, Ti, Si, K, Zn, and Sr appear to retard cement hydration. Changes in hydration characteristics can have a strong bearing on the physical characteristics of cementitious systems incorporating incineration ashes. Thus, to selectively screen ashes that synergistically enhance the physical characteristics, we introduce a novel “Incineration Ash Coefficient (IAC),” which shows a strong correlation with the compressive strength (R 2 =0.79) of cement-ash binary mixtures.

42 ENGINEERING↗
DOE OSTI2021

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

An emerging area of sustainable energy and environmental research is focused on the development of novel electrolytes that can increase the solubility of target species and improve subsequent reaction performance. Electrolytes with chemical and structural tunability have allowed for significant advancements in flow batteries and CO 2 conversion integrated with CO 2 capture. Liquid-like nanoparticle organic hybrid materials (NOHMs) are nanoscale fluids that are composed of inorganic nanocores and an ionically tethered polymeric canopy. NOHMs have been shown to exhibit enhanced conductivity making them promising for electrolyte applications, though they are often challenged by high viscosity in the neat state. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids, water, chloroform, toluene, acetonitrile, and ethyl acetate, were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (e.g., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors, including viscosity and diffusivity. We report our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 ($λ_{\text{SF}}$) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nanoscale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species.

25 ENERGY STORAGE↗
DOE OSTI2025

Extracted Water Induces Concentration Fluctuations in Model Ternary Liquid–Liquid Extraction System

Organic phase aggregation and phase splitting are two important (and connected) phenomena in liquid–liquid extraction of metal ions. Previously, we demonstrated how structure in binary mixtures of extractant and diluent originates from concentration fluctuations associated with the so-called “third-phase formation” liquid–liquid phase instability. For more complex systems, we sought to understand how extracted aqueous components affect these concentration fluctuations. Here, in this study, we use small-angle X-ray scattering and molecular dynamics simulations to investigate organic phase structural changes upon contact with water in a model ternary system of water/alkane/extractant. Critical exponents were determined from scattering with temperature variation and were consistent with mean field values. Then, by controlling the water content in the organic phase through direct dissolution of fixed quantities at constant temperature, we relate the observed increase in the fluctuation length scale to changes to the spinodal temperature of the third-phase formation phase boundary. We find a roughly linear relationship between water concentration and the spinodal temperature and a similar slope in that relationship for different linear alkane diluents. This suggests that the mechanism by which water extraction impacts the organic phase structure is to enhance concentration fluctuations through the introduction of additional polar extractant-water complexes, which increases the spinodal temperature and thereby decreases the reduced temperature, i.e., the distance to the instability. This explanation for how solutes induce aggregation in liquid–liquid extraction organic phases may extend to more complex systems, explaining the large increases in correlation lengths reported under high acid and metal loading.

Bonnett, Brittany L. [Argonne National Laboratory ↗
DOE OSTI2025

Effect of Solvents on Lignin–Surface Interactions via Molecular Dynamics Simulations

Lignin, an essential building block of lignocellulosic biomass, is a potential abundant source of aromatic monomers for the polymer and chemical industry. Reductive catalytic fractionation (RCF) is one promising process that can produce high yields of phenolic monomers and oligomers from lignin under different catalytic conditions. An important choice in optimizing RCF is the selection of solvent; however, detailed insights into solvent effects on lignin behaviors and interactions remain limited. Here, in this work, we perform all-atom molecular dynamics simulations to study the solvation of lignin, solvent-mediated conformational changes, and the interaction of solvated lignin oligomers with model surfaces. We focus on the behavior of an oligomeric lignin model compound in methanol, ethanol, a binary mixture of ethanol and water, and water at both the RCF reaction temperature (473 K) and room temperature. Analysis of structural features of lignin suggests that these three organic solvent systems favorably solvate lignin, resulting in a more extended conformation suitable for catalytic conversion to valuable chemicals. We further introduce model palladium (Pd) and carbon (C) surfaces to understand how solvent choice impacts adsorption onto a representative catalytic surface and support, and to quantify the competition among the reactant and solvent molecules for the surface. Unbiased simulations suggest strong adsorption of lignin on both Pd and C surfaces at 473 K, with notable solvent-mediated differences in adsorption energies. Additionally, our findings indicate that lignin adsorption is promoted by the entropy change resulting from the displacement of solvent molecules from the surface. This study provides a molecular perspective of adsorption of lignin onto varying surfaces, which is a step towards understanding and optimizing the catalytic conversion of lignin into valuable chemicals.

adsorption↗
DOE OSTI2026

Tuning the Solvation and Solubility Properties of Molecularly Heterogeneous Nonionic Deep Eutectic Solvents via Interface Organization

Common separation techniques, such as liquid− liquid extraction, are usually used for extractions and purifications due to their industrial scalability and affordability. However, these well-established practices are hindered by low selectivity and challenges in recovering solutes and solvents. Deep eutectic solvents (DES), a fairly new type of solvent, have the potential to overcome these issues. DESs are binary mixtures whose physical properties can be tuned by selecting the appropriate precursors to facilitate and/or enhance processes such as extraction. A promising DES for selective separations is formed when lauric acid (LA) is mixed with N-methylacetamide (NMA). This LA-NMA DES has a heterogeneous microscopic structure that can solvate compounds with completely different polarities. This study explores how forming an organized structure on the mesoscale affects the solubility of nonpolar solutes in nonionic DESs. To this end, the molecular and mesoscale structures and their effect on the solubility and solvation properties are evaluated for the LA-NMA DES and two new DESs with slight chemical variations in their precursors. It is observed that the organization of the nonpolar DES domains and, consequently, of their interfaces directly relates to the solubility of nonpolar compounds. Specifically, correctly selecting the DES precursors that form organized nonpolar domains leads to an organized interface in which the nonpolar solutes are solvated, thereby increasing the solubility. Additionally, enhanced dissolution power was observed in a completely different DES with mesoscale order in its molecular structure and composed of menthol and lauric acid. The latter result further validates the proposed tunability of the DES dissolution power through organized interfaces, extending it beyond a specific DES family and opening the possibility of new extraction-tailored designer solvents.

Extraction↗
DOE OSTI2023

Unexpected Thermomechanical Behavior of Off-Stoichiometry Epoxy/Amine Materials

Recent studies on off-stoichiometric thermosets reveal unique viscoelastic behavior derived from increased free volume and physical interactions between chain ends. To understand structural characteristics arising from cure and its effect on properties, we developed a Monte Carlo model based on step-growth polymerization. Our model accurately predicted structure–property trends for a two-component system of EPON 828 (EPON) and ethylenediamine. A second epoxy monomer, D.E.R. 732 (DER), was investigated to modulate T g . Binary mixtures of EPON and DER in off-stoichiometric, amine-rich formulations resulted in nonlinear evolution of thermomechanical properties with respect to initial formulation stoichiometry. Modifying our model with kinetic parameters allowing for differential epoxide/amine reaction kinetics only partially accounted for trends in T g , suggesting that spatiotemporal contributions-not captured by our model-were significant determinants of material properties compared to polymer architecture for three-component systems. Here these findings underpin the importance of spatial awareness in modeling to inform the development of dynamic thermosets.

36 MATERIALS SCIENCE↗