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At least 451 records · Page 25

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DOE OSTI2022

Na + -gated nanochannel membrane for highly selective ammonia (NH 3 ) separation in the Haber-Bosch process

Currently, cryogenic condensation is the predominant process for recovering ammonia (NH 3 ) in the Haber-Bosch (HB) process, which is highly energy intensive. To be more compatible with the reaction conditions in the HB process and thus minimize the pressure and temperature swing during reactant recycling, energy-efficient technologies for NH 3 extraction at elevated temperature and pressure are greatly needed. In this work, the Na + -gated nanochannel membrane, shown exclusively for water conduction in our previous work, also exhibited highly NH 3 -selective performance, with NH 3 /H 2 selectivity as high as 4,280 and NH 3 /N 2 selectivity > 10,000 at temperature up to 250 °C and pressure up to 35 bar. Excellent stability of the Na + -gated nanochannel membrane was demonstrated during a 100-h run in ternary NH 3 /H 2 /N 2 gas mixture at 200 °C and 35 bar, consistent with structural characterization by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transfer infrared (FTIR) spectroscopy. A techno-economic analysis (TEA) was conducted for the HB process using the Na + -gated nanochannel membrane and the traditional HB process with condenser. Finally, under the optimized separation conditions, > 80% energy savings and approximately 20% reduction of the net NH 3 production cost can be achieved, demonstrating the great potential of the Na + -gated nanochannel membrane for NH 3 separation in the HB process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Microphase Separation in Polyelectrolyte Blends: Weak Segregation Theory and Relation to Nuclear "Pasta".

We develop the weak segregation theory of micro phase separation in stoichiometric blends of oppositely and weakly charged polyelectrolytes, which would be immiscible in the absence of charged units. Short-range repulsions between polycation and polyanion monomers induce the formation of oppositely charged domains, the size of which is controlled by their excess Coulomb energy. The diagram of blend morphologies is constructed in the framework of Leibler's mean-field approach and to account for fluctuations within the Brazovskii-Fredrickson-Helfand approximation. Phase behavior of the polyelectrolyte blends is fully analogous to that of neutral diblock copolymers. The mean-field analysis predicts that the order-disorder transition (ODT) is second order for the symmetric blend. In asymmetric mixtures, an increasing incompatibility between polyelectrolytes triggers the usual cascade of first-order phase transitions, dis -> bcc -> hex -> lam. Fluctuations alter the phase diagram topology and allow the direct transitions from the disordered state (dis) to hex and lam microphases; for the symmetric blend, ODT becomes weakly first order. We also discuss that both microphase separation in polyelectrolyte blends and the formation of nuclear "pasta" phases within neutron stars are governed by similar physical principles, despite the 6 orders of magnitude difference in the periods of these structures.

Rumyantsev, Artem M.↗

DOE OSTI2026

Cost-effective valorization of 2,3-butanediol to high-value chemicals and jet fuel

Here, this work outlines an optimized process for converting 2,3-butanediol (BDO) into sustainable aviation fuel (SAF) and C4 chemicals. BDO is reactively separated from fermentation broth by forming dioxolanes, which are converted to isobutyraldehyde, methyl ethyl ketone (MEK), and 1,3-butadiene. These intermediates are reduced and dehydrated over Cu/ZSM-5 to form alkenes, which can be oligomerized and hydrotreated to jet-range alkanes. Previous BDO-dioxolane-alkene processes are limited by the requirement for a continuous aldehyde source for dioxolane formation. Brønsted acidic zeolites catalyze dioxolane deacetalization to form isobutyraldehyde and MEK in a >2:1 molar ratio, providing an internal, recyclable aldehyde source. Dioxolane formation optimization was performed to achieve >95% dioxolane yields over Amberlyst-15 and minimize isobutyraldehyde recycle. The overall BDO-dioxolane-fuel process yields an alkane mixture that enables at least a 50% v/v blend with Jet-A. Techno-economic analyses and life cycle assessments for this BDO-dioxolane-fuel process yield scenarios with <$2.50 per gallon gas equivalent and >58% reduction in CO2 emissions.

2,3-butanediol↗

DOE OSTI2020

A phenomenological rate of injection model for predicting fuel injection with application to mixture formation in light-duty diesel engines

Fuel injection rate laws are one of the most important pieces of information needed when modeling engine combustion with computational fluid dynamics. In this study, a simple phenomenological model of a common-rail injector was developed and calibrated for the Bosch CRI2.2 platform. The model requires three tunable parameter fits, making it relatively easy to calibrate and suitable for injector modeling when high-fidelity information about the internal injector’s geometry and electrical circuit details are not available. Each injection pulse is modeled as a sequence of up to four stages: an injection needle mechanical opening transient, a full-lift viscous flow inertial transient, a Bernoulli steady-state stage, and a needle descent transient. Parameters for each stage are obtained as polynomial fits from measured injection rate properties. The model enforces total injected mass, and the intermediate stages are only introduced if the injection pulse duration is long enough. Experimental rates of injection from two separate campaigns on the same injector were used to calibrate the model. The model was first validated against measured injection rate laws featuring pilot injections, short partially premixed combustion pulses, and conventional diesel combustion injection strategies. Then, it was employed as an input to engine computational fluid dynamics simulations, which were run to simulate experiments of mixture formation in an optically accessible light-duty diesel engine. It was found that, though simple, this model is capable of predicting both pilot and main injection pulse mass flow rates well: the simulations yielded accurate predictions of in-cylinder equivalence ratio distributions from injection strategies for both partially premixed combustion and pilot injections. Also, once calibrated, the model produced appropriate results for a wide range of injected mass and rail pressure values. Finally, it was observed that usage of such a relatively simple model can be a good choice when high-fidelity injection rate input and highly detailed information of the injector’s geometry and operation are not available, particularly as noticeable discrepancies can be present also among different experimental campaigns on similar hardware.

42 ENGINEERING↗

DOE OSTI2024

Closed‐Loop Recycling of Mixed Plastics of Polyester and CO 2 ‐Based Polycarbonate to a Single Monomer

Abstract Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single‐monomer – multiple‐materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers – specifically lactone‐based polyester and CO 2 ‐based polycarbonate – but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiL O ) undergoes ring‐opening polymerization through the lactone manifold to produce polyester, PE(BiL O ), and is also applied to ring‐opening copolymerization with CO 2 , via the epoxide manifold, to yield polycarbonate, PC(BiL O ). Remarkably, a one‐pot recycling process of a BiL O ‐derived PE/PC blend back to the constituent monomer BiL O in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.

Shi, Changxia↗

DOE OSTI2024

Closed‐Loop Recycling of Mixed Plastics of Polyester and CO 2 ‐Based Polycarbonate to a Single Monomer

Chemistry↗

DOE OSTI2020

Role of the Solvent–Surfactant Duality of Ionic Liquids in Directing Two-Dimensional Particle Assembly

Nanoparticle self-assembly plays a key role in formation of superlattices, which exhibit remarkable physical and chemical properties. However, controlling assembly remains a challenge partly due to a lack of understanding of the assembly dynamics and the difficulty in linking interfacial solution properties to interparticle forces. In this study, using liquid-cell transmission electron microscopy, self-assembly of gold nanoparticles (NPs) into superlattices in mixtures of water and ionic liquid (IL) was visualized, revealing a dual role of the IL in the assembly process. At intermediate concentrations, the IL acts as a surfactant stabilizing the particles at a well-defined equilibrium separation corresponding to the length of hydrogen bonded IL cations adsorbed onto neighboring NPs. Analysis of the interparticle forces reveals attractive long-range interactions of a van der Waals nature. At separations of 1-3 nm, interactions are dominated by attractive ion correlation and repulsive hydration forces giving rise to an energy minimum at 1.5 nm separation. The superlattice is further stabilized by hydrogen bonding, which shifts the equilibrium interparticle distance to 1.1 nm. In contrast, at higher concentrations, IL accumulates and forms a structured network in the gap between nanoparticles, where it acts as a solvent that eliminates the repulsive barrier and thus promotes particle coalescence. This solvent-surfactant duality of IL opens new opportunities for their use in directing particle assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Influence of Ions on the Size Dependent Morphology of Aerosol Particles

The study of aerosol particles composed of mixtures of organic and inorganic compounds provides insights for understanding chemistry in the atmosphere as well as information about phase transitions of systems under confinement. In the submicron size regime, we have previously found that liquid-liquid phase separation can be inhibited at sufficiently small particle diameters leading to phase separated particles at larger sizes and homogeneous particles below a threshold diameter. In this paper, we have investigated the influence of cations and anions in the inorganic compound (NH 4 + , Na + , SO 4 2- , HSO 4 - , and Cl-) on the phase separation of submicron aerosol particles. Each of five salts were studied with two different organic compounds. Surprisingly, a strong dependence on the identity of the cation is evident in the size dependence of the particle morphology and no dependence on the anion was found. Sodium containing samples exhibit phase separation in particles below 20 nm in diameter whereas ammonium containing samples cease to undergo phase separation in particles between 45 and 65 nm in diameter. The separation relative humidity for supermicron droplets also depends on the identity of the cation in the inorganic component if the anion is the same across the salts compared. In addition, the correlation between the separation relative humidity and size dependence was investigated and displays a trend, but is not a dominant feature of the data. We explain the results in terms of hard and soft ions, where the harder cation (Na + ) leads to phase separation down to smaller sizes while the softer cation (NH 4 + ) prevents phase separation and causes particles up to a larger diameter to remain homogenous. This study has implications for atmospheric chemistry in regions dominated by sea spray aerosol, which contains sodium as the primary cation, when compared to continental aerosol, where ammonium is an abundant cation. Additionally, these findings can be used to understand the influence of cations on the phase transitions of confined materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Pulsed power to control growth of silicon nanoparticles in low temperature flowing plasmas

Low-temperature plasmas have seen increasing use for synthesizing high-quality, mono-disperse nanoparticles (NPs). Recent work has highlighted that an important process in NP growth in plasmas is particle trapping—small, negatively charged nanoparticles become trapped by the positive electrostatic potential in the plasma, even if only momentarily charged. In this article, results are discussed from a computational investigation into how pulsing the power applied to an inductively coupled plasma (ICP) reactor may be used for controlling the size of NPs synthesized in the plasma. The model system is an ICP at 1 Torr to grow silicon NPs from an Ar/SiH 4 gas mixture. This system was simulated using a two-dimensional plasma hydrodynamics model coupled to a three-dimensional kinetic NP growth and trajectory tracking model. The effects of pulse frequency and pulse duty cycle are discussed. We identified separate regimes of pulsing where particles become trapped for one pulsed cycle, a few cycles, and many cycles—each having noticeable effects on particle size distributions. For the same average power, pulsing can produce a stronger trapping potential for particles when compared to continuous wave power, potentially increasing particle mono-dispersity. Pulsing may also offer a larger degree of control over particle size for the same average power. Experimental confirmation of predicted trends is discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2024

Uncertainty quantification of mass models using ensemble Bayesian model averaging

Developments in the description of the masses of atomic nuclei have led to various nuclear mass models that provide predictions for masses across the whole chart of nuclides. These mass models play an important role in understanding the synthesis of heavy elements in the rapid neutron capture ( r ) process. However, it is still a challenging task to estimate the size of uncertainty associated with the predictions of each mass model. In this work, a method called ensemble Bayesian model averaging (EBMA) is introduced to quantify the uncertainty of one-neutron separation energies (S 1 n ) which are directly relevant in the calculations of r -process observables. Here, this Bayesian method provides a natural way to perform model averaging, selection, and uncertainty quantification, by combining the mass models as a mixture of normal distributions whose parameters are optimized against the experimental data, employing the Markov chain Monte Carlo method using the no-u-turn sampler. The EBMA model optimized with all the experimental S 1 n from the AME2003 nuclides are shown to provide reliable uncertainty estimates when tested with the new data in the AME2020.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2026

Influence of Nd(II) and Nd(III) Ions on the Speciation and Kinetic Dynamics of Radiolytic Transients in Molten LiCl-KCl Eutectic Salt Mixtures

In the pyrochemical reprocessing of used nuclear fuel, understanding the effects of ionizing radiation on the chemical behavior of fission products in molten chloride eutectic salt is crucial. Here, this study investigates the impact of radiation on the chemical and kinetic speciation of Nd ions in molten LiCl-KCl eutectic, which are challenging to separate due to their multivalent oxidation states and comproportionation reactions. Electron pulse radiolysis techniques were used to determine transient absorption spectra, chemical kinetics, and activation parameters for the reaction of Nd ions with the primary products of molten LiCl-KCl eutectic radiolysis: the solvated electron (e S - ) and dichlorine radical anion (Cl 2 •- ). Initially, Nd(III) reacted rapidly with e S - , forming Nd(II) with a second-order rate coefficient of k = (4.54 ± 0.07) × 10 10 M -1 s -1 at 673 K. The resulting Nd(II) ions then reacted slowly with Cl 2 •- , regenerating Nd(III) with an estimated rate of k = (1.72 ± 0.04) × 10 10 M -1 s -1 at 673 K. Additionally, the comproportionation reaction of Nd(III) and Nd(s) to form Nd(II) was monitored chemically and electrochemically. This work suggests that the comproportionation reaction of Nd(III) with Nd(s) to form Nd(II) is unstable in molten LiCl-KCl eutectic.

36 - MATERIALS SCIENCE↗

DOE OSTI2024

Hydrogen-Steam Separation Using Mechanical Vapor Recompression Cycle

Solar thermochemical hydrogen and fuel production is a promising pathways for producing sustainable fuels and chemicals. One of the main challenges in the development of these systems is their low steam conversion extent, dictated by its restrictive thermodynamics requiring extremely high temperatures and low oxygen partial pressure to obtain conversions over 10 \%. While condensing the unreacted steam is technically simple, the latent heat is thus lost, which can be larger than the producd hydrogen higher heating value. We propose to use a modified mechanical vapor recompression cycle, allowing to recover the latent heat by compressing the steam-hydrogen mixture prior to the condensation process, thus creating a temperature different between the hot exhaust and cold inlet streams. We show that this method can recover over 90 % of the latent heat, thus increasing the viability of solar thermochemical hydrogen production cycles even under limited conversion conditions.

hydrogen technology↗

DOE OSTI2022

Comparative Critical Mass Calculations for NNL and ENDF/B-VIII.0 Zirconium Hydride Thermal Neutron Scattering Laws

Zirconium hydride (ZrH x ) is a moderator material for TRIGA reactors and historical space reactor systems, such as SNAP-10A. Thermal neutron scattering laws (TSL) for two phases of this material, δ and ε, have been previously evaluated by Naval Nuclear Laboratory (NNL) and submitted to the National Nuclear Data Center (NNDC) for inclusion in the US national ENDF/B-VIII.1 nuclear data library. In contrast to the current ENDF/B-VIII.0 TSL evaluations, which consider only a single phase, the new evaluations are derived from separate ab initio calculations for both phases and include coherent elastic effects of the zirconium sublattice. To estimate the impact of these changes to the TSL evaluation of this material, comparative critical mass calculations were performed with MC21 for homogenous mixtures of high- enriched uranium (HEU) and ZrH x in bare and water reflected sphere configurations. These calculations yield an impact on the estimated critical mass as a function of 235 U loading density with maximum differences as large as 1% - 5% for over-moderated thermal spectrum systems. Consequently, the NNL TSL evaluations are anticipated to have a small impact on criticality calculations of thermal reactor systems regardless of the material phase. Nevertheless, characteristic differences exist in the predicted thermal spectra as function of energy for the two sets of TSL evaluations, which are attributed to difference in the underlying phonon density of states of hydrogen bound in ZrH x .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Refining PeakDecoder Version 2

Novel computational tools for processing multidimensional mass spectrometry (MS) data are necessary to enable deeper and automated detection and quantification of metabolites in complex backgrounds. Multidimensional MS data includes measurements from liquid chromatography (LC) and ion mobility spectrometry (IM) separations, and precursor and fragment ion spectra collected in data-independent acquisition (DIA) mode. PeakDecoder is an artificial intelligence (AI)-based software that enables automated interpretation of this kind of data to identify and quantify individual metabolites in complex mixtures. The goal of this project was to improve and re-implement PeakDecoder in a better suited programming language to enable its commercialization.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2022

Comparative critical mass calculations for NNL and ENDF/B-VIII.0 - Zirconium hydride thermal neutron scattering laws

Zirconium hydride (ZrH{sub x}) is a moderator material for TRIGA reactors and historical space reactor systems, such as SNAP-10A. Thermal neutron scattering laws (TSL) for two phases of this material, δ and ε, have been previously evaluated by Naval Nuclear Laboratory (NNL) and submitted to the National Nuclear Data Center (NNDC) for inclusion in the US national ENDF/B-VIII.1 nuclear data library. In contrast to the current ENDF/B-VIII.0 TSL evaluations, which consider only a single phase, the new evaluations are derived from separate ab initio calculations for both phases and include coherent elastic effects of the zirconium sublattice. To estimate the impact of these changes to the TSL evaluation of this material, comparative critical mass calculations were performed with MC21 for homogenous mixtures of high-enriched uranium (HEU) and ZrH{sub x} in bare and water reflected sphere configurations. These calculations yield an impact on the estimated critical mass as a function of {sup 235}U loading density with maximum differences as large as 1% - 5% for over-moderated thermal spectrum systems. Consequently, the NNL TSL evaluations are anticipated to have a small impact on criticality calculations of thermal reactor systems regardless of the material phase. Nevertheless, characteristic differences exist in the predicted thermal spectra as function of energy for the two sets of TSL evaluations, which are attributed to difference in the underlying phonon density of states of hydrogen bound in ZrH{sub x}. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2026

Effect of NO on DME-Methanol HCCI Experimental Observations

Methanol is an attractive fuel for the maritime sector due to its wide availability. Its direct use as a fuel, however, is accompanied by challenges such as high latent heat of vaporization and low cetane number. A potential solution to overcome the ignition properties of methanol could be through on-board generation of dimethyl ether (DME) via catalytic dehydration of methanol. The resulting mixture from dehydration can be mixed in with the intake air to generate a homogenous charge compression ignition (HCCI) preburn for subsequent direct injection (DI) and successful ignition methanol at diesel–like timescales. However, if the preburn species are treated separately from the complete methanol MCCI approach the preburn heat release rate (HRR) phasing and behavior do not replicate the preburn behavior of the complete approach. Thus, the presence of the main methanol mixing controlled compression ignition (MCCI) combustion event influences the DME/methanol preburn kinetics. Specifically, it was found that trapped residual temperature alone was insufficient alone to be responsible for the observed differences, and that trace species concentrations of NO in the trapped residual gas also influenced DME/methanol kinetics increasing low temperature heat release (LTHR) magnitude and advancing high temperature heat release (HTHR) phasing. NO is not present in HCCI combustion of neat DME or DME/methanol blends nor is elevated gas temperature in the trapped residuals; both of which result in failure to accurately predict the HCCI combustion of DME/methanol blends when coupled with subsequent DI methanol MCCI. This work experimentally explores the effect of trapped residual temperature and NO on DME and DME/methanol HCCI combustion.

Jatana, Gurneesh [ORNL] (ORCID:0000000288903225)↗

DOE OSTI2025

Multi-Ion Complexes and Competition from Bulky BArF – Anions for Chloride Binding in Ion Pairing Conditions

Cationic charges have long been used to enhance anion binding. Embedding charge introduces strong ion pairing for target anions but also for off-target ions, ultimately generating a mixture of multi-ion species that are hard to identify and quantify. While many sidestep this problem using polar solvents and weakly coordinating ions, these approaches exclude a substantial cross-section of conditions found in applications spanning recognition, assembly, separations, templation, and catalysis. To confront this complexity, we study the binding of an anion to a cationic receptor featuring low shape complementarity in a low-polarity solvent to maximize ionic interactions. We prepared the receptor as a salt of the weakly coordinating tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF – ) anion and studied the binding of small chloride (Cl – ) and medium-sized iodide (I – ) anions. Surprisingly, the use of the bulky BArF – anion does not suppress ion pairing interactions, with 65% of the receptor being paired at 0.5 mM in dichloromethane. We observe multi-ion receptor-Cl – complexes (2:1, 1:1, 1:2), reinforcing the complexity that emerges when working in low-polarity media. Here, we reveal the dependence of affinity on anion charge density and size and that bulky BArF – counteranions compete for chloride binding. These studies reveal the noninnocence of BArF – anions and strategies to quantify multi-ion species.

Ion pairing↗

DOE OSTI2023

Thermodynamics of diamond formation from hydrocarbon mixtures in planets

Hydrocarbon mixtures are extremely abundant in the Universe, and diamond formation from them can play a crucial role in shaping the interior structure and evolution of planets. With first-principles accuracy, we first estimate the melting line of diamond, and then reveal the nature of chemical bonding in hydrocarbons at extreme conditions. We finally establish the pressure-temperature phase boundary where it is thermodynamically possible for diamond to form from hydrocarbon mixtures with different atomic fractions of carbon. Notably, here we show a depletion zone at pressures above 200 GPa and temperatures below 3000 K-3500 K where diamond formation is thermodynamically favorable regardless of the carbon atomic fraction, due to a phase separation mechanism. The cooler condition of the interior of Neptune compared to Uranus means that the former is much more likely to contain the depletion zone. Our findings can help explain the dichotomy of the two ice giants manifested by the low luminosity of Uranus, and lead to a better understanding of (exo-)planetary formation and evolution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗