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At least 109 records · Page 6

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DOE OSTI2022

Investigation of Rare Earth Elements Mobility Using Molecular Dynamics

Rare Earth Elements (REE) are critical many applications such as electronics, permanent magnets, agricultural etc. Effective separation of REEs is a challenge due to their similarities in chemical and physical properties. Current separation processes are costly and environmentally detrimental. Therefore, research on REEs mobility in water-based solvents is necessary to design effective separation processes. In this research, the key kinetic and thermodynamic parameters, including diffusion coefficient and hydration shell are determined under the influence of external electric field. The diffusion coefficient of metal ions increases due to electric field in pure water.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2022

Investigation of Rare Earth Elements Mobility Using Molecular Dynamics

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2023

Modular Solar-to-Fuel Electrolysis at Low Cell Potentials Enabled by Glycerol Electrooxidation and a Bipolar Membrane Separator

Solar fuel generation through water electrolysis or electrochemical CO 2 reduction is thermodynamically limited when paired with the oxygen evolution reaction (OER). The glycerol electrooxidation reaction (GEOR) is an alternative anodic reaction with lower anodic electrochemical potential that utilizes a renewable coproduct produced during biodiesel synthesis. We show that GEOR on a Au-Pt-Bi ternary metal electrocatalyst in a model alkaline crude glycerol solution can provide significant cell potential reductions even when paired to reduction reactions in seawater and acidic catholytes via a bipolar membrane (BPM). We showed that the combination of GEOR electrooxidation and a BPM separator lowers the total cell potential by 1 V at an electrolysis current of 10.0 mA cm -2 versus to an anode performing OER when paired with hydrogen evolution and CO 2 reduction cathodes. The observed voltage reduction was steady for periods of up to 80 hours, with minimal glycerol crossover observed through the membrane. Furthermore, these results motivate new, high-performance cell designs for photoelectrochemical solar fuels integrated systems based on glycerol electrooxidation.

25 ENERGY STORAGE↗

DOE OSTI2023

A thermodynamic explanation of the Invar effect

The anomalously low thermal expansion of Fe–Ni Invar has long been associated with magnetism, but to date, the microscopic underpinnings of the Invar behaviour have eluded both theory and experiment. Here we present nuclear resonant X-ray scattering measurements of the phonon and magnetic entropies under pressure. By applying a thermodynamic Maxwell relation to these data, we obtain the separate phonon and magnetic contributions to thermal expansion. We find that the Invar behaviour stems from a competition between phonons and spins. In particular, the phonon contribution to thermal expansion cancels the magnetic contribution over the 0–3 GPa pressure range of Invar behaviour. At pressures above 3 GPa, the cancellation is lost, but our analysis reproduces the positive thermal expansion measured separately by synchrotron X-ray diffractometry. Ab initio calculations informed by experimental data show that spin–phonon interactions improve the accuracy of this cancellation over the range of Invar behaviour. Further, spin–phonon interactions also explain how different phonon modes have different energy shifts with pressure.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Looking at extremal black holes from very far away

Near-extremal black holes are subject to large quantum effects, which modify their low-temperature thermodynamic behavior. Hitherto, these quantum effects were analyzed by separating the geometry into the near-horizon region and its exterior. It is desirable to understand and reproduce such corrections from the full higher-dimensional asymptotically flat or AdS geometry’s perspective. We address this question in this article and fill this gap. Specifically, we find off-shell eigenmodes of the quadratic fluctuation operator of the Euclidean gravitational dynamics, with eigenvalues that vanish linearly with temperature. We illustrate this for BTZ and neutral black holes with hyperbolic horizons in AdS in Einstein-Hilbert theory, and for the charged black holes in Einstein-Maxwell theory. The linear scaling with Matsubara frequency, which is a distinctive feature of the modes, together with the fact that their wavefunctions localize close to the horizon as we approach extremality, identifies them as responsible for the aforementioned quantum effects. We provide a contour prescription to deal with the sign indefiniteness of the Euclidean Einstein-Maxwell action, which we derive to aid our analysis. We also resolve a technical puzzle regarding modes associated with rotational isometries in stationary black hole spacetimes.

AdS-CFT Correspondence↗

NASA NTRS1979

Modelling turbulent flame ignition and blowout

A statistical mixing model incorporating an overall rate equation to describe the fuel oxidation process was developed for studies of ignition and blowout in a combustor primary zone. This zone is treated as a partially stirred reactor whose composition is described by a statistical ensemble of equal mass fluid elements. This ensemble experiences mixing interactions, which represent the turbulent mixing process, at time intervals governed by an empirically determined mixing frequency. Each mixing interaction is computed by ramdomly selecting two different elements which are then allowed to mix completely so that they reach a mean composition depending on their thermodynamic states prior to mixing. The two elements then separate, and the chemical kinetics proceed depending on their new composition and temperature.

Radhakrishnan, K.↗

NASA NTRS1981

Saturation and energy-conversion efficiency of auroral kilometric radiation

A quasi-linear theory is used to study the saturation level of the auroral kilometric radiation. The investigation is based on the assumption that the emission is due to a cyclotron maser instability as suggested by Wu and Lee and Lee et al. The thermodynamic bound on the radiation energy is also estimated separately. The energy-conversion efficiency of the radiation process is discussed. The results are consistent with observations.

Wu, C. S.↗

NASA NTRS1985

NBS (National Bureau of Standards): Materials measurements

NBS work for NASA in support of NASA's Microgravity Science and Applications Program under NASA Government Order H-27954B (Properties of Electronic Materials) covering the period April 1, 1984 to March 31, 1985 is described. The work has been carried out in three independent tasks: Task 1--Surface Tensions and Their Variations with Temperature and Impurities; Task 2--Convention during Unidirectional Solidification; Task 3--Measurement of High Temperature Thermodynamic Properties. The results for each task are given separately in the body of the report.

Manning, J. R.↗

DOE OSTI2022

Selective Sulfidation for Rare Earth Element Separation

Rare earth metals and compounds are critical components of advanced materials for energy, structural alloys, and transportation. These low-tonnage elements are sourced together as by- and co-products, and presently require complete hydrometallurgical dissolution followed by liquid–liquid separation for their isola- tion and production. There is great interest in developing alternatives to those hydrometallurgical processes in order to limit the environmental impact of rare earth element supply. Herein, we present selective sulfidation as a novel, high- temperature alternative to facilitate physical separation of rare earth by- and co- product elements. We explore the thermodynamics of rare earth oxide sulfidation with elemental sulfur, and discuss the role of carbon in controlling sulfidation selectivity. We apply these findings to the demonstration of selective sulfidation for iron-rare earth and lanthanide-lanthanide separations.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Rational design of photosynthetic reaction center protein maquettes

New technologies for efficient solar-to-fuel energy conversion will help facilitate a global shift from dependence on fossil fuels to renewable energy. Nature uses photosynthetic reaction centers to convert photon energy into a cascade of electron-transfer reactions that eventually produce chemical fuel. The design of new reaction centers de novo deepens our understanding of photosynthetic charge separation and may one day allow production of biofuels with higher thermodynamic efficiency than natural photosystems. Recently, we described the multi-step electron-transfer activity of a designed reaction center maquette protein (the RC maquette), which can assemble metal ions, tyrosine, a Zn tetrapyrrole, and heme into an electron-transport chain. Here, we detail our modular strategy for rational protein design and show that the intended RC maquette design agrees with crystal structures in various states of assembly. A flexible, dynamic apo-state collapses by design into a more ordered holo-state upon cofactor binding. Crystal structures illustrate the structural transitions upon binding of different cofactors. Spectroscopic assays demonstrate that the RC maquette binds various electron donors, pigments, and electron acceptors with high affinity. We close with a critique of the present RC maquette design and use electron-tunneling theory to envision a path toward a designed RC with a substantially higher thermodynamic efficiency than natural photosystems.

09 BIOMASS FUELS↗

DOE OSTI2023

Chemical and Structural Evolution of AgCu Catalysts in Electrochemical CO 2 Reduction

Silver–copper (AgCu) bimetallic catalysts hold great potential for electrochemical carbon dioxide reduction reaction (CO 2 RR), which is a promising way to realize the goal of carbon neutrality. Although a wide variety of AgCu catalysts have been developed so far, it is relatively less explored how these AgCu catalysts evolve during CO 2 RR. The absence of insights into their stability makes the dynamic catalytic sites elusive and hampers the design of AgCu catalysts in a rational manner. Here, in this study, we synthesized intermixed and phase-separated AgCu nanoparticles on carbon paper electrodes and investigated their evolution behavior in CO 2 RR. Our time-sequential electron microscopy and elemental mapping studies show that Cu possesses high mobility in AgCu under CO 2 RR conditions, which can leach out from the catalysts by migrating to the bimetallic catalyst surface, detaching from the catalysts, and agglomerating as new particles. Besides, Ag and Cu manifest a trend to phase-separate into Cu-rich and Ag-rich grains, regardless of the starting catalyst structure. The composition of the Cu-rich and Ag-rich grains diverges during the reaction and eventually approaches thermodynamic values, i.e., Ag 0.88 Cu 0.12 and Ag 0.05 Cu 0.95 . The separation between Ag and Cu has been observed in the bulk and on the surface of the catalysts, highlighting the importance of AgCu phase boundaries for CO 2 RR. In addition, an operando high-energy-resolution X-ray absorption spectroscopy study confirms the metallic state of Cu in AgCu as the catalytically active sites during CO 2 RR. Taken together, this work provides a comprehensive understanding of the chemical and structural evolution behavior of AgCu catalysts in CO 2 RR.

Chen, Peng-Cheng↗

NASA NTRS1990

Electrochemical measurements and thermodynamic calculations of redox equilibria in pallasite meteorites - Implications for the eucrite parent body

The intrinsic oxygen fugacity (IOF) of olivine separates from the Salta, Springwater, and Eagle Station pallasites was measured between 850 and 1150 C using oxygen-specific solid zirconia electrolytes at 100,000 Pa. Thermodynamic calculations of redox equilibria involving equalibrium pallasite assemblages are in good agreement with the experimental results and provide a lower limit to pallasite redox stability; others involving disequilibrium assemblages, suggest that pallasites experienced localized, late-stage oxidation and reduction effects. Consideration of the redox buffer metal-olivine-orthopyroxene utilizing calculated Eucrite Parent Body (EPB) mantle phase compositions indicates that small redox gradients may have existed in the EPB. Such gradients may have produced strong compositional variation within the EPB. In addition, there is apparently significant redox heterogeneity in the source area of Eagle Station Trio pallasites and Bocaiuva iron meteorites.

Righter, Kevin↗

DOE OSTI2022

Experimental Investigation of the Effect of Atomizing Electrospray Nozzles on the Cooling and Reduced Humidification of Air

Separating sensible and latent cooling have shown the potential to reduce energy consumption in A/C systems for building HVAC applications. Several technologies exist based on vapor-compression refrigeration, enthalpy wheels, chemical adsorption and absorption materials, and mechanical cooling. However, their thermodynamics limits and high energy consumption hinder their deployment in hot and humid climatic regions. This paper focuses on separating sensible and latent cooling by using a new thermodynamics process and in-kind (i.e., non-vapor compression-based) technology. Highly electrically charged water droplets were sprayed in the airflow. These droplets attracted water vapor molecules to their surfaces and promoted condensation. The phenomenon was the result of simultaneous dielectrophoresis and electro-diffusion interactions. Studies in the literature have shown that using multiple capillary electrodes reduced air moisture by up to 5% when using nanometer-size droplets in the spray. Unfortunately, these studies were limited to low airflow rates, and the objective of this paper was to investigate how to scale up this in-kind approach to airflows typical of buildings. In the present paper, droplets of micrometer size were utilized to control the humidity for a 5-cfm flow rate. While this airflow was still low for building applications, it was 100 times fold the airflows in the literature studies. The air was tested at 20°C and at 50 and 80% relative humidity. A two-fluid atomizing nozzle produced the droplets in the spray, and high DC electric potential, up to 25 kV, was used to charge the fine droplets electrically. The air atomizing nozzle with high voltage potential resembled an evaporative cooler process. However, a measurable reduction of the absolute humidity of up to 2% was observed compared to the case of the nozzle with no high voltage potential. The entire device had one small nozzle selected from off-the-shelf components and had less than a 9 cm2 footprint area.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

NASA NTRS2001

Stage Separation Performance Analysis Project

Stage separation process is an important phenomenon in multi-stage launch vehicle operation. The transient flowfield coupled with the multi-body systems is a challenging problem in design analysis. The thermodynamics environment with burning propellants during the upper-stage engine start in the separation processes adds to the complexity of the-entire system. Understanding the underlying flow physics and vehicle dynamics during stage separation is required in designing a multi-stage launch vehicle with good flight performance. A computational fluid dynamics model with the capability to coupling transient multi-body dynamics systems will be a useful tool for simulating the effects of transient flowfield, plume/jet heating and vehicle dynamics. A computational model using generalize mesh system will be used as the basis of this development. The multi-body dynamics system will be solved, by integrating a system of six-degree-of-freedom equations of motion with high accuracy. Multi-body mesh system and their interactions will be modeled using parallel computing algorithms. Adaptive mesh refinement method will also be employed to enhance solution accuracy in the transient process.

Chen, Yen-Sen↗

DOE OSTI2021

Using a Chromatographic Pseudophase Model To Elucidate the Mechanism of Olefin Separation by Silver(I) Ions in Ionic Liquids

Silver(I) ions undergo selective olefin complexation and have been utilized in various olefin/paraffin separation techniques such as argentation chromatography and facilitated transport membranes. Ionic liquids (ILs) are solvents known for their low vapor pressure, high thermal stability, low melting points, and ability to promote a favorable solvation environment for silver(I) ion–olefin interactions. To develop highly selective separation systems, a fundamental understanding of analyte partitioning to the stationary phase and the thermodynamic driving forces behind solvation is required. In this study, a chromatographic model treating silver(I) ions as a pseudophase is constructed and employed for the first time to investigate the olefin separation mechanism in silver(I) salt/IL mixtures. Stationary phases containing varying amounts of noncoordinated silver(I) salt ([Ag + ][NTf 2 – ]) dissolved in the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 10 MIM + ][NTf 2 – ]) IL are utilized to determine the partition coefficients of various analytes including alkanes, alkenes, alkynes, aromatics, aldehyde, esters, and ketones. As ligand coordination to silver(I) ions is known to lower its olefin complexation capability, this study also examines two different types of coordinated silver(I) ion pseudophases, namely, monocoordinated silver(I) salt ([Ag + (1-decyl-2-methylimidazole, DMIM)][NTf 2 – ]) and dicoordinated silver(I) salt ([Ag + (1-methylimidazole, MIM)(DMIM)][NTf 2 – ]). The extent of olefin partitioning to the coordinated silver(I) ion pseudophases over the carrier gas and IL decreased by up to two orders of magnitude. Values for enthalpy, entropy, and free energy of solvation were determined for the three silver(I) ion-containing systems. Olefin retention was observed to be enthalpically dominated, while ligand coordination to the silver(I) ion pseudophase resulted in variations for both enthalpic and entropic contributions to the free energy of solvation. Furthermore, the developed model can be used to study chemical changes that occur in silver(I) ions over time as well as identify optimal silver(I) salt/IL mixtures that yield high olefin selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Separation of volatile organic contaminants from water using a direct-contact dehumidifier: An experimental study and modeling

A packed-bed, direct-contact dehumidifier (PB-DCD) has been developed to selectively condense water from a gaseous mixture of organic contaminants. In this process, hot air is humidified by mixing with wastewater vapor in a static mixer and is dehumidified by subcooled fresh water passing through the PB-DCD in a counter-current configuration. The goal of this study is to understand the relationship between various operating parameters and how they affect separation of isopropyl alcohol (IPA) from the gaseous mixture with the purpose of expanding the investigation to other contaminants in the future. The process has been successfully used to separate IPA from wastewater. Different parameters including the concentration of IPA in water, feed temperature, air-to-vapor ratio, and cooling-water-to-vapor mass ratio, as well as residence time were examined to determine their influence on contaminant separation and clean water recovery rate. The Buckingham Pi theorem was applied to reduce the number of studying variables by generating non-dimensional groups. Experiments were performed to determine the relationship between the non-dimensional parameters and model mass transfer in the system. Mass transfer coefficients for multicomponent gaseous mixture condensation in a packed-bed direct contact condenser column are calculated and a modified correlation of mass transfer is developed. The parameters of the mass transfer model are obtained from operating conditions of the PB-DCD, stream conditions and thermodynamic properties. A modified Sherwood correlation is developed to predict IPA separation from a gaseous mixture consisting of air, water, and IPA. The modified Sherwood correlation is applied to successfully predict the Sherwood number with a mean absolute error equal to 6.6 %. According to the experimental results, the maximum IPA separation achieved was 76.3 %, which corresponds to a water recovery rate of 58.7 %.

42 ENGINEERING↗

DOE OSTI2024

Thermodynamic origin of nonvolatility in resistive memory

Electronic switches based on the migration of high-density point defects, or memristors, are poised to revolutionize post-digital electronics. Despite significant research, key mechanisms for filament formation and oxygen transport remain unresolved, hindering our ability to predict and design device properties. For example, experiments have achieved 10 orders of magnitude longer retention times than predicted by current models. Here, using electrical measurements, scanning probe microscopy, and first-principles calculations on tantalum oxide memristors, we reveal that the formation and stability of conductive filaments crucially depend on the thermodynamic stability of the amorphous oxygen-rich and oxygen-poor compounds, which undergo composition phase separation. Including the previously neglected effects of this amorphous phase separation reconciles unexplained discrepancies in retention and enables predictive design of key performance indicators such as retention stability. Furthermore, this result emphasizes non-ideal thermodynamic interactions as key design criteria in post-digital devices with defect densities substantially exceeding those of today’s covalent semiconductors.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Experimental Demonstration of Alkalinity Concentration Swing for Direct Air Capture of CO 2

This work constitutes the first lab-scale experimental demonstration of the alkalinity concentration swing (ACS) for direct air capture (DAC) of CO 2 . ACS can be implemented by taking a dilute alkaline solution that has contacted ambient air, and then concentrating it using commercially available desalination technologies. The more concentrated solution has a higher partial pressure of CO 2 relative to the initial solution, allowing the CO 2 to be separated and stored. The ACS approach is based on simple thermodynamics but had never been verified experimentally in terms of extracting CO 2 from air until now. We tested two distinct methods for concentrating the alkaline liquid: reverse osmosis (RO) and capacitive deionization (CDI). We found that to complete the DAC cycle in feasible operating conditions, a bicarbonate-enrichment step needed to be introduced, which selects on bicarbonate ions over carbonate ions. Two approaches for CO 2 extraction to measure the CO 2 yield per amount of water processed by the ACS method were tested. The energy required per amount of CO 2 captured was quantified. We further applied an energy model to study how operating the ACS cycle under different conditions would affect energy requirements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗